WO2007145249A1

WO2007145249A1 - Positive photosensitive resin composition containing polymer having ring structure

Info

Publication number: WO2007145249A1
Application number: PCT/JP2007/061903
Authority: WO
Inventors: Tadashi Hatanaka; Junpei Kobayashi
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-06-15
Filing date: 2007-06-13
Publication date: 2007-12-21
Also published as: KR20090016670A; TW200817840A; JP5163899B2; TWI411885B; JPWO2007145249A1; CN101467100A; CN101467100B; KR101388998B1

Abstract

[PROBLEMS] To provide a positive photosensitive resin composition which has high sensitivity and is reduced in film thickness reduction in unexposed areas and which, after film formation, retains a high transmission and a film thickness even through high-temperature burning or treatment with a liquid resist stripper and does not crack during ITO sputtering; and a cured film suitable for use as a film material for various displays. [MEANS FOR SOLVING PROBLEMS] The positive photosensitive resin composition comprises: ingredient (A) which is an alkali-soluble acrylic polymer having at least one of carboxy and phenolic hydroxy and at least one of hydroxy other than phenolic hydroxy and amino having active hydrogen and having a number-average molecular weight of 2,000-30,000; ingredient (B) which is an alkali-soluble resin having a ring structure in the backbone; ingredient (C) which is a compound having a vinyl ether group; ingredient (D) which is a compound having a blocked isocyanate group; ingredient (E) which is a photo-acid generator; and a solvent (F). The cured film is obtained from the composition.

Description

Specification

Technical Field of Positive Type Photosensitive Resin Composition Containing Polymer Compound with Ring Structure

[0001] The present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a positive photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.

Background art

[0002] Generally, in display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements, patterned electrode protective films and planarization films

An insulating film or the like is provided. As a material for forming these films, among photosensitive resin compositions, the photosensitive resin has the characteristics that the number of steps for obtaining a required pattern shape is small and the force is sufficiently flat. Compositions are more widely used than ever before.

[0003] These films described above have excellent process resistance such as heat resistance, solvent resistance, long-time firing resistance, metal sputtering resistance, and good adhesion to the substrate. Various characteristics such as having a wide process margin that can form patterns under various process conditions according to the purpose of use, high sensitivity and high transparency, and low film unevenness after development. Is required. Therefore, from the viewpoint of such required characteristics, heretofore, resins containing a naphthoquinonediazide compound have been widely used as the photosensitive resin composition.

[0004] By the way, among the required characteristics of such photosensitive resin materials, sensitivity is one of important characteristics. The improvement in sensitivity makes it possible to significantly reduce the production time in industrial production of display elements and the like. For this reason, in the current situation where the demand for liquid crystal displays is significantly increasing, sensitivity is one of the most important properties required for this type of photosensitive resin material.

[0005] However, the conventional photosensitive resin material containing the naphthoquinone diazide compound described above is not sufficiently satisfactory in terms of sensitivity. Alkalis for polymers in materials The ability to improve the sensitivity by increasing the solubility in the developer solution. This method has its limitations, and dissolution of unexposed areas also occurs, resulting in a decrease in the remaining film ratio, which is used for large displays. However, this substrate has the disadvantage of causing unevenness of the film.

[0006] Thus, several patent applications have been filed so far for the purpose of increasing the sensitivity of photosensitive resin materials. For example, a radiation-sensitive resin composition containing alkali-soluble resin and at least one of a specific polyhydroxy compound and a derivative thereof has been proposed (see, for example, Patent Document 1). However, this proposed material has problems in storage stability due to the high symmetry of the photosensitizer.

[0007] Also, a positive-type radiation-sensitive resin composition containing an alkali-soluble phenol resin and a radiation-sensitive compound (see, for example, Patent Document 2), and a specific alkali-soluble resin and a quinonediazide compound A positive photosensitive resin composition (see, for example, Patent Document 3) has been proposed. However, since these use novolac resin as the binder polymer, they have problems in transparency and stability during firing for a long time.

As described above, it is very difficult to develop a photosensitive resin composition that satisfies other characteristics and has a desired level of high sensitivity. It was difficult to obtain a satisfactory photosensitive resin composition.

[0009] In general, in a conventional photosensitive resin material containing a naphthoquinone diazide compound, after exposure and development, a photo film is used to prevent coloring of the cured film and deterioration of transparency due to the naphthoquinone diazide compound. The force of bleaching Even after this photobleaching process, the film obtained is colored with reduced light transmittance when baked at a high temperature of about 250 ° C, and at lower temperatures. For example, even when baked at 230 ° C for a long time, the light transmittance is reduced (colored). Furthermore, chemical treatment such as an amine-based solution of the resist stripping solution also reduces the light transmittance and improves transparency. The conventional photosensitive resin material containing naphthoquinone diazide compound has a problem in terms of heat resistance and chemical resistance (for example, Patent Document 4). reference).

[0010] On the other hand, a chemically amplified resist has been developed as a photosensitive material with high sensitivity and high resolution. Conventional chemically amplified resists that have been developed as resists for semiconductors can be applied to light sources (KrF, ArF) with shorter wavelengths than i-line, enabling finer pattern formation. At high temperatures such as those used for film curing and in the presence of resist stripping solutions, the protective group bond and ether bond thermal cross-links easily decompose, resulting in heat resistance and chemical resistance. It was almost impossible to use as a permanent film having extremely low properties (see, for example, Patent Document 5). In addition, in order to enable thermosetting, even if an epoxy-caminoplast cross-linking system is introduced into a chemically amplified resist, the effect of the acid generated by the photoacid generator (PAG) force in the resist due to exposure. As a result, new problems such as the cross-linking of the exposed part progressing and the dissolution contrast with the unexposed part disappearing, it was difficult to introduce such a cross-linked chemical amplification type resist into the resist.

[0011] Further, these materials are formed on the film by metal force sputtering such as ITO, Al, and Cr after the formed pattern is thermally cured. In general, when acrylic resin is used, it is known that ITO, which is sputtered at a high temperature, easily cracks in the film. Therefore, a material having high-temperature sputtering resistance, high sensitivity and high heat-resistant transparency has been demanded.

Patent Document 1: Japanese Patent Laid-Open No. 4-211255

Patent Document 2: JP-A-9-006000

Patent Document 3: JP-A-8-044053

Patent Document 4: Japanese Patent Laid-Open No. 4-352101

Patent Document 5: US Patent No. 5075199

Disclosure of the invention

Problems to be solved by the invention

[0012] The present invention has been made in view of the above circumstances, and the first problem is that the pattern film has sufficiently high sensitivity, and has substantially no force so that an unexposed portion is not observed during development. It is to provide a positive photosensitive resin composition capable of forming

The second problem is to obtain a cured film and such a cured film that maintain a high transmittance even when baked at a high temperature or treated with a resist stripper and that do not crack when ITO is sputtered. It is an object of the present invention to provide a positive photosensitive resin composition that can be used.

Means for solving the problem

[0013] That is, as a first aspect, the following (A) component, (B) component, (C) component, (D) component and (E) It is a positive photosensitive resin composition containing a solvent.

Component (A): at least one selected from the group power of carboxyl group and phenolic hydroxy group, and at least one selected from the group power of hydroxy group other than phenolic hydroxy group and amino group having active hydrogen, and several Alkali-soluble acrylic polymer having an average molecular weight of 2,000 to 3,000

Component (B): alkali-soluble rosin having an aromatic ring or alicyclic structure in the main chain

Component (C): Compound having two or more vinyl ether groups in one molecule

Component (D): Compound having two or more block isocyanate groups in one molecule

(E) component: photoacid generator

(F) Solvent

As a second aspect, the positive photosensitive resin composition according to the first aspect, wherein the component (B) is an alkali-soluble resin selected from the group consisting of polyimide and polyimide precursor power.

As a third aspect, the positive photosensitive resin composition according to the first aspect or the second aspect, wherein the number average molecular weight of the alkali-soluble resin of component (B) is 2,000 to 30,000.

As a fourth aspect, the positive photosensitive resin according to any one of the first to third aspects, wherein the component (B) is an alkali-soluble resin having an alkyl group substituted with a fluorine atom. Braid composition.

