WO2010010899A1

WO2010010899A1 - Positive-type photosensitive resin composition and cured film production method using the same

Info

Publication number: WO2010010899A1
Application number: PCT/JP2009/063117
Authority: WO
Inventors: 敏滝田
Original assignee: 富士フイルム株式会社
Priority date: 2008-07-24
Filing date: 2009-07-22
Publication date: 2010-01-28
Also published as: TW201011470A; JP2010026460A

Abstract

Disclosed is a positive-type photosensitive resin composition which is characterized by comprising: a resin which has a specific acrylic acid type constituent unit, is alkali-insoluble or poorly alkali-soluble, and can become alkali-soluble upon the dissociation of an acid-dissociative group contained therein, wherein the specific acrylic acid type constituent unit can produce a carboxyl group upon the dissociation of a dissociative group contained therein; a compound having at least two epoxy groups in the molecule; and a compound capable of generating an acid upon the irradiation with an active ray having a wavelength of 300 nm or longer. Also disclosed is a method for forming a cured film by using the positive-type photosensitive resin composition.

Description

Positive photosensitive resin composition and cured film forming method using the same

The present invention relates to a positive photosensitive resin composition and a cured film forming method using the same. More specifically, a positive photosensitive resin composition suitable for forming a flattening film, protective film or interlayer insulating film of electronic components such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, and an organic EL, and its use The present invention relates to a cured film forming method.

Conventionally, in electronic parts such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, organic EL, etc., in general, a flattening film for imparting flatness to the surface of electronic parts, to prevent deterioration and damage of electronic parts A photosensitive resin composition is used when forming a protective film or an interlayer insulating film for maintaining insulation. For example, a TFT type liquid crystal display element is provided with a polarizing plate on a glass substrate, a transparent conductive circuit layer such as ITO and a thin film transistor (TFT) are formed, and covered with an interlayer insulating film to form a back plate, while on a glass substrate A polarizing plate is provided, and a pattern of a black matrix layer and a color filter layer is formed as necessary. Further, a transparent conductive circuit layer and an interlayer insulating film are sequentially formed as a top plate, and the back plate and the top plate are separated by a spacer. It is manufactured by enclosing the liquid crystal between both plates facing each other, but the photosensitive resin composition used when forming the interlayer insulating film in this is sensitivity, residual film rate, heat resistance, adhesion Excellent in transparency and transparency. Furthermore, the photosensitive resin composition is required to have excellent temporal stability during storage.

As the photosensitive resin composition, for example, Patent Document 1 discloses (A) (a) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radical polymerizable compound having an epoxy group, and (c) other A resin soluble in an alkaline aqueous solution, which is a polymer of a radical polymerizable compound, and (B) a photosensitive resin composition containing a radiation-sensitive acid generating compound, Patent Document 2 discloses an alkali-soluble acrylic polymer binder, A photosensitive resin composition comprising a quinonediazide group-containing compound, a crosslinking agent, and a photoacid generator has been proposed. However, these methods are not satisfactory for producing a high-quality liquid crystal display element because the sensitivity, unexposed part residual film ratio, resolution, and temporal stability are not sufficient. Patent Document 3 discloses that a crosslinking agent, an acid generator, and itself is insoluble or hardly soluble in an alkaline aqueous solution, but has a protecting group that can be cleaved by the action of an acid, and the protecting group is cleaved. Has proposed a positive chemically amplified resist composition characterized by containing a resin that is soluble in an alkaline aqueous solution. However, adhesion and transmittance are not sufficient, and it is not satisfactory for producing a high-quality liquid crystal display element. Patent Document 4 proposes a radiation-sensitive resin composition characterized by containing an acetal structure and / or a ketal structure, a resin containing an epoxy group, and an acid generator. It was not a thing.

JP-A-5-165214 Japanese Patent Laid-Open No. 10-153854 JP 2004-4669 A JP 2004-264623 A

Accordingly, the object of the present invention is a positive photosensitive resin composition excellent in sensitivity, remaining film ratio, and storage stability, and a cured film forming method using the same, and is cured by heat resistance and adhesion. It is to provide a positive photosensitive resin composition and a cured film forming method using the same, from which a cured film having excellent transmittance and the like can be obtained.

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention.
The present invention is as follows.
(1) (A) a resin containing a structural unit represented by the following general formula (1), which is insoluble in alkali or hardly soluble in alkali, and becomes alkali-soluble when an acid-dissociable group is dissociated, (B A positive photosensitive resin composition comprising: a compound having two or more epoxy groups in the molecule; and (C) a compound capable of generating an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more.

