JP4924013B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, UV-exposed portions suitable for semiconductor device surface protection films, interlayer insulation films, organic electroluminescence element insulation layers and spacer layers, thin film transistor substrate planarization films, organic transistor insulation layers, etc. The present invention relates to a photosensitive resin composition that dissolves in an aqueous solution.

A positive photosensitive resin precursor containing a polyamic acid ester and / or a polyamic acid polymer, a quinonediazide compound, and a phenolic hydroxyl group-containing thermally crosslinkable compound as a method for increasing the resolution of the positive photosensitive resin composition. A photosensitive polymer composition containing a composition (see, for example, Patent Document 1), a polyimide precursor or polyimide, a compound that generates an acid by light, a compound having a phenolic hydroxyl group, a thermally crosslinkable compound, and a dissolution inhibitor ( For example, Patent Document 2), a polyamic acid ester, a photosensitive resin precursor composition containing two or more photoacid generators and a thermally crosslinkable compound (for example, see Patent Document 3) have been proposed. Although these compositions have the effect of suppressing the shrinkage after thermosetting by the reaction of the crosslinking agent, sufficient chemical resistance could not be obtained. In particular, when the film thickness after thermosetting was 1 μm or less, there was a problem that the fine pattern was deformed during curing, and sufficient resolution could not be obtained.
JP 2002-328472 A (Claims 1 to 7) JP 2001-42527 A (Claims 1 to 12) JP 2005-43883 A (Claims 1 to 5)

  In view of the above problems, an object of the present invention is to provide a positive photosensitive resin composition having excellent post-cure resolution and chemical resistance.

  That is, the present invention is a positive photosensitive resin composition containing (a) an alkali-soluble resin and (b) a quinonediazide compound having an alkoxymethyl group.

  According to the present invention, a positive photosensitive resin composition having high sensitivity, high post-curing resolution, and high chemical resistance can be obtained.

  The positive photosensitive resin composition of the present invention contains (a) an alkali-soluble resin. By containing the alkali-soluble resin, development with an aqueous alkali solution becomes possible. Here, the alkali-soluble resin has an alkali-soluble group in at least the repeating unit of the resin, and exhibits solubility in alkali. Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Solubility in alkali means that a solution of resin dissolved in γ-butyrolactone with a solid content of 39% by weight is applied on a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a thickness of 10 μm ± 0.5 μm. The dissolution rate when formed and immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ± 1 ° C. for 3 minutes is 50 nm / min or more.

  Examples of the alkali-soluble resin include (a-1) a phenol resin, (a-2) a polymer obtained from a radical polymerizable monomer having an alkali-soluble group, (a-3) an alkali-soluble polyimide, and (a-4) an alkali-soluble resin. Examples include, but are not limited to, polybenzoxazole, polyamic acid that is a polyimide precursor, polyamic acid ester, polyhydroxyamide, polyaminoamide that is a polybenzoxazole precursor, and polyamide. Among these alkali-soluble resins, it has excellent heat resistance and exhibits excellent characteristics as a surface protection film for semiconductor elements, an insulating layer for organic electroluminescent elements, and a spacer layer. Therefore, after heat treatment, it is degassed at a high temperature of 200 ° C. or higher. A small amount is preferred. Specifically, a polyimide precursor such as alkali-soluble polyimide, polyhydroxyamide, polyamic acid or polyamic acid ester or a polybenzoxazole precursor is preferable.

  (A-1) As phenol resins, there are novolak phenol resins and resol phenol resins, which are obtained by polycondensation of various phenols alone or a mixture of plural types of phenols with aldehydes such as formalin. .

  Examples of phenols constituting the novolak phenol resin and resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, , 4,5-trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichloro Phenol m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α -Naphthol, beta-naphthol, etc. are mentioned. Two or more of these may be used.

  Examples of aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like. Two or more of these may be used.

  The weight average molecular weight of the phenol resin used in the present invention is preferably 2,000 or more, more preferably 3,000 or more in terms of polystyrene using gel permeation chromatography. Moreover, 50,000 or less is preferable and 30,000 or less is more preferable. When the weight average molecular weight is 2,000 or more, the pattern shape, post-development resolution, and developability become good, and the chemical resistance becomes better. On the other hand, when it is 50,000 or less, developability and sensitivity are improved.