As a fifth aspect, the component (B) is an alkali-soluble resin containing polyimide, and the polyimide is contained in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A). The positive photosensitive resin composition according to any one of the fourth aspects.

As a sixth aspect, the component (B) is an alkali-soluble resin containing a polyimide precursor, and the polyimide precursor is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the component (A). The positive photosensitive resin composition according to any one of the first aspect to the fourth aspect.

As a seventh aspect, the positive photosensitive resin composition according to any one of the first to sixth aspects, wherein the component (E) is a compound that generates sulfonic acid by light irradiation.

As an eighth aspect, the positive photosensitive resin composition according to any one of the first aspect to the seventh aspect, which further contains an amine compound as the component (G).

As a ninth aspect, as the first aspect, the component (H) further contains a fluorosurfactant. The positive photosensitive resin composition according to any one of the eighth aspect.

As a tenth aspect, a cured film obtained using the positive photosensitive resin composition according to any one of the first to ninth aspects.

An eleventh aspect is an interlayer insulating film comprising the cured film of the tenth aspect.

As a twelfth aspect, a microlens comprising the cured film according to the tenth aspect.

The invention's effect

[0014] The positive photosensitive resin composition of the present invention has sufficiently high sensitivity, and can form a pattern film that is virtually free to the extent that no film loss in the unexposed area is observed during development. Further, it is possible to provide a cured film that maintains a high transmittance even when it is baked at a high temperature or treated with a resist stripping solution, and that does not cause cracks during ITO sputtering.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The photosensitive resin composition of the present invention comprises (A) an alkali-soluble acrylic polymer, (B) a component alkali-soluble resin, (C) a compound having a butyl ether group, (D Component) having a block isocyanate group, (E) a photoacid generator and (F) a solvent, and optionally (G) an amine compound and Z or (H) A composition containing a component surfactant.

Hereinafter, details of each component will be described.

[0016] <(A) component>

In the structure of the polymer, the component (A) is at least one selected from the group power of a carboxyl group and a phenolic hydroxy group, and the group power of an amino group having a hydroxy group other than a phenolic hydroxy group and an active hydrogen. It is an alkali-soluble acrylic polymer having one kind and having a polystyrene-equivalent number average molecular weight (hereinafter referred to as number average molecular weight) of 2,000 to 30,000.

[0017] At least one selected from the group power of the carboxyl group and the phenolic hydroxy group reacts with a butyl ether group in the compound of the component (C) described later at an elevated temperature, and the component (C) It is a group capable of forming a resist film by thermal crosslinking with the compound. In addition, at least one selected from the group of hydroxy groups other than the phenolic hydroxy groups and amino groups having active hydrogen is a thermally cross-linked product of the components (A) and (C). (In the exposed part, in the decrosslinked product in which the thermally crosslinked product is further dissociated), the isocyanate in which the block part is dissociated with the compound of the component (D) described later at a higher temperature. It is a group capable of undergoing a crosslinking reaction via the group and curing the film.

The amino group having active hydrogen means a primary or secondary amino group that has high reactivity and can release protons. Therefore, the amide group does not have an active hydrogen and therefore does not correspond to an amino group having an active hydrogen.

[0018] The polymer of the component (A) is not particularly limited as long as it is an alkali-soluble acrylic polymer having such a structure, and the type of the main chain skeleton and side chain of the polymer constituting the polymer. Not.

[0019] However, the polymer of component (A) has a number average molecular weight in the range of 2,000 to 30,000, more preferably in the range of 2,000 to 15,000. There is. If the number average molecular weight is over 30,000, development residues are likely to occur, and the sensitivity is significantly reduced.On the other hand, if the number average molecular weight is less than 2,000, the development is At this time, a considerable amount of film loss occurs in the unexposed areas, which may result in insufficient curing.

[0020] The alkali-soluble acrylic polymer (Α) is a polymer obtained by homopolymerization or copolymerization of a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester, or styrene. It is soluble in an alkaline aqueous solution.

[0021] In the present invention, a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) uses a strong alkali-soluble acrylic polymer as the component (ii). You can also. In this case, the alkali-soluble acrylic polymer (component) may be a blend of a plurality of specific copolymers.

[0022] That is, the specific copolymer is a monomer group having a functional group for thermal crosslinking reaction, that is, a monomer group having at least one of a carboxyl group and a phenolic hydroxy group. A group of monomers and a monomer having a functional group for film curing, that is, a monomer having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen, and at least one monomer selected as appropriate. And a copolymer formed as an essential constituent unit having a number average molecular weight of 000 to 30,000. [0023] The above-mentioned "monomer having at least one of carboxyl group and phenolic hydroxy group" includes a monomer having a carboxyl group, a monomer having a phenolic hydroxy group, and a carboxyl group and a phenolic hydroxy group. Monomers having both groups are included. These monomers are not limited to those having one carboxyl group or phenolic hydroxy group, and may have a plurality thereof.

[0024] The above "monomer having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen" includes a monomer having a hydroxy group other than a phenolic hydroxy group, and active hydrogen. A monomer having an amino group, and a monomer having both a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen. These monomers are not limited to those having one hydroxyl group other than a phenolic hydroxy group or one amino group having an active hydrogen, and may have a plurality.

[0025] In the following, the power to give specific examples of the monomer is not limited to these.

[0026] Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N -(Carboxyphenol) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

[0027] Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N (hydroxyphenol) acrylamide, N- (hydroxyphenol) methacrylamide, N- (hydroxyphenol) maleimide and the like. It is done.

[0028] Monomers having a hydroxy group other than a phenolic hydroxy group include, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-ataryl oxy-6-hydroxy norbornene 2, carboxy 6-latatone, 2-hydroxy And ethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy 6-hydroxynorbornene 2 carboxy 6-latathon, and the like.

[0029] Further, examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

[0030] The specific copolymer includes a monomer having a functional group for thermal crosslinking reaction and film curing. It may be a copolymer formed with a monomer other than the monomer having a functional group for the purpose (hereinafter referred to as other monomer) as a structural unit.

[0031] The other monomer specifically includes at least one of a monomer having at least one of a carboxyl group and a phenolic hydroxy group, and a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen. As long as it can be copolymerized with a monomer having one, it is not particularly limited as long as the properties of the component (A) are not impaired.

[0032] Specific examples of other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

[0033] Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenol acrylate, 2, 2,2-trifluoroethyl butyl acrylate, tert butyl acrylate, cyclohexyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2 ethoxyethyl acrylate Tetrahydrofurfuryl acrylate, 3-methoxy butyl acrylate, 2-methyl 2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl 8-tricyclodecyl acrylate and 8 —Vegetable— Examples include 8-tricyclodecyl acrylate.

[0034] Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropylino methacrylate, benzino methacrylate, naphthino methacrylate, antholinole methacrylate, anthryl methyl methacrylate. Rate, phenyl methacrylate, 2, 2, 2-trifluoroethyl methacrylate, tert butyl methacrylate, cyclohexyl methacrylate, isobutyl methacrylate, 2-methoxyethyl methacrylate , Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl 2- -Adamantyl metatalylate, 8-methyl-8 -Tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like. [0035] Examples of the bur compound include methyl butyl ether, benzyl butyl ether, 2-hydroxyethyl butyl ether, vinyl butyl ether, and propyl butyl ether.

[0036] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

[0037] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0038] The method for obtaining the specific copolymer used in the present invention is not particularly limited. For example, the group power of the monomer having at least one of a carboxyl group and a phenolic hydroxy group is selected from at least one monomer selected as appropriate. , At least one monomer appropriately selected from the group of monomers having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen, and optionally a monomer other than the above monomers, and optionally polymerization initiation It can be obtained by subjecting an agent or the like to a polymerization reaction in a solvent at a temperature of 50 to 110 ° C. In that case, the solvent used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include the solvents described in (F) Solvent described later.

[0039] The specific copolymer thus obtained is usually in a solution state in which the specific copolymer is dissolved in a solvent.

[0040] In addition, the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as jetyl ether or water, and the generated precipitate is filtered and washed. The powder of the specific copolymer can be obtained by drying at normal temperature or heat under pressure or reduced pressure. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification is not possible with a single operation, the obtained powder may be redissolved in a solvent and the above operation repeated.