In general formula (1),
R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group.
R ² and R ³ each independently represents a hydrogen atom, a linear or branched alkyl group. However, the case where R ² and R ³ are hydrogen atoms at the same time is excluded.
R ⁴ represents a linear, branched or cyclic alkyl group or aralkyl group which may be substituted.
Any one of R ² and R ⁴ or R ³ and R ⁴ may be linked to form a cyclic ether.

(2) The positive photosensitive resin composition as described in (1) above, wherein the component (A) further contains a structural unit containing a carboxyl group.

(3) The positive photosensitive resin as described in (1) or (2) above, wherein the component (C) contains a compound containing an oxime sulfonate group represented by the following general formula (2): Composition.

In general formula (2),
R ⁵ represents a linear, branched or cyclic alkyl group which may be substituted, or an aryl group which may be substituted.

(4) The positive type as described in (3) above, wherein the compound containing an oxime sulfonate group represented by the general formula (2) is an oxime sulfonate compound represented by the following general formula (3) Photosensitive resin composition.

In general formula (3),
R ⁵ is the same as R ⁵ in formula (2).

X represents an alkyl group, an alkoxy group, or a halogen atom.
m represents an integer of 0 to 3. When m is 2 or 3, the plurality of X may be the same or different.

(5) The positive photosensitive resin composition as described in any one of (1) to (4) above, further comprising (D) an adhesion assistant.

(6) The positive photosensitive resin composition according to any one of (1) to (5) above is applied on a substrate and dried to form a coating film. Actinic rays having a wavelength of 300 nm or more through a mask A method for forming a cured film, comprising: a step of exposing the substrate using an alkali developer; a step of developing with an alkali developer to form a pattern; and a step of heat-treating the obtained pattern.

(7) In the cured film forming method described in (6) above, a cured film formation including a step of exposing the entire surface after the step of forming the pattern and before the step of heat-treating the obtained pattern. Method.

Hereinafter, preferred embodiments of the present invention will be further described.

(8) The positive photosensitive resin as described in any one of (1) to (5) above, wherein 1 to 50 parts by mass of component (B) is contained per 100 parts by mass of component (A). Resin composition.

(9) The component (C) is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). The positive photosensitive resin composition as described.

(10) Any of (5), (8) and (9) above, wherein 0.1 to 20 parts by mass of component (D) is contained per 100 parts by mass of component (A) The positive photosensitive resin composition described in 1.

According to the present invention, a positive photosensitive resin composition excellent in sensitivity, remaining film ratio, and storage stability and a cured film forming method using the same, and by curing, heat resistance, adhesion, transmittance, etc. A positive photosensitive resin composition and a cured film forming method using the same can be provided.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(A) component (A) component contains the structural unit represented by General formula (1), is alkali-insoluble or alkali-insoluble, and becomes alkali-soluble when the acid-dissociable group is dissociated. It is. Here, the acid dissociable group represents a functional group capable of dissociating in the presence of an acid.

In general formula (1),
R ¹ represents a hydrogen atom, a methyl group, a halogen atom, or a cyano group.
R ² and R ³ each independently represents a hydrogen atom, a linear or branched alkyl group. However, the case where R ² and R ³ are hydrogen atoms at the same time is excluded.
R ⁴ represents an optionally substituted linear, branched or cyclic alkyl group, or an aralkyl group.
Any one of R ² and R ⁴ or R ³ and R ⁴ may be linked to form a cyclic ether.

In the general formula (1), R ¹ is preferably a hydrogen atom or a methyl group.
R ² and R ³ are preferably linear or branched alkyl groups having 1 to 6 carbon atoms.
R ⁴ is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted. Here, the substituent is preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom.

The aralkyl group as R ⁴ is preferably an aralkyl group having 7 to 10 carbon atoms.
When R ² and R ⁴ are linked to form a cyclic ether, it is preferable that R ² and R ⁴ are linked to form an alkylene chain having 2 to 5 carbon atoms.

Examples of the radical polymerizable monomer used to form the structural unit represented by the general formula (1) include 1-alkoxyalkyl acrylate, 1-alkoxyalkyl methacrylate, 1- (haloalkoxy) alkyl acrylate, Examples thereof include 1- (haloalkoxy) alkyl methacrylate, 1- (aralkyloxy) alkyl acrylate, 1- (aralkyloxy) alkyl methacrylate, tetrahydropyranyl acrylate, and tetrahydropyranyl methacrylate. Among these, 1-alkoxyalkyl acrylate, 1-alkoxyalkyl methacrylate, tetrahydropyranyl acrylate and tetrahydropyranyl methacrylate are preferable, and 1-alkoxyalkyl acrylate and 1-alkoxyalkyl methacrylate are particularly preferable.