  (A-2) The following monomers are mentioned as a radically polymerizable monomer which comprises the polymer obtained from the radically polymerizable monomer which has an alkali-soluble group. Examples of the radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group include o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, and ester thereof. Carboxy substitution products; polyhydroxyvinylphenols such as vinyl hydroquinone, 5-vinyl pyrogallol, 6-vinyl pyrogallol, 1-vinyl phloroglicinol; o-vinyl benzoic acid, m-vinyl benzoic acid, and p-vinyl benzoic acid As well as their alkyl, alkoxy, halogen, nitro, cyano, amide, ester substituents, methacrylic acid and acrylic acid, and their α-position haloalkyl, alkoxy, halogen, nitro, Substituted substances: divalent unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid and 1,4-cyclohexenedicarboxylic acid, and their methyl, ethyl, And propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, phenyl, o-, m-, p-toluyl half ester and half amide. Two or more of these may be used.

  Among these, o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and alkyl and alkoxy substituted products thereof are sensitive to patterning, resolution after development, residual film ratio after development, heat deformation resistance, It is preferably used from the standpoints of chemical properties, adhesion to the substrate, and storage stability of the solution.

Moreover, the copolymer of the radically polymerizable monomer which has the said alkali-soluble group, and the radically polymerizable monomer which does not have an alkali-soluble group can also be used. Examples of the polymerizable monomer having no alkali-soluble group include styrene and alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, α-position, o-position, m-position, or p-position of styrene, Diesters such as butadiene, isoprene, chloroprene; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, pentyl, neopentyl, isoamyl of methacrylic acid or acrylic acid Hexyl, cyclohexyl, adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenethyl, cresyl, glycidyl, 1,1,1-trifluoroethyl, perfluoroethyl, per Ruoro -n- propyl, perfluoro -i- propyl, triphenylmethyl, tricyclo [5.2.1.0 ^2,6] decan-8-yl (common name: "dicyclopentenyl"), cumyl, 3 -(N, N-dimethylamino) propyl, 3- (N, N-dimethylamino) ethyl, furyl, furfuryl esters, anilides, amides of methacrylic acid or acrylic acid, or N, N-dimethyl, N, N-diethyl, N, N-dipropyl, N, N-diisopropyl, anthranilamide, acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, acetic acid Vinyl, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, - methacryloyl phthalimide, may be used N- acryloyl phthalimide and the like. Two or more of these may be used.

Of these, styrene, and styrene α-, o-, m-, and p-alkyl, alkoxy, halogen, haloalkyl substituents; butadiene, isoprene; methacrylic acid, or methyl, ethyl of acrylic acid, Each ester of n-propyl, N-butyl, glycidyl and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl has a sensitivity during patterning, a resolution after development, a remaining film ratio after development, It is particularly preferably used from the viewpoints of heat distortion resistance, chemical resistance, adhesion to the substrate, storage stability of the solution, and the like.

  When using a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and a radical polymerizable monomer having no alkali-soluble group as the alkali-soluble resin, the ratio of the radical polymerizable monomer having no alkali-soluble group is determined by radical polymerization. The amount is preferably 30% by weight or less, particularly preferably 5 to 20% by weight, based on the total amount of the polymerizable monomer. In addition, when a copolymer of a radical polymerizable monomer having a carboxyl group and a radical polymerizable monomer having no alkali-soluble group is used as the alkali-soluble resin, the ratio of the radical polymerizable monomer having no alkali-soluble group is the radical Preferably it is 90 weight% or less with respect to the total amount of a polymerizable monomer, Most preferably, it is 10 to 80 weight%. If it is this range, the alkali developability of the photosensitive resin composition obtained will become favorable.

Solvents used when polymerizing radically polymerizable monomers having an alkali-soluble group include, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; propylene glycol monomethyl ether and propylene glycol Ethyl ether, propylene glycol monopropyl ether, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol alkyl ethers such as propylene glycol butyl ether acetate acetates; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol alkyl ether propionates such as propylene glycol butyl ether propionate; toluene, xylene Which aromatic hydrocarbons; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, Ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxy Butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, Butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxypropion Acid butyl, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Examples include esters such as propyl and butyl 3-butoxypropionate. The amount of these solvents used is preferably 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

  Examples of the polymerization initiator used when polymerizing a radical polymerizable monomer having an alkali-soluble group include 2,2′-azobisisobutyronitrile and 2,2′-azobis- (2,4-dimethylvaleronitrile). ), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t Organic peroxides such as -butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  The weight average molecular weight of the polymer obtained from the radically polymerizable monomer having an alkali-soluble group is preferably 2,000 or more, more preferably 3,000 or more, and further preferably 5 in terms of polystyrene using gel permeation chromatography. 30,000 or more, preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less. When the weight average molecular weight is 2,000 or more, the pattern shape, post-development resolution, and developability become good, and the chemical resistance becomes better. On the other hand, if it is 100,000 or less, developability and sensitivity are improved.