In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (F) described later and used as a solution.

[0042] <(B) component> Component (B) is an alkali-soluble rosin having an aromatic ring or alicyclic structure in the main chain. The aromatic ring here is a cyclic hydrocarbon such as benzene, naphthalene, and anthracene, and the alicyclic ring is a cyclic hydrocarbon such as cyclobutane, cyclopentane, cyclohexane, and tricyclodecane.

[0043] Examples of the alkali-soluble resin having such a ring structure include polyimide precursors, alkali-soluble polyimides, phenol novolac resins, cresol novolac resins, naphthol novolac resins and the like. Among these resins, polyimide precursors and alkali-soluble polyimides are preferable because they can maintain high transparency.

[0044] In addition, the alkali-soluble coagulum of the component (B) preferably has a number average molecular weight in the range of 2,000 to 30,000, more preferably <2,000 to 15, It is in the range of 000. If the number average molecular weight is over 30,000, development residues are likely to occur and the sensitivity is significantly reduced.On the other hand, if the number average molecular weight is less than 2,000 and the number is too low, In this case, a considerable amount of film loss occurs in the unexposed area, which may result in insufficient curing.

[0045] Further, the alkali-soluble resin of component (B) is an alkali-soluble resin having an alkyl group substituted with a fluorine atom, preferably a polyimide precursor having an alkyl group substituted with a fluorine atom. It is desirable. At this time, if the polyimide precursor having an aromatic ring has a fluorine-substituted alkyl group, the transparency is further improved compared to the polyimide precursor having no fluorine-substituted alkyl group. Preference is given to having an alkyl group substituted with a fluorine atom, in particular having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, most preferably 1 to 5 carbon atoms.

[0046] The alkali-soluble coagulum of component (B) used in this manner is used in a proportion of 0.5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer of component (A). The ratio of use can be arbitrarily selected according to the fat used.

[0047] <Polyimide precursor>

The polyimide precursor contained in the positive photosensitive resin of the present invention as the alkali-soluble resin (B) is a polyamic acid, a polyamic acid ester, a partially imidized polyamic acid, and is generally (a) tetracarboxylic dianhydride compound and (b) diamine compound Can be built.

[0048] The (a) tetracarboxylic dianhydride compound used in the production of the polyimide precursor used in the present invention is not particularly limited, and these may be used alone or in combination of two or more. Can be used. Specific examples include pyromellitic dianhydride, 3, 3 ', 4, 4, biphenyl tetracarboxylic dianhydride, 3, 3', 4, 4, monobenzophenone tetracarboxylic dianhydride 3, 3 ', 4, 4'-diphenyl ether tetracarboxylic dianhydride, 3, 3', 4, 4'-diphenyl sulfone tetracarboxylic dianhydride, etc. , 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2 dimethyl-1, 2, 3, 4 cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl— 1, 2, 3 , 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4 cyclopentanetetraforce rubonic acid dianhydride, 1, 2, 3, 4-cyclohexanetetracarboxylic dianhydride, 3, 4-di Carboxy 1, 2, 3, 4-tetrahydro 1 Alicyclic tetracarboxylic dianhydride, such as naphthalene succinic dianhydride 1 , 2, 3, 4 Aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride.

[0049] The (b) diamine compound used for the production of the polyimide precursor used in the present invention is not particularly limited, and these may be used alone or in combination of two or more. be able to. Specific examples include 2,4 diaminobenzoic acid, 2,5 diaminobenzoic acid, 3,5 diaminobenzoic acid, 4,6 diamino-1,3 benzenedicarboxylic acid, 2,5 diamino-1,4 benzenedicarboxylic acid, bis (4 amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino) 3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3, -dicarboxybiphenyl, 4,4'-diamino-3,3, -dicarboxy-5,5'-dimethylbiphenyl, 4, 4 '-Diamino-3,3'-dicarboxyl 5,5,1-dimethoxybiphenyl, 1,4 bis (4 amino-3-carboxyphenoxy) benzene, 1,3 bis (4 amino-3-carboxyphenoxy) B) Benzene, Bis [4— (4 — Ami No 3—Carboxyphenoxy) phenol] sulfone, bis [4— (4-Amino-3—force Ruboxyphenoxy) phenol] propane, 2, 2 bis [4— (4 Amino-3-carboxy Phenoxy) phenol] hexafluoropropane, 2,4 diaminophenol, 3,5 di Aminophenol, 2,5 Diaminophenol, 4,6 Diaminole: / Noresinole, 2,5 Diaminohydroquinone, Bis (3-amino-4-hydroxyphenol) ether, Bis (4-amino) 3-hydroxyphenyl ether, bis (4-amino-3,5-dihydroxyphenol) ether, bis (3-amino-4-hydroxyphenol) methane, bis (4-amino-3-hydroxyphenyl) ) Methane, bis (4-amino-1,3,5-dihydroxyphenol) methane, bis (3-amino-4-hydroxyphenol) sulfone, bis (4-amino-3-hydroxyphenol) sulfone, bis (4 amino-3,5 dihydroxyphenyl) sulfone, 2,2 bis (3 amino 4-hydroxyphenyl) hexafluoropropane, 2,2 bis (4 amino-3 hydroxyphenyl) hexafluoro propane 2, 2 bis (4 amino-3,5 dihydroxyphenyl) hexafluoropropane, 4,4, diamino-3,3, dihydroxybiphenyl 4,4,1-diamino-1,3'-dihydroxy-5 , 5,1-dimethylbiphenyl, 4,4'-diamino-1,3,3'-dihydroxy-1,5,5,1-dimethoxybiphenyl, 1,4 bis (3 amino-4-hydroxyphenoxy) benzene, 1 , 3 bis (3 amino-4 hydroxyphenoxy) benzene, 1, 4 bis (4 amino-3 hydroxyphenoxy) benzene, 1, 3 bis (4 —amino-3-hydroxyphenoxy) benzene, bis [4— (3-Amino-4-hydroxyphenoxy) phenol] sulfone, bis [4- (3-Amino-4-hydroxyphenoxy) phenol] propane, 2,2bis [4 -— (3 Amino-4-hydroxyphene) Enoxy) Fuel] Hexafluoro Diamine compounds with isophenolic hydroxy groups of propane, 1,3 diamine 4-mercaptobenzene, 1,3 diamine 5-mercaptobenzene, 1,4 diamine —2-mercaptobenzene, bis (4 amino-3-mercapto Phenyl) ether, 2, 2 bis (3-amino-4-mercaptophenol) hexafluoropropane and other diamine compounds having a thiophenol group, 1, 3 diaminobenzene-4-sulfonic acid, 1, 3 Diaminobenzene 5-snorephonic acid, 1,4-diaminobenzene 2-snolephonic acid, bis (4-aminobenzene-1,3-sulfonic acid) ether, 4, 4, monodiaminobiphenyl) 3, 3, monodisulfonic acid 4,4, -diamino-3,3, -dimethylbiphenyl 6,6, -diamine compounds having a sulfonic acid group such as disulfonic acid. P-Phenylenediamine, m-Phenylenediamine, 4,4'-methylenebis (2,6 ethylaniline), 4,4'-methylenbis (2-isopropylidenoyl 6-methylenorea-phosphorus), 4, 4, One methylene one screw (2, 6 —Diisopropyl-line), 2, 4, 6 trimethyl-1,3,3-dienediamine, 2, 3, 5,6—tetramethyl-1,4-diylenediamine, o-tridine, m-tolidine, 3, 3 ' , 5, 5, 1-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenol] sulfone, 2,2-bis [4- (3-aminophenoxy) phenol] propane, 2,2-bis [4— (3aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-1,3'-dimethyldioxyhexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl Ether, 4, 4'-diaminodiphenylmethane, 2, 2 bis (4 lino) hexafluoropropane, 2, 2 bis (3 lino) hexafluoropropane, 2, 2 bis (3 Amino —4 toluyl) hexafluoropropane, 1, 4 bis (4 aminophenoxy) ) Benzene, 1,3 bis (4-aminophenoxy) benzene, bis [4 (4-aminophenoxy) phenol] sulfone, 2,2 bis [4- (4 aminophenoxy) phenol] propane, 2, 2 bis A diamine compound such as [4-((4 aminophenoxy) phenol] hexafluoropropane can be mentioned.