Specific examples of the radical polymerizable monomer used for forming the structural unit represented by the general formula (1) include 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, and the like. It can be used in combination of the above.

As the radical polymerizable monomer used for forming the structural unit represented by the general formula (1), a commercially available one may be used, or one synthesized by a known method may be used. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst.

Wherein, R ^1, R ³ and R ⁴ correspond to R ^1, R ³ and R ⁴ in the general formula (1), R ¹³ and R ^14, -CH (R ¹³⁾ as (R ^14), This corresponds to R ² in the general formula (1).

In the component (A), a monomer having a structural unit other than the monomer for forming the structural unit represented by the general formula (1) can be copolymerized as necessary.

As structural units other than the structural unit represented by the general formula (1), styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, α-methyl-acetoxystyrene, methoxystyrene, ethoxy Styrene, chlorostyrene, vinyl benzoic acid, methyl vinyl benzoate, ethyl vinyl benzoate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n methacrylate -Propyl, isopropyl acrylate, isopropyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methacryl Examples of the structural unit include 2-hydroxypropyl acid, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, acrylonitrile, and the like. These can be used alone or in combination of two or more. .

The component (A) preferably contains a structural unit containing a carboxyl group such as acrylic acid, methacrylic acid or vinyl benzoic acid as a structural unit other than the structural unit represented by the general formula (1).

In the repeating unit constituting the component (A), the content of the structural unit represented by the general formula (1) is preferably 10 to 100 mol%, more preferably 20 to 90 mol%, and particularly preferably 30 to 80 mol%. preferable. The content of the structural unit containing a carboxyl group is preferably 40 mol% or less, more preferably 5 to 25 mol%. 10 to 20 mol% is particularly preferred.

The molecular weight of the component (A) is a polystyrene-equivalent weight average molecular weight, preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000.

As the component (A), two or more kinds of resins containing different constitutional units can be mixed and used, or two or more kinds of resins comprising the same constitutional unit and having different compositions can be used in combination. it can.

Various methods for synthesizing the component (A) are known. To give an example, at least a radical polymerizable monomer used to form the structural unit represented by the general formula (1) is given. It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a monomer in an organic solvent using a radical polymerization initiator.

In addition, the composition of this invention may contain resin other than (A) component and (B) component explained in full detail below, The content rate of this resin is with respect to 100 mass parts of (A) component. The amount is preferably 50 parts by mass or less.

(B) Compound having two or more epoxy groups in the molecule Specific examples of the compound having two or more epoxy groups in the molecule (also referred to as “component (B)”) include bisphenol A type epoxy resins and bisphenols. Examples thereof include an F-type epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, and an aliphatic epoxy resin.

These are available as commercial products. For example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 , Manufactured by Dainippon Ink and Chemicals, Inc.), as bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above) , Manufactured by Dainippon Ink & Chemicals, Inc.), LCE-21, RE-602S (above Nippon Kayaku Co., Ltd.), etc., as phenol novolac type epoxy resins, JER152, JER154, JER157S70 (above, Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N- 770, EPICLON N-775 (manufactured by Dainippon Ink & Chemicals, Inc.), etc., as cresol novolac type epoxy resins, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), etc. are aliphatic epoxy resins. ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, 700 and above PB 4 Daicel Chemical Co., Ltd.).

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.) and the like can be mentioned, and these can be used alone or in combination of two or more.
Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. A bisphenol A type epoxy resin is particularly preferable.
The content of the epoxy resin (B) is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the component (A).
The component (B) is effective for improving the adhesion with a metal layer such as chromium, molybdenum, aluminum, tantalum, titanium, copper, cobalt, tungsten, and nickel. When these metal layers are formed by a sputtering method, the effect is remarkable.

(C) Compound that generates acid upon irradiation with actinic rays having a wavelength of 300 nm or longer As the compound that generates acid upon irradiation with actinic rays having a wavelength of 300 nm or longer, which is used in the present invention (also referred to as “component (C)”), It represents a compound that is sensitive to actinic rays having a wavelength of 300 nm or more and generates an acid, and is not limited to the structure. As the generated acid, a compound that generates an acid having a pKa of 3 or less is preferable, and a compound that generates a sulfonic acid is particularly preferable. For example, a sulfonium salt, an iodonium salt, a diazomethane compound, an imide sulfonate compound, an oxime sulfonate compound, and the like can be given, and these can be used alone or in combination of two or more.
Among these, a compound containing an oxime sulfonate group represented by the general formula (2) is preferable.

In general formula (2),
R ⁵ represents a linear, branched or cyclic alkyl group which may be substituted, or an aryl group which may be substituted.
The alkyl group for R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group for R ⁵ includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group). Etc.).
The aryl group for R ⁵ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ⁵ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

The compound containing an oxime sulfonate group represented by the general formula (2) is more preferably an oxime sulfonate compound represented by the following general formula (3).

In general formula (3),
R ⁵ is the same as R ⁵ in formula (2).
X represents an alkyl group, an alkoxy group, or a halogen atom.
m represents an integer of 0 to 3. When m is 2 or 3, the plurality of X may be the same or different.

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m is preferably 0 or 1.
In particular, in general formula (3), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

Specific examples of the oxime sulfonate compound include, for example, the following compound (i), compound (ii), compound (iii), compound (iv), compound (v), etc., alone or in combination of two or more. Can be used. It can also be used in combination with other types of component (C).

Compounds (i) to (v) can be obtained as commercial products.
(D) Adhesion aid The positive photosensitive resin composition of the present invention may further contain (D) an adhesion aid.
As the adhesion assistant (D) used in the present invention, the adhesion between an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the like and an insulating film is used. It is a compound that improves. Specific examples include silane coupling agents and thiol compounds.

The silane coupling agent as an adhesion aid used in the present invention is for the purpose of modifying the interface, and any known one can be used without any particular limitation.

Preferred silane coupling agents include, for example, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, Examples thereof include γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane.

Γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is even more preferable.

These can be used alone or in combination of two or more. These are effective for improving the adhesion to the substrate and also for adjusting the taper angle with the substrate.

In the positive photosensitive resin composition of the present invention, the mixing ratio of the component (A), the component (B), the component (C), and the component (D) is (B) with respect to 100 parts by mass of the component (A). As described above, the component is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass. Also, Component (C) is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 10 parts by mass. The component (D) is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass.

<Other ingredients>
In addition to the components (A), (B), (C), and (D), the positive photosensitive resin composition of the present invention includes a basic compound, a surfactant, and an ultraviolet absorber as necessary. An agent, a sensitizer, a plasticizer, a thickener, an organic solvent, an adhesion promoter, an organic or inorganic precipitation inhibitor, and the like can be added.

<Basic compound>
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like.

Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,3,0] -7 Undesen.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

Examples of carboxylic acid quaternary ammonium salts include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The compounding ratio of the basic compound is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.2 part by mass per 100 parts by mass of the component (A).

<Surfactant>
As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. it can. The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by JEMCO), Mega Fuck (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Each series such as Surflon (manufactured by Asahi Glass) PolyFox (manufactured by OMNOVA) can be listed.

Surfactant can be used individually or in mixture of 2 or more types.
The compounding ratio of the surfactant is usually 10 parts by mass or less per 100 parts by mass of the component (A), preferably 0.01 to 10 parts by mass, more preferably 0.01 to 1 part by mass.

<Plasticizer>
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.

The blending ratio of the plasticizer is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass per 100 parts by mass of the component (A).

<Solvent>
The positive photosensitive composition of the present invention is used as a solution by dissolving the above components in a solvent. As the solvent used in the positive photosensitive composition of the present invention, for example,
(A) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(A) Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether;
(C) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(D) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(E) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;
(F) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
(G) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(H) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(G) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
(Co) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether;
(Sa) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
(L) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(S) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(C) Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropion methyl, 3-ethoxypropion ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, aceto Other esters such as methyl acetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(So) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
(Ta) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(H) Lactones such as γ-butyrolactone can be mentioned.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.

A solvent can be used individually or in mixture of 2 or more types.
The mixing ratio of the solvent is usually 50 to 3,000 parts by weight, preferably 100 to 2,000 parts by weight, more preferably 100 to 500 parts by weight per 100 parts by weight of component (A).

According to the present invention, a positive photosensitive resin composition having excellent sensitivity, remaining film ratio, and stability over time, and by curing, a positive film can be obtained that has excellent heat resistance, adhesion, transparency, and the like. Type photosensitive resin composition can be provided.

<Method for forming cured film>
Next, a method for forming a cured film using the positive photosensitive resin composition of the present invention will be described.
The positive photosensitive resin composition according to the present invention is applied on a substrate and heated to form a coating film on the substrate.