[0050] Among the compounds listed as examples of the (b) diamine compound, 2, 2 bis [4 (4-amino-3-carboxyphenoxy) phenol] hexafluoropropane, 2,2bis (3 amino-4hydroxyphenol) hexafluoropropane, 2,2bis (4 amino-3hydroxyphenol) hexafluoropropane, 2,2bis (4 amino-3,5) Dihydroxyphenyl) hexafluoropropane, 2,2bis [4- (3-amino-4-hydroxyphenoxy) phenol] hexafluoropropane, 2,2bis (3 amino-4-mercaptophenol) Hexafluoropropane, 2,2bis [4- (3-aminophenoxy) phenol] hexafluoropropane, 4,4'-diaminodiphenylmethane, 2,2bis (4-amino) ) Hexafluoropropane, 2, 2 bis (3-amino) hexafluoropro Alkyl substituted with fluorine atoms such as bread, 2,2bis (3 amino-4toyl) hexafluoropropane, 2,2bis [4- (4-aminophenoxy) phenol] hexafluoropropane A polyimide precursor having an alkyl group substituted with a fluorine atom can be produced from a diamine compound having a ru group and the (a) tetracarboxylic dianhydride compound.

[0051] The polyimide precursor used in the present invention is converted to the above (a) tetracarboxylic dianhydride. Compound and (b) Diamine Compound Strength When manufactured, the compounding ratio of both compounds, i.e. (b) Total moles of diamine compound> / <(a) Total moles of tetracarboxylic dianhydride compound > Is preferably 0.7 to 1.2. Similar to the normal polycondensation reaction, the closer this molar ratio is to 1, the higher the degree of polymerization of the polyimide precursor produced, and the higher the molecular weight.

[0052] Further, when the polymerization is carried out by using the (b) diamine compound in excess, the terminal amino group of the produced polyimide precursor can be reacted with a carboxylic acid anhydride to protect the terminal amino group. .

[0053] Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, anhydrous maleic acid, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene 2, 3 Dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and the like can be mentioned.

[0054] During the production of the polyimide precursor, the reaction temperature of the reaction between the (a) tetracarboxylic dianhydride compound and the (b) diamine compound is -20 to 150 ° C, preferably — Any temperature from 5 ° to 100 ° C can be selected. A high molecular weight polyimide precursor can be obtained at a reaction temperature of 5 ° C to 40 ° C and a reaction time of 1 to 48 hours. To obtain a polyimide precursor with low molecular weight and high storage stability, the reaction is carried out at a reaction temperature of 40 ° C to 90 ° C and a reaction time of 10 hours or more.

[0055] In addition, when the terminal amino group is protected with an acid anhydride, the reaction temperature may be 20 to 150 ° C, preferably -5 to 100 ° C.

[0056] The reaction of the (a) tetracarboxylic dianhydride compound and the (b) diamine compound can be carried out in a solvent. Solvents that can be used in this case include N, N-dimethylformamide, N, N dimethylacetamide, N-methylpyrrolidone, N burpyrrolidone, N-methylcaprolatatam, dimethyl sulfoxide, tetramethylurea, pyridine , Dimethyl sulfone, hexamethyl sulfoxide, m cresol, y butyrolatatone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, 2-methoxypropionic acid Ethyl, 3 ethoxycyclopropionate, 2-ethoxypropionate, ethylene glycol dimethylenoate, diethylene glycol dimethyl ether, diethylene glycol decyl Ether, Diethylene glycol methyl ethyl ether, Propylene glycol dimethyl alcohol, Dipropylene glycol dimethyl ether, Ethylene glycol alcohol monomethyl alcohol, Ethylene glycol alcohol monomer alcohol, Diethylene glycol alcohol monomer alcohol, Diethylene glycol alcohol monomer Tenoré, Propylene Glycole Monomethinoleateoret, Propylene Glyconole Monoethylenoleetenole, Dipropylene Glyconore Monomethenore Ether, Dipropylene Glyconore Monomethinoreether, Propylene Glyconore Monoethyl Etherate, Carbitol Acetate, Ethyl acetate sorb acetate

, Cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and the like. These may be used alone or in combination. Furthermore, even if it is a solvent without dissolving the polyimide precursor, the polyimide precursor produced by the polymerization reaction may not be precipitated.

[0057] The solution containing the polyimide precursor thus obtained can be used as it is for the preparation of a positive photosensitive resin. In addition, the polyimide precursor can be recovered by precipitation by isolation in a poor solvent such as water, methanol, ethanol or the like.

[0058] The polyimide precursor is used in a proportion of 5 to 100 parts by weight, preferably 10 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble acrylic polymer of component (A). If the amount of the polyimide precursor used is too small below the lower limit of the above range, cracks may occur during ITO sputtering. On the other hand, if the amount of the polyimide precursor used exceeds the upper limit of the above range, the transparency after curing decreases.

[0059] <Polyimide>

Further, as the alkali-soluble resin (B) used in the positive photosensitive resin of the present invention, any polyimide can be used. The polyimide used in the present invention is obtained by imidizing 50% or more of the polyimide precursor described above chemically or thermally. These polyimides include copolymers such as polyamideimide and polyetherimide. Preferably, a polyimide having an alkyl group substituted with a fluorine atom, particularly from the viewpoint of improving solubility, 1 to 10 carbon atoms substituted with a fluorine atom, preferably 1 to 7 carbon atoms, most preferably U, which is preferably a polyimide having an alkyl group of 1 to 5 carbon atoms. The polyimide used in the positive photosensitive resin composition of the present invention gives alkali solubility. Therefore, it is preferable to have a carboxyl group or a phenolic hydroxy group, or a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or an acid. The method for introducing a carboxyl group or a phenolic hydroxy group is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing an amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method of making the imidity ratio 99% or less when imidizing the polyimide precursor is used. The method of introducing a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or an acid uses a monomer that generates a carboxyl group or a phenolic hydroxy group by the action of heat or an acid. Alternatively, there is a method in which a phenolic hydroxy group or a carboxylic acid residue after imidation is reacted with a group that is dissociated by the action of heat or acid. Such a polyimide can be obtained by synthesizing the above polyimide precursor and then performing chemical imidization or thermal imidization.

[0060] The alkali-soluble polyimide is used in a proportion of 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, per 100 parts by mass of the alkali-soluble acrylic polymer of component (A). If the amount of the alkali-soluble polyimide used is too small below the lower limit of the above range, cracks may occur during ITO sputtering. On the other hand, if the amount of the alkali-soluble polyimide used exceeds the upper limit of the above range, the transparency after curing is lowered.

[0061] <Component (C)>

Component (C) is a compound having two or more butyl ether groups in one molecule. This may be any compound having at least two vinyl ether groups per molecule that can be thermally crosslinked with the alkali-soluble acrylic polymer of component (A) at a conventional prebeta temperature. It ’s not particularly limited.

[0062] The compound of component (C) is formed by the acid generated by exposure in the presence of a photoacid generator after thermal crosslinking with the alkali-soluble acrylic polymer of component (A). It is separated (decrosslinked) from the alkali-soluble acrylic polymer, and then the alkali-soluble acrylic polymer of component (A) is removed by development using an alkali developer. Therefore, this type of compound is commonly used as a component of bull ether used as a component of a bull ether type chemically amplified resist. A tellurium compound or the like can be applied. The use of such a compound has the advantage that the shape of the formed film can be controlled by adjusting the thermal crosslinking density by changing the compounding amount of the compound.

[0063] As the compound of the component (C), among the above vinyl ether compounds, the compound force represented by the formula (1) and the formula (2) is developed especially in the exposed part! This is preferable.

[0064] [Chemical 1]

[Wherein, n is an integer of 2 to 10, k is an integer of 1 to 10, and R ¹ represents an n-valent organic group.

[0066] [Chemical 2]

[0067] (wherein m represents an integer of 2 to 10)

[0068] In formula (1), n is more preferably an integer of 2 to 4 as the force n representing the number of butyl ether groups in one molecule. And m in the formula (2) also represents the number of vinyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.