By irradiating the obtained coating film with an actinic ray having a wavelength of 300 nm or more, the component (C) is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid dissociable group in the structural unit represented by the general formula (1) contained in the component (A) is dissociated by a hydrolysis reaction, and a carboxyl group is generated. By developing this using an alkali developer, an exposed portion containing a resin having a carboxyl group that is easily dissolved in the alkali developer is removed, and a positive image is formed.
The reaction formula of this hydrolysis reaction is shown below.

In order to accelerate the hydrolysis reaction, post-exposure heat treatment: Post-Exposure-Bake (hereinafter referred to as PEB) can be performed as necessary. However, when the heating temperature becomes high, the generated carboxyl group causes a crosslinking reaction with the epoxy group in the component (B), so that development cannot be performed.

Actually, when tert-butyl methacrylate is used in place of the repeating unit represented by the general formula (1), the activation energy of the acid dissociation reaction is high. Therefore, PEB at a high temperature is required to dissociate the acid dissociable group. However, at the same time, a cross-linking reaction occurs and an image cannot be obtained.

On the other hand, the acid dissociable group represented by the general formula (1) of the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group. The positive image can be formed by development.

In addition, you may accelerate | stimulate decomposition | disassembly of an acid dissociable group, without raise | generating a crosslinking reaction by performing PEB at comparatively low temperature.

The PEB temperature is preferably 130 ° C. or lower, more preferably 110 ° C. or lower, and particularly preferably 80 ° C. or lower.

Next, by heating the obtained positive image, the acid dissociable group in the general formula (1) is thermally decomposed to generate a carboxyl group, and then cured by crosslinking with the epoxy group in the component (B). A film can be formed. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., particularly preferably 200 to 250 ° C.
The heating time can be appropriately set depending on the heating temperature or the like, but is generally 10 to 90 minutes.

If a step of irradiating the entire surface with actinic rays is added before the heating step, the crosslinking reaction can be promoted by the acid generated by the irradiation of actinic rays.

Next, a method for forming a cured film using the positive photosensitive resin composition of the present invention will be specifically described.

Preparation method of composition solution: (A) component, (B) component, (C) component and other compounding agents are mixed at a predetermined ratio and in an arbitrary method, and stirred and dissolved to prepare a composition solution. For example, each component can be dissolved in a solvent in advance to obtain a solution, and then mixed at a predetermined ratio to prepare a composition solution. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Method for creating coating film>
A desired coating film can be formed by applying the composition solution to a predetermined substrate and removing the solvent by heating (hereinafter referred to as pre-baking). Examples of the substrate include a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as required, and a transparent conductive circuit layer in manufacturing a liquid crystal display element. The coating method on the substrate is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, or the like can be used.

The heating conditions during pre-baking are such that the acid dissociable group in the repeating unit represented by the formula (1) in the (A) component in the unexposed area is dissociated and the (A) component is soluble in the alkali developer. However, it is preferably about 80 to 130 ° C. for about 30 to 120 seconds, although it varies depending on the type and mixing ratio of each component.

<Pattern formation method>
After irradiating the substrate on which the coating film is provided with actinic rays through a mask having a predetermined pattern, heat treatment (PEB) is performed as necessary, and then the exposed portion is removed using a developer to form an image pattern. Form.

For the emission of actinic rays, low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, chemical lamps, excimer laser generators, and the like can be used. Actinic rays having wavelengths of 300 nm or more such as g-line, i-line, and h-line Is preferred. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

Examples of the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metals such as sodium bicarbonate and potassium bicarbonate Bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is usually 30 to 180 seconds, and the developing method may be any of the liquid piling method and the dipping method. After development, washing with running water can be performed for 30 to 90 seconds to form a desired pattern.

<Crosslinking process>
For a pattern having an unexposed portion obtained by development, a heating device such as a hot plate or an oven is used to set the oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 30 minutes on the hot plate. Then, by heat treatment for 30 to 90 minutes, the acid-dissociable group in component (A) is eliminated, a carboxyl group is generated, and the epoxy group in component (B) is cross-linked to have heat resistance and hardness. It is possible to form a protective film and an interlayer insulating film excellent in the above. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Prior to the heat treatment, it is preferable to generate an acid from the component (C) present in the unexposed portion by irradiating the patterned substrate with actinic rays.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[Synthesis Example 1: Synthesis of A1]
500 ml of 67.1 g (0.36 mol) of 1-n-butoxyethyl methacrylate, 21.1 g (0.12 mol) of benzyl methacrylate, 10.3 g (0.12 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone A three-necked flask was charged with a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) as a radical polymerization initiator, and polymerized at 80 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A1 (1-n-butoxyethyl methacrylate / benzylbenzyl methacrylate / (Methacrylic acid) was obtained as a propylene glycol monomethyl ether acetate solution.

As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 2: Synthesis of A2]
15.7 g (0.48 mol) of 1-benzyloxyethyl methacrylate, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate, 5.2 g (0.06 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone A 500 ml three-necked flask was charged, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, followed by polymerization at 80 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A2 (1-benzyloxyethyl methacrylate / 2-hydroxyethyl methacrylate / methacrylate). Acid) was obtained as a diethylene glycol dimethyl ether solution.

As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 4000 and the molecular weight distribution (Mw / Mn) was 1.6.

[Synthesis Example 3: Synthesis of A3]
66.4 g (0.42 mol) of 1-ethoxyethyl methacrylate, 21.1 g (0.12 mol) of benzyl methacrylate, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate and 300 ml of methyl isobutyl ketone A 500 ml three-necked flask was charged, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, followed by polymerization at 80 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A3 (1-ethoxyethyl methacrylate / benzyl methacrylate / methacrylic acid 2 -Hydroxyethyl) was obtained as a diethylene glycol ethyl methyl ether solution.

[Synthesis Example 4: Synthesis of A4]
11.9 g (0.36 mol) of 1-ethoxyethyl acrylate, 31.7 g (0.18 mol) of benzyl methacrylate, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate and 300 ml of methyl isobutyl ketone A 500 ml three-necked flask was charged, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, followed by polymerization at 80 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A4 (1-ethoxyethyl acrylate / benzyl methacrylate / methacrylic acid). 2-hydroxyethyl) was obtained as a propylene glycol monomethyl ether acetate solution.

As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 5000 and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 5: Synthesis of A5]
1-Ethoxyethyl methacrylate 30.8 g (0.24 mol), benzyl methacrylate 42.3 g (0.24 mol), 2-hydroxyethyl methacrylate 7.8 g (0.06 mol), methacrylic acid 5.2 g (0.06 mol) and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator to the nitrogen stream. The polymerization was carried out at 80 ° C. for 6 hours. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A5 (1-ethoxyethyl methacrylate / benzyl methacrylate / 2-hydroxy methacrylate). Ethyl / methacrylic acid) was obtained as a diethylene glycol dimethyl ether solution.

As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 7000 and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 6: Synthesis of A6]
63.7 g (0.30 mol) of 1-cyclohexyloxyethyl methacrylate, 40.3 g (0.30 mol) of p-methoxystyrene and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, to which a radical polymerization initiator was added. Then, a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added and polymerized at 80 ° C. for 6 hours under a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals are collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and heptane and methyl isobutyl ketone contained in the solution are distilled off under reduced pressure to obtain polymer A6 (1-cyclohexyloxyethyl methacrylate / p-methoxystyrene). Obtained as a diethylene glycol ethyl methyl ether solution.

As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 7: Synthesis of A7]
71.5 g (0.42 mol) 2-tetrahydropyranyl methacrylate, 19.5 g (0.12 mol) p-acetoxystyrene, 7.8 g (0.06 mol) 2-hydroxyethyl methacrylate, and methyl isobutyl Charge 300 ml of ketone into a 500 ml three-necked flask, add a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) as a radical polymerization initiator, and polymerize at 80 ° C. for 6 hours in a nitrogen stream. It was. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in a mixed solvent of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A7 (2-tetrahydromethacrylate methacrylate). Pyranyl / p-acetoxystyrene / 2-hydroxyethyl methacrylate) was obtained as a mixed solvent solution of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether.

As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 6000 and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Comparative Example 1: Synthesis of A′8]
500 ml 3-neck flask containing 51.2 g (0.36 mol) of tert-butyl methacrylate, 21.1 g (0.12 mol) of benzyl methacrylate, 10.3 g (0.12 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone Then, a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, and the mixture was polymerized at 80 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A′8 (tert-butyl methacrylate / benzyl methacrylate / methacrylic acid). Acid) was obtained as a propylene glycol monomethyl ether acetate solution.

As for the molecular weight and molecular weight distribution of the polymer obtained, GPC measurement using polystyrene as a standard revealed that the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.6.