[0069] Specific examples of the compounds represented by the formulas (1) and (2) include bis (4- (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipine Acid dibule ester, diethylene glycol dibule ether, tris (4-bi-loxy) butyl trimellrate, bis (4- (bi-n-oxy) butyl) terephthalate, bis (4 (bi-n-oxy) butyl isophthalate, And cyclohexane dimethanol dibi- And ruether.

[0070] Further, the compound of component (C) is used in a ratio of 1 to 80 parts by weight, preferably 5 to 40 parts by weight, with respect to 100 parts by weight of the total of components (A) and (B). The When the amount of the component (C) compound used is an excessive amount less than the lower limit of the above range, the reduction of the film in the unexposed area becomes remarkable and the pattern-like relief shape becomes poor. On the other hand, if the amount of the component (C) compound used exceeds the upper limit of the above range, the sensitivity of the film is remarkably reduced, and residues between patterns are generated after development.

[0071] <(D) component>

Component (D) is a compound having two or more block isocyanate groups in one molecule. This is because, for example, a conventional post-beta is used for a film which also has an alkali-soluble acrylic polymer strength of (A) component which has been thermally cross-linked with (C) component compound or further de-crosslinked with it. As long as it is a compound having two or more block isocyanate groups in one molecule that can be thermally cured at a temperature, the type and structure are not particularly limited.

[0072] The compound of component (D) has two or more blocked isocyanate groups in which one or more isocyanate groups (-NCO) are blocked by an appropriate protecting group, and is heated at a high temperature during thermal curing. Exposure to the functional group for thermosetting in the alkali-soluble acrylic polymer of component (A) (for example, phenolic properties) Crosslinking reaction proceeds between each other (hydroxy group other than hydroxy group and amino group having active hydrogen).

[0073] [Chemical Formula 3] Equation (3)

[0074] (In the formula, R ² represents an organic group in the block part) Two or more groups in one molecule (this group may be the same or different! /) Well, there are compounds that have).

[0075] The compound of component (D) having two or more blocked isocyanate groups in one molecule is, for example, a suitable blocking agent for a compound having two or more isocyanate groups in one molecule. It can be obtained from the action.

[0076] Examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethylhexamethyate. Examples thereof include diisocyanate and the like, or dimers, trimers thereof, or a reaction product of these with diols, triols, diamines, and triamines.

[0077] Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol. , Phenol, o--trophenol, p-chlorophenol, m- or p-taresol and other phenols, ε-force prolatata and other ratatams, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, Examples include oximes such as cyclohexanone oxime, acetophenone oxime, benzophenone oxime, pyrazoles such as pyrazole, 3,5-dimethylbiazole, and 3-methylpyrazole, and thiols such as dodecanethiol and benzenethiol. .

[0078] The compound of component (D) is such that at higher temperatures such as the post-beta temperature, the block portion undergoes thermal desorption and the crosslinking reaction proceeds via the isocyanate group. In order to prevent crosslinking by isocyanate groups from proceeding at lower temperatures, the component (D) has a temperature at which the thermal dissociation of the block portion is considerably higher than the pre-beta temperature, for example, 120 ° C to 230 ° C. Particularly preferred as the compound.

[0079] Examples of the compound of the component (D) include the following specific examples.

[0080] [Chemical 4]

[0081] In the formula, isocyanate compound strength is derived from S isophorone diisocyanate

Examples of such a compound in which the compound of component (D) is more preferable than the point of heat resistance and coating properties include the following.

R in the following formula represents an organic group.

[0082] [Chemical 5]

§§

[Lake 0]

£ 06190 / LOOZdT / lDd zz

In the present invention, the compound of component (D) may be used alone or in combination of two or more. [0086] The compound of component (D) is used in a ratio of 1 to 80 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total of component (A) and component (B). The If the amount of the component (D) compound is too small below the lower limit of the above range, the thermosetting is insufficient and a satisfactory cured film cannot be obtained, while the amount of the component (D) compound used. If the amount exceeds the upper limit of the above range, the development is insufficient and a development residue is generated.

[0087] <(E) component>

The component (E) is a photoacid generator (PAG). This is a substance that generates acids (sulfonic acids, carboxylic acids, etc.) directly or indirectly by irradiation of light used for exposure. If it has such properties, its type and The structure and the like are not particularly limited, but those that generate sulfonic acid upon irradiation with light are particularly preferable.

[0088] Photoacid generators for component (E) include, for example, diazomethane compounds, form salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin. Examples include tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without particular limitation. In the present invention, the photoacid generator of component (E) may be used alone or in combination of two or more.

[0089] Specific examples of the photoacid generator include

[0090] [Chemical 8]

Equation (4) Equation (5) Equation (6) Equation (7) Equation (8)

Jihue-noredo-um chloride, jihue-nyoru-trimu-noroforolomethane sulphonate, ji-hue-nyoru-doum mesylate, jihue-nyoru-do-mutosylate, jihue-nyoru-do-mu-bum-mido Dounium tetrafunoleroborate, diphenylodo-umhexafluoroantimonate, diphenyl-hexafluoroarsenate, bis (p-tert-butynolefenore) Phosphate, bis (p-tert-butylphenol) iodine mesylate, bis (p-tert-butylphenol) odomumutosylate, bis (p-tert-butylphenol) jordoni Umtrifluoromethane sulfonate, bis (p-tert-butylphenol) odonitrium tetrafluorobore Bis (p-tert-butylphenol) tert-butyl chloride, bis (p-clonal phthalate), uni-denum chloride, bis (p-clonal phthalate) jorden tetrafluoroborate, trifノ -Nolesnoureumum chloride, Trifé-Noresnorehonumubu-mido, Trifé-Noresnorehon mutrifluoromethanesulfonate, Tri (p-methoxyphenol) sulfo-mu-tetrafluoroborate, Tri (p-methoxyphenol) sulfo-sulfur Muhexafluorophosphonate, tri (p ethoxyphenol) snorephonium tetrafluororeborate, triphenol-phosphoro-mum chloride, triphenyl phospho-mum bromide, tri (p-methoxyphenol) phospho-m-tetrafluoro norborate , Tri (p-methoxyphenol) phospho-hexahexenoreophos Sulfonate, tri (p Etokishifue - Le) phospho - © beam tetrafluoropropoxy O robo rate,

[Chemical 9]

[0093] [Chemical 10]

[0095] [Chemical 12]

[0096] [Chemical 13]

[0097] [Chemical 14]

16])

[0100] The photoacid generator of component (E) is 0.5 to 80 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of components (A) and (B). Used in proportions. When the amount of the photoacid generator used as the component (E) is less than the lower limit of the above range, the alkali-soluble acrylic as the component (A) of the component (C) that has been thermally crosslinked at the time of exposure is used. The dissociation from the polymer does not proceed sufficiently, making it difficult to obtain a desired pattern-like relief, while the amount of the photoacid generator used as the component (E) is excessive in excess of the upper limit of the above range. Thus, the storage stability of the positive photosensitive resin composition becomes inferior.

[0101] Ku (F) Solvent>

The (F) solvent used in the present invention dissolves the (A) component to the (E) component and dissolves the (G) component and the Z or (H) component, which will be added later if desired. The type and structure of the solvent are not particularly limited as long as it has such a solubility.

[0102] Such (F) solvents include, for example, ethylene glycol monomethyl ether, ethylenic glycolenomonotinoreethenore, methinoreserosonolebacetate, ethinorecerosonolevacetate, diethyleneglycolenomonomono Methylenol ether, diethyleneglycolenomonoethylenate ether, propylene glycol, propyleneglycololemonomethinoleether, propyleneglycololemonomethinoatenoacetate, propyleneglycololepropenoatenoate acetate, toluene, xylene, methyl ether Tyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolatatone, 2-hydroxyethyl ethionate, 2-hydroxyethyl 2-methylpropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, acetic acid Ethyl, butyl acetate, ethyl lactate, butyl lactate, Ν, ジメチル dimethylformamide, Ν, ジメチル dimethylacetamide, Ν-methylpyrrolidone and the like.

These solvents can be used singly or in combination of two or more.

[0103] Among these (F) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl acetate, butyl lactate, etc. Strength It is preferable from the viewpoint of good coating properties and high safety. These solvents are generally used as solvents for photoresist materials.

[0104] Ku (G) component>

Component (G) is an amine compound. The positive photosensitive resin composition of the present invention may further contain an amine compound for the purpose of enhancing the storage stability, as long as the effects of the present invention are not impaired.

[0105] The amine compound of component (G) is not particularly limited. For example, triethanolamine, tributanolamine, triisopropanolamine, trimethylamine, triethylamine, trinormalpropylamine, triamine. Tertiary amines such as isopropylamine, tri-normal butylamine, tri-tert-butylamine, trioctylamine, triphenylamine and diazabicyclooctane, and aromatics such as pyridine and 4-dimethylaminopyridine In addition, primary amines such as benzylamine and normal butylamine, and secondary amines such as jetamine and dinormalbutylamine are also included.

[0106] The amine compound of component (G) can be used singly or in combination of two or more.

[0107] When the amine compound is used, the content thereof is, for example, 0.001 to 5 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). 005 to 1 part by mass, and preferably 0.01 to 0.5 part by mass. If the amount of the amine compound of component (G) is too small below the lower limit of the above range, the storage stability of the positive photosensitive resin composition cannot be sufficiently improved, while (G ) If the amount of the amine compound used as the component exceeds the upper limit of the above range, the sensitivity of the positive photosensitive resin composition may decrease.

[0108] <(H) component>

Component (H) is a surfactant. The positive photosensitive resin composition of the present invention may further contain a surfactant for the purpose of improving the coating properties as long as the effects of the present invention are not impaired.

[0109] The surfactant of the component (H) is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, and non-ionic surfactants. This kind of world As the surfactant, for example, commercially available products such as those manufactured by Sumitomo 3EM Co., Ltd., Dainippon Ink & Chemicals, Inc., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they are readily available. Specific examples include F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFuck F171, F173 (manufactured by Dainippon Ink & Chemicals), Florard FC430, FC431 (Sumitomo 3EM) ), Asahi Guard A G710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SCIO 6 (manufactured by Asahi Glass Co., Ltd.) and the like.

[0110] The surfactant of component (H) can be used singly or in combination of two or more.

[0111] When a surfactant is used, its content is usually 0.2% by mass or less, preferably 0.1% by mass or less in 100% by mass of the positive photosensitive resin composition. is there. Even if the amount of the component (H) surfactant used is set to an amount exceeding 0.2% by mass, the effect of improving the coating property will be dull and not economical.

[0112] <Other additives>

Furthermore, the positive photosensitive resin composition of the present invention can be used, if necessary, as long as the effects of the present invention are not impaired. Adhesion aids such as rheology modifiers and silane coupling agents, facial materials, and dyes. In addition, a storage stabilizer, an antifoaming agent, or a solubility promoter such as a polyhydric phenol or a polycarboxylic acid can be contained.

[0113] <Positive photosensitive resin composition>

The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble acrylic polymer, (B) an alkali-soluble resin, (C) a compound having a vinyl ether group, (D) A compound having a block isocyanate group, (E) a photoacid generator and (F) a solvent, and optionally, an (A) amine compound and an (H) surfactant In addition, the composition may further contain one or more of other additives.

[0114] Among them, preferred examples of the positive photosensitive resin composition of the present invention are as follows.

[1]: Based on 100 parts by mass of component (A) 0.5 to 100 parts by mass of component (B), (A) and component (B) based on 100 parts by mass of 1 to 80 parts by mass (C) component, 1 to 80 quality A positive photosensitive resin composition containing an amount of (D) component and 0.5 to 80 parts by mass of (E) component, wherein these components are dissolved in (F) solvent.

[2]: The composition of [1] above further comprises 0.001 to 5 parts by mass of component (G) based on a total of 100 parts by mass of component (A) and component (B). Positive photosensitive resin composition.

[3]: A positive photosensitive resin composition further comprising 0.2% by mass or less of component (H) in the positive photosensitive resin composition of [1] or [2] above.

[0115] The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. For example, 1 to 80% by mass Also, for example, 5 to 60% by mass, or 10 to 50% by mass. Here, the solid content is obtained by removing (F) the solvent from all the components of the positive photosensitive resin composition.

[0116] The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited. Examples of the preparation method include dissolving the component (A) (alkali-soluble acrylic polymer) in the solvent (F). In this solution, component (B) (alkali-soluble resin), component (C) (compound having a vinyl ether group), component (D) (compound having a block isocyanate group), component (E) ( Photoacid generator) and (H) component (surfactant) are mixed in a prescribed ratio to make a uniform solution, or at an appropriate stage of this preparation method, component (G) (Amin compound) and Z or other additives may be further added and mixed.

[0117] In preparing the positive photosensitive resin composition of the present invention, (F) a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In the same way as above, add (B) component, (C) component, (D) component, etc. to the solution of component), and add (F) additional solvent for the purpose of concentration adjustment. May be. At this time, the solvent (F) used in the process of forming the specific copolymer and the solvent (F) used for concentration adjustment at the time of preparing the positive photosensitive resin composition may be the same. However, it may be different.

[0118] Thus, the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 m.

[0119] The polyimides mentioned as the component (B) of the acrylic polymer as the component (A) of the present invention are conventionally widely used as base polymers in photosensitive resin materials, respectively. Yes. However, when both are in polymer form, there is a problem that the compatibility is poor. For this reason, for example, an acrylic monomer and a polyimide (for example, JP-A-10-55065, JP-A-11-052572 and Patent 3211108). O) or at least one of the monomers must be used in monomeric form, such as talyl monomer and imide monomer.

In addition to the above acrylic polymer (component (A)) and polyimide (component (B)), the positive photosensitive resin composition of the present invention comprises (C) component to (F) solvent. As a result of the inclusion, the above-mentioned compatibility problem, which could not be solved so far, has been solved and a stable system has been obtained, which can be used for the preparation of a cured film thereafter. .

[0120] Coating and cured film>

The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon z-dioxide-silicon-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, or a glass substrate. , Quartz substrate, ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-drying with a hot plate or oven, etc. Thus, a coating film can be formed. Thereafter, the coating film is heated to form a positive photosensitive resin film.

[0121] As the conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C to 160 ° C and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 ° C to 140 ° C and 0.5 to 10 minutes.

[0122] The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 m, and for example, 0.2 to 10 m. For example, te from 0.2 to 5 μm.

[0123] Then, in the formed positive photosensitive resin film, the compound having a butyl ether group as the component (C) bridges the alkali-soluble acrylic polymer as the component (A) by the heat treatment at the time of formation. As a result, the film is hardly soluble in an alkali developer. In this case, when the temperature of the heat treatment is lower than the lower limit of the above temperature range, the thermal crosslinking is insufficient, and film loss may occur in the unexposed area. In addition, the temperature of the heat treatment is above the above temperature range. If it exceeds the limit and is too high, the once formed thermal cross-linked part may be cut again, and the film may be reduced in the unexposed part.

[0124] The positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F laser light using a mask having a predetermined pattern.

2

The exposed portion of the film is soluble in an alkaline developer by the action of the acid generated from the photoacid generator (PAG) of the component (E) contained in the positive photosensitive resin film. It becomes.

[0125] Next, post-exposure heating (PEB) is performed on the positive photosensitive resin film. As heating conditions in this case, a heating temperature and a heating time appropriately selected from the range of a temperature of 80 ° C. to 150 ° C. and a time of 0.3 to 60 minutes are employed.

[0126] Thereafter, development is performed using an alkaline developer. As a result, the exposed portion of the positive photosensitive resin film is removed, and a pattern-like relief is formed.

Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. Examples include alkaline aqueous solutions such as aqueous solutions of quaternary ammonium hydroxides such as urea and choline, and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.

[0128] Among the above, tetraethylammonium hydroxide 0.1 to 2. 38% by mass aqueous solution is generally used as a photoresist developer, and is also used in the photosensitive resin composition of the present invention. By using this alkaline developer, it is possible to develop a good image without causing problems such as swelling.

[0129] Further, as a developing method, a V-deviation, such as a liquid piling method, a dating method, or a rocking dipping method, can also be used. The development time is usually 15 to 180 seconds.

[0130] After development, the positive photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried using compressed air or compressed nitrogen or by spinning. The top moisture is removed and a patterned film is obtained.