[Synthesis Comparative Example 2: Synthesis of A′9]
72.1 g of poly 4-hydroxystyrene (Nippon Soda Co., Ltd. VP-8000), 16.4 g of ethyl vinyl ether and 300 ml of ethyl acetate were charged into a 500 ml three-necked flask, and a catalytic amount of paratoluenesulfonic acid was added thereto. The reaction was performed for 3 hours at room temperature under a nitrogen stream. After adding a small amount of triethylamine, wash with pure water. Propylene glycol monomethyl ether acetate was added to the ethyl acetate layer, and ethyl acetate was distilled off under reduced pressure to obtain polymer A′9 (p-1-ethoxyethoxystyrene / p-hydroxystyrene) as a propylene glycol monomethyl ether acetate solution. It was.

The constituent ratio of the p-1-ethoxyethoxystyrene unit and the p-hydroxystyrene unit in the obtained polymer was about 35:65 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 9000, and the molecular weight distribution (Mw / Mn) was 1.2.

[Synthesis Comparative Example 3: Synthesis of A′10]
According to Synthesis Example 1 of JP-A No. 2004-264623, A′-10 was synthesized.
A 3-neck flask was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether, followed by 40 parts by mass of 1- (cyclohexyloxy) ethyl methacrylate and 5 parts by mass of styrene. Then, 45 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate and 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, and then gently agitated. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A′10). As a result of GPC measurement using polystyrene as a standard, the polymer obtained had a weight average molecular weight of about 11,000 and a molecular weight distribution (Mw / Mn) of 1.9.

[Examples 1 to 7 and Comparative Examples 1 to 4]
(1) Preparation of positive photosensitive resin composition solution Each component shown in Table 1 below is mixed to obtain a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm. A positive photosensitive resin composition solution was prepared.

(2) Evaluation of storage stability The viscosity of the positive photosensitive resin composition solution at 23 ° C. was measured using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. The viscosity after storing the composition in a thermostatic layer at 23 ° C. for 1 month was measured. When the viscosity increase after storage for 1 month at room temperature is less than 5% with respect to the viscosity after preparation, the case of ◯ and 5% or more was evaluated as x. The results are shown in Table 2 below.

(3) Evaluation of sensitivity and remaining film ratio during development After a positive photosensitive resin composition solution is spin-coated on a silicon wafer having a silicon oxide film, the film thickness is pre-baked on a hot plate at 100 ° C. for 60 seconds. A 3 μm coating film was formed.

Next, exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.). Then, after baking at 50 ° C. for 60 seconds, development was performed at 23 ° C. for 60 seconds with an alkali developer (2.38 mass% or 0.4 mass% tetramethylammonium hydroxide aqueous solution) shown in Table 2. Rinse with pure water for 1 minute. By these operations, the optimum exposure dose (Eopt) when resolving 5 μm line and space at 1: 1 was defined as sensitivity.

The film thickness of the unexposed area after development is measured, and the ratio to the film thickness after coating (the film thickness of the unexposed area after development ÷ film thickness after coating × 100 (%)) is obtained to determine the remaining film thickness during development. The film rate was evaluated.

Table 2 shows the evaluation results of the sensitivity and the remaining film ratio during development.

(4) Evaluation of heat resistance In (3) above, except that a transparent substrate (Corning 1737 manufactured by Corning) was used instead of the silicon wafer having a silicon oxide film, a coating film was formed in the same manner as (3) above. Using a proximity exposure apparatus (UX-1000SM manufactured by Ushio Electric Co., Ltd.), a predetermined mask was brought into close contact, and exposure was performed using ultraviolet rays having a light intensity at 365 nm of 18 mW / cm ² . Next, development was performed at 23 ° C. for 60 seconds using an alkali developer (2.38 mass% or 0.4% mass% tetramethylammonium hydroxide aqueous solution) described in Table 2, followed by ultrapure water for 10 seconds. Rinse. By these operations, a pattern with a 10 μm line and space of 1: 1 was created. The entire surface of the obtained pattern was further exposed for 100 seconds and heated in an oven at 230 ° C. for 1 hour to form a heat-cured film on the glass substrate.

The heat resistance was evaluated by measuring the rate of change in the bottom dimension before and after heat curing (1—bottom dimension of heat-cured film ÷ bottom dimension after development) × 100 (%). The case where this change rate was less than 5% was evaluated as ◯, and the case where it was 5% or more was evaluated as x.
The evaluation results of heat resistance are shown in Table 2.