[0131] Subsequently, the pattern forming film is subjected to post-beta for thermosetting, and specifically, heated using a hot plate, oven, etc., thereby being heat resistant and transparent. Excellent relief, flatness, low water absorption, chemical resistance, etc., with good relief pattern A film is obtained.

[0132] As a post-beta, in general, a medium force in the range of 140 ° C to 250 ° C is also selected at a heating temperature of 5 to 30 minutes on a hot plate and 3 in an oven. If treated for 0 to 90 minutes, the dredging method is used.

[0133] Thus, with such a post beta, a target cured film having a good pattern shape can be obtained.

[0134] As described above, the positive photosensitive resin composition of the present invention has a sufficiently high sensitivity and a fineness that is virtually absent so that no film loss in the unexposed area is observed during image formation. A coating film having a pattern can be formed.

As described above, the positive photosensitive resin composition of the present invention has a composition containing the above-mentioned (A) component to (F) solvent, and optionally (G) component and Z or (H) component. By obtaining a cured film from the resin composition, a cured film free from damage such as cracks during ITO sputtering is obtained.

[0135] Therefore, the use of various film materials in liquid crystal or organic EL displays such as TFT flat crystal films of TFT type liquid crystal elements where chemical amplification resist has not been applied so far, and microlenses, etc. The effect that it is suitable also for this use is acquired. Example

[0136] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[Abbreviated symbols used in Examples]

The meanings of the abbreviations used in the following examples are as follows.

MAA: Methacrylic acid

MMA: Methyl metatalylate

HEMA: 2 Hydroxyethyl methacrylate

CHMI: N cyclohexylmaleimide

AIBN: Azobisisobutyronitrile

CBDA: cyclobutane tetracarboxylic dianhydride

ABL: 2, 2'-trifluoromethyl-1,4'-diaminobiphenyl NMP: N Methinolepyrrolidone

TA: trimellitic anhydride

6FDA: 4, 4 '(Hexafluoroisopropylidene) diphthalic dianhydride

DDS: 4, 4 '-Diaminodiphenyl sulfone

DBA: 3, 5—Diaminobenzoic acid

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

PAG1: Tinoku 'Specialty' Chemicals Co., Ltd. CGI1397 (trade name) (2-methyl-a [5 [[(propylsulfol) oxy] imino]-2 (5H) -ceridene] benzene acetononitrile )

PVE1: 1,4-cyclohexanedimethanol divinyl ether

NCOl: Degussa AG VESTAGON (registered trademark) B 1065 (trade name)

[Chemical 17]

(In the formula, R represents an organic group.)

NC02: Degussa AG VESTAGON (registered trademark) BF 1540 (trade name)

[Chemical 18]

(In the formula, R represents an organic group.)

R30: Dai Nippon Ink Chemical Co., Ltd. Mega Fuck R—30 (trade name)

GT4: Daicel-Egaku Kogyo Co., Ltd. Eporide GT-401 (trade name) (epoxy butyl butane tetrakisate (3-cyclohexylmethyl) modified ε-force prolatatone) MPTS: γ-methacryloxypropyltri Methoxysilane

Ρ200: manufactured by Toyo Gosei Co., Ltd. Ρ— 200 (trade name) 4, 4, — [1— [4— [1— (4 hydroxyphenyl) 1-methylethyl] phenyl] ethylidene] bisphenol 1 mol Photosensitizer synthesized by the condensation reaction of 1,2 naphthoquinone-2 diazido 5 sulphoyl chloride with 2 moles

Ρ5: Residue Top PSM—4327 manufactured by Gunei Chemical Co., Ltd. (Product name) Funol novolak 榭脂 Ρ6: Marukarinkaichi manufactured by Maruzen Petrochemical Co., Ltd. A copolymer of chill.

[Measurement of number average molecular weight and weight average molecular weight]

The number average molecular weight and weight average molecular weight of the specific copolymer obtained in accordance with the following synthesis example were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF8034) manufactured by JASCO Corporation and the elution solvent tetrahydrofuran was flowed. The measurement was conducted under the condition that elution was carried out in a column (column temperature 40 ° C) at lmlZ minutes. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

[0139] [Production of specific copolymer, polyimide and polyimide precursor]

MAA 15.5 g, CHMI 35.3 g, HEMA 25.5 g, and MMA 23.7 g are used as monomer components constituting the specific copolymer, and AIBN 5 g is used as a radical polymerization initiator, and these are PGMEA 200 g. The solution of component (A) (specific copolymer) that is Mn4, 100, Mw7, 600 (specific copolymer concentration: 27.5% by mass) ) (P1)

[0140] <Synthesis example 2>

CBDA 25. Og, ABL 48. Og in NMP 242.1 23. React with C for 24 hours A polyimide precursor solution was obtained. Add 8.6 g of TA and 34.6 g of NMP to this polyimide precursor solution and react at 23 ° C for 24 hours, so that component (B) (Mamine ends are blocked) of Mn4,000, Mw7, 400 Solution of polyimide precursor) (polyimide precursor concentration: 20.0% by mass). (P2)

[0141] <Synthesis Example 3>

Polyimide precursor solution obtained in Synthesis Example 2 (P2) 250. After diluting Og with N-methylpyrrolidone 250. Og, add 35.8 g of acetic anhydride and 27.6 g of pyridine. Dehydration ring closure reaction was performed for a time. This solution was poured into a 50% aqueous methanol solution and then filtered and dried to obtain component (B) (polyimide) as a powder. The obtained polyimide had an Mn of 4,000, an Mw of 7,400, and an imidi ratio of 78%. (P3)

[0142] <Synthesis Example 4>

6 FDA 17.8g, DDS 4.92g and DBA 3.12g 75 out of PGMEA 145.6. Reaction was carried out with C for 20 hours to obtain a solution of component (B) (polyimide precursor) of Mn4, 200 and Mw8,400. (P4)

[Production of positive photosensitive resin composition]

In accordance with the composition shown in Table 1 below, the solution of component (A) is mixed with the solution of component (B) or component (B) (in the comparative example, does not include component (B)), component (C), (D) Ingredients, (E) and (F) solvents, and (H) are mixed in the prescribed proportions and stirred at room temperature for 3 hours to obtain uniform solutions. A positive photosensitive resin composition was prepared.

[0144] [Table 1]

1]

*? ? And P4 is the solution of component (B)

[0145] <Comparative Example 5>

As an alkali-soluble acrylic polymer, 5.5 g of the specific copolymer solution obtained in Synthesis Example 1 (P1), 1.lg of P200 as 1,2-quinonediazide compound, GT4 as an epoxy crosslinkable compound 1.lg, 30.30g of R30 as a surfactant, 0.25g of MPTS as an adhesion assistant, 25.6g of PGMEA as a solvent, and stirred for 8 hours at room temperature to obtain a positive photosensitive resin composition. It was adjusted.

[0146] For each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 5 thus obtained, sensitivity, film reduction (in the unexposed area), and light transmittance after high-temperature firing (transparency) ), ITO sputtering resistance, MEA resistance and heat resistance were evaluated according to the following procedures.

[0147] Incidentally, when obtaining a cured film with a positive photosensitive resin composition, Comparative Example 5 is subjected to photobleaching after development and before post-beta, while Examples 1 to 10 and Comparative Example 5 For Comparative Examples 1 to 4, post-exposure heating (PEB) is performed after exposure and before development without performing photobleaching. In this respect, the evaluation procedure for both is as follows. It is different.

[0148] [Evaluation of sensitivity]

<Examples 1 to 3, Comparative Examples 1 to 4> After coating the positive photosensitive resin composition on a silicon wafer using a spin coater, pre-beta is applied on a hot plate for 120 seconds at a temperature of 110 ° C. 2.

The coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The coated film Canon KK ultraviolet irradiation apparatus PLA-600FA by light intensity at 365nm was irradiated 5. 5mWZcm ² UV for a predetermined time, next, in post-exposure at 120 seconds on a hot plates on a temperature 110 ° C Heating (PEB) was performed. Thereafter, the film was developed by immersing it in an aqueous solution of 0.4% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, followed by washing with ultrapure water for 20 seconds. Sensitivity was defined as the lowest exposure (mj / cm ² ) at which no undissolved portion remained in the exposed area.

[0149] <Comparative Example 5>

After coating the positive photosensitive resin composition on a silicon wafer using a spin coater, pre-beta is applied on a hot plate for 120 seconds at a temperature of 110 ° C. 2.

The coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The coated film Canon KK ultraviolet irradiation apparatus PLA-600FA light intensity at 365nm by the ultraviolet rays 5. 5mWZcm ² irradiates a predetermined time, then 0.4% by weight of Mizusani匕Tetoramechirua Nmoniumu (hereinafter, TMAH Development was performed by immersing in an aqueous solution for 60 seconds, followed by washing with running ultrapure water for 20 seconds. Sensitivity was defined as the lowest exposure (mj / cm ² ) that left no undissolved residue in the exposed area.

[0150] [Evaluation of film loss]

After coating the positive photosensitive resin composition on a silicon wafer using a spin coater, pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C. to form a coating film having a thickness of 2.5 μηι. This membrane was immersed in a 0.4% by mass aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation is made by FILMETRICS

Measured using F20.

[0151] [Evaluation of ITO sputter resistance]

After coating the positive photosensitive resin composition on a silicon wafer using a spin coater, pre-beta is performed on a hot plate at a temperature of 110 ° C for 120 seconds to obtain a film thickness of 2.5 μm. m coatings were formed. This coating film was heated at 230 ° C for 30 minutes to perform post-beta, and a cured film having a thickness of 1.9 m was formed. This film was subjected to ITO sputtering under the conditions of an ITO film thickness of 5000 A, a sputtering pressure of 0.35 Pa, an Ar flow rate of 74 cm ³ / min, a substrate heating temperature of 200 ° C., and a sputtering time of 37.6 minutes. The surface of the sputtered film was observed with an optical microscope, and the surface was cracked with もの, the one with cracks, and the one with cracks.

[0152] [Evaluation of transparency]

A positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-betaged on a hot plate for 120 seconds at a temperature of 120 ° C to form a coating film with a thickness of 2.5 μm. . This coating film was immersed in a 0.4 TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Subsequently, post-beta was performed by heating at 230 ° C for 30 minutes to form a cured film having a film thickness of 1.9 m. This cured film was measured at a wavelength of 200 to 800 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model number, manufactured by Shimadzu Corporation). Further, this coating film was heated at 250 ° C. for 30 minutes, and then the transmittance was measured. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[0153] <Comparative Example 5>

A positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-betaged on a hot plate for 120 seconds at a temperature of 120 ° C to form a coating film with a thickness of 2.4 μm. . This coating film was immersed in a 0.4 TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. The coated film Canon KK ultraviolet irradiation apparatus PLA-600FA light intensity at by Ri 365nm in the ultraviolet rays 5. 5mWZcm ^² 800mjZcm ² irradiated, post beta by heating 30 minutes at 230 ° C in about And a cured film having a thickness of 1.9 / zm was formed. The cured film was measured at a wavelength of 200 to 800 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model, manufactured by Shimadzu Corporation). Further, the coating film was heated at 250 ° C. for 30 minutes, and the transmittance was measured. The film thickness in this evaluation was measured using F20 manufactured by FILMETRIC S.

[0154] [Evaluation of MEA resistance]

<Examples 1 to 3, Comparative Examples 1 to 4> A positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-betaged on a hot plate for 120 seconds at a temperature of 120 ° C to form a coating film with a thickness of 2.5 μm. . This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, post-baking was performed by heating at a temperature of 230 ° C for 30 minutes to form a cured film having a thickness of 1.9. This coating film was immersed in monoethanolamine heated to a temperature of 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Next, after drying for 10 minutes on a hot plate at a temperature of 180 ° C., the film thickness and transmittance were measured. The film thickness after the boost beta and MEA treatment, the film thickness after the drying and the change in transmittance were marked as ME A resistance ○, and the film thickness decreased as X.

[0155] <Comparative Example 5>

A positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-betaged on a hot plate for 120 seconds at a temperature of 120 ° C to form a coating film with a thickness of 2.5 μm. . This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. The coated film Canon KK ultraviolet irradiation apparatus by PLA-600 FA light intensity at 365 nm 5. the ultraviolet 5mW / cm ^² 800mj / cm ² was irradiated, then heating for 30 minutes at 230 ° C · Post-beta with thickness 1.

A cured film was formed. This coating film was immersed in monoethanolamine heated to a temperature of 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Then, after drying for 10 minutes on a hot plate at a temperature of 180 ° C., the film thickness and the transmittance were measured. The film thickness after post-beta and MEA treatment, the film thickness after drying and the film with no change in transmittance were marked as MEA resistance ○, and those with decreased were marked as X.

[0156] [Evaluation of heat resistance]

In the above [Evaluation of MEA resistance], a cured film having a film thickness of 1.9 / zm was formed in the same manner except that the substrate was changed to a quartz substrate-powered silicon wafer. The cured film was scraped and used as a test to measure DTA-TG. The temperature at which the mass of the sample decreased by 5 mass% was evaluated as a 5% mass decrease temperature.

[0157] [Result of evaluation]

The results of the above evaluation are shown in Table 2 below. [0158] [Table 2]

[Table 2]

* “No membrane reduction” means that there was no film reduction from the measurement results.

[0159] In all of Examples 1 to 3, the sensitivity is high, the film loss in the unexposed area is virtually not observed in the measurement results, the ITO sputtering resistance is high, and the transmittance is high. The resistance to was also high.

[0160] Comparative Examples 1 and 2 had high sensitivity, and the film loss in the unexposed areas was virtually not observed, and cracks were observed during ITO sputtering, which showed high transmittance, MEA resistance and heat resistance. Although Comparative Example 3 had ITO sputtering resistance, it was inferior in transmittance and heat resistance, and the film was reduced after ME A treatment.

In Comparative Example 4, cracks were observed due to ITO sputtering, the transmittance and heat resistance were inferior, and film loss was observed after MEA treatment.

In Comparative Example 5, the film was thin in the unexposed area with low sensitivity, cracks were observed during ITO sputtering, and the transmittance was reduced due to MEA treatment.

Industrial applicability

[0161] The positive photosensitive resin composition according to the present invention forms a hardened film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element. It is suitable as a material, especially for TFT type liquid crystal element interlayer insulating film, color filter protective film, array flat film, uneven film under reflective film of reflective display, organic EL element insulating film, etc. It is also suitable as a material to be formed, and also suitable as various electronic materials such as a microlens material.

Claims

The scope of the claims

[1] A positive photosensitive resin composition containing the following component (A), component (B), component (C), component (D) and solvent (E).

Component (C): Compound having two or more vinyl ether groups in one molecule

(E) component: photoacid generator

(F) Solvent

[2] The positive photosensitive resin composition according to claim 1, wherein the component (B) is an alkali-soluble resin selected from the group consisting of polyimide and a polyimide precursor.

[3] The positive photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin of component (B) has a number average molecular weight of 2,000 to 30,000.

[4] The positive photosensitive resin according to any one of claims 1 to 3, wherein the component (B) is an alkali-soluble resin having an alkyl group substituted with a fluorine atom. Composition.

[5] Component (B) is an alkali-soluble resin containing polyimide, and the polyimide is the component (A) 10

The positive photosensitive resin composition according to any one of claims 1 to 4, which is contained in an amount of 0.5 to 20 parts by mass with respect to 0 part by mass.

[6] The component (B) is an alkali-soluble resin containing a polyimide precursor, and the polyimide precursor is

The positive photosensitive resin composition according to any one of claims 1 to 4, which is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the component (A).

[7] The positive photosensitive resin composition according to any one of [1] to [6], wherein the component (E) is a compound that generates sulfonic acid when irradiated with light.

[8] The positive photosensitive resin composition according to any one of [1] to [7], further containing an amine compound as the component (G).

[9] The positive photosensitive resin composition according to any one of [1] to [8], further comprising a fluorine-based surfactant as the component (H).

[10] A cured film obtained by using the positive photosensitive resin composition according to any one of claims 1 to 9.

[11] An interlayer insulating film comprising the cured film according to [10].

[12] A microlens comprising the cured film according to [10].