(5) Evaluation of transmittance and adhesion The coating film was formed in the same manner as in the above (4), and the alkaline developer described in Table 2 (2.38% by mass or 0.4% by mass) without exposure. Development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution, and then rinsed with ultrapure water for 10 seconds. Next, using a proximity exposure apparatus (UX-1000SM manufactured by Ushio Electric Co., Ltd.), the entire surface was exposed for 100 seconds using ultraviolet light having a light intensity at 365 nm of 18 mW / cm ² . Next, it heated at 220 degreeC in oven for 1 hour, and formed the thermosetting film on the glass substrate.

The transmittance of the obtained heat cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). Separately, the film thickness was measured using Dektak 3 manufactured by ULVAC, and the transmittance per 1 μm film thickness was determined.

Using a cutter on the heat-cured film, cuts were made at intervals of 1 mm vertically and horizontally, and a tape peeling test was performed using scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The case where the area was less than 1% was marked as ◯, the case where it was less than 1 to 5%, and the case where it was 5% or more as x.

The evaluation results of transmittance and adhesion are shown in Table 2.

The (A) component, (B) component, (C) component, (D) component, basic compound, solvent and surfactant described in Table 1 are as follows.

(A) Component The numerical value on the right side of the structural unit represents the molar ratio of the structural unit.

(B) Component B1: JER1001 (made by Japan Epoxy Resin Co., Ltd.)
B2: JER834 (made by Japan Epoxy Resin Co., Ltd.)
B3: JER157S70 (Japan Epoxy Resin Co., Ltd.)
B4: JER154 (made by Japan Epoxy Resin Co., Ltd.)
(C) component

Component (D) D1: γ-glycidoxypropyltrimethoxysilane D2: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane D3: γ-methacryloxypropyltrimethoxysilane [basic compound]
E1: 4-dimethylaminopyridine E2: 1,5-diazabicyclo [4,3,0] -5-nonene [solvent]
F1: Propylene glycol monomethyl ether acetate F2: Diethylene glycol dimethyl ether F3: Diethylene glycol ethyl methyl ether [Surfactant]
G1: Fluorard F-430 (manufactured by 3M)
G2: Megafuck R-08 (manufactured by Dainippon Ink and Chemicals)
G3: PolyFox PF-6320 (manufactured by OMNOVA)

From Table 2, the positive photosensitive resin composition of the present invention is excellent in sensitivity, remaining film rate, storage stability, and cured to form a cured film having excellent heat resistance, adhesion, transmittance, and the like. It is clear to get.

Claims

(A) A resin containing a structural unit represented by the following general formula (1), alkali-insoluble or alkali-insoluble, and alkali-soluble when the acid-dissociable group is dissociated, (B) intramolecular A positive photosensitive resin composition comprising: a compound having two or more epoxy groups; and (C) a compound capable of generating an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more.

In general formula (1),
R 1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group.
R 2 and R 3 each independently represents a hydrogen atom, a linear or branched alkyl group. However, the case where R 2 and R 3 are hydrogen atoms at the same time is excluded.
R 4 represents a linear, branched or cyclic alkyl group or aralkyl group which may be substituted.
Any one of R 2 and R 4 or R 3 and R 4 may be linked to form a cyclic ether.
The positive photosensitive resin composition according to claim 1, wherein the component (A) further contains a structural unit containing a carboxyl group.
The positive photosensitive resin composition according to claim 1, wherein the component (C) contains a compound containing an oxime sulfonate group represented by the following general formula (2).

In general formula (2),
R 5 represents a linear, branched or cyclic alkyl group which may be substituted, or an aryl group which may be substituted.
The positive photosensitive resin composition according to claim 3, wherein the compound containing an oxime sulfonate group represented by the general formula (2) is an oxime sulfonate compound represented by the following general formula (3). object.

In general formula (3),
R 5 is the same as R 5 in the general formula (2).
X represents an alkyl group, an alkoxy group, or a halogen atom.
m represents an integer of 0 to 3. When m is 2 or 3, the plurality of X may be the same or different.
The positive photosensitive resin composition according to claim 1, further comprising (D) an adhesion assistant.
Applying the positive photosensitive resin composition according to claim 1 onto a substrate and drying to form a coating film, exposing to light using an actinic ray having a wavelength of 300 nm or more through a mask, an alkaline developer A cured film forming method comprising: a step of developing using a pattern to form a pattern; and a step of heat-treating the obtained pattern.
7. A cured film forming method according to claim 6, comprising a step of exposing the entire surface after the step of forming the pattern and before the step of heat-treating the obtained pattern.