  The polymers obtained from these radically polymerizable monomers having an alkali-soluble group may be used alone or in combination of two or more. Alternatively, an alkali-soluble resin may be synthesized by a method of imparting alkali solubility by introducing a protecting group into a carboxyl group or a phenolic hydroxyl group before the polymerization and deprotecting after the polymerization. Further, the transparency and softening point in visible light may be changed by hydrogenation or the like.

  (A-3) The alkali-soluble polyimide can be obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and the like with diamine, a corresponding diisocyanate compound, and trimethylsilylated diamine. At this time, a compound having an alkali-soluble group in part or all of at least one of an acid and an amine is used. Polyimide can be obtained by dehydrating and ring-closing polyamic acid, which is one of polyimide precursors generally obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment such as acid or base.

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Anhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone Tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis ( 2,3-dicarboxyfe E) Methane dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic Aromatic tetracarboxylic dianhydrides such as acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3 , 4-Dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, and An aromatic acid dianhydride such as an acid dianhydride having an alkali-soluble group shown in FIG. These are used alone or in combination of two or more.

In the above formula, R ³⁵ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclopropane or cyclohexane. R ³⁶ and R ³⁷ represent a hydrogen atom, a hydroxyl group or a thiol group.

  Moreover, 1,2,3,4-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-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid Dianhydride, 2, 3 Aliphatic tetracarboxylic dianhydrides such as 4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic dianhydride, 1,2,3,4-butanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides may be used.

  Specific examples of diamines include 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, and 2,6-naphthalenediamine. 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3 ′ -Diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'- Diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or these aromatic rings substituted with alkyl groups or halogen atoms Compounds, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Such diamines having scan (3-amino-4-hydroxyphenyl) hexafluoropropane or alkali-soluble group shown in compounds and the following substituted with an alkyl group or a halogen atom in these aromatic rings. These are used alone or in combination of two or more.

In the above formula, R ³⁵ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclopropane or cyclohexane. R ^{36 to} R ³⁹ represent a hydrogen atom, a hydroxyl group or a thiol group.

  Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Scan (3-amino-4-hydroxyphenyl) hexafluoropropane or diamine shown in compound and the following substituted with an alkyl group or a halogen atom in these aromatic rings are preferred.

In the above formula, R ³⁵ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclopropane or cyclohexane. R ³⁶ and R ³⁷ represent a hydrogen atom, a hydroxyl group or a thiol group.

  (A-4) Alkali-soluble polybenzoxazole contains dicarboxylic acid, corresponding dicarboxylic acid chloride, dicarboxylic acid active ester, etc. with respect to aromatic diamine having bisaminophenol and an alkali-soluble group other than the ortho position of the amino group. It can be obtained by reaction. In general, polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting bisaminophenol with dicarboxylic acid, is dehydrated and closed by heating or chemical treatment with phosphoric anhydride, base, carbodiimide compound, etc. A polybenzoxazole having a soluble group can be obtained.

  Examples of bisaminophenol include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, 2,2-bis (3- Amino-4-hydroxyphenyl) cyclohexane, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene and the like.

  Examples of the aromatic diamine having an alkali-soluble group other than the ortho position of the amino group include 3,5-diaminobenzoic acid, 1,5-diamino-4,8-dihydroxyanthraquinone, 2,4-diamino-6-hydroxypyrimidine, Examples include 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid.

  By adjusting the amount of the alkali-soluble group contained in the (a-3) alkali-soluble polyimide and (a-4) the alkali-soluble polybenzoxazole polymer, the dissolution rate with respect to the aqueous alkali solution changes. A positive photosensitive resin composition having a speed can be obtained. A preferred range is such that the molar content of the alkali-soluble group is 5 mol% to 100 mol% with respect to the sum of the total number of moles of acid dianhydride and the total number of moles of diamine. Polymer polymerization is preferably performed by combining an alkali-soluble group-containing monomer and a monomer that does not contain an alkali-soluble group so that the number of moles of the alkali-soluble group falls within this range.

  The weight average molecular weight of (a-3) alkali-soluble polyimide and (a-4) alkali-soluble polybenzoxazole is preferably 2,000 or more, more preferably 3,000, in terms of polystyrene using gel permeation chromatography. More preferably, it is 5,000 or more, preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 50,000 or less. When the weight average molecular weight is 2,000 or more, the pattern shape, post-development resolution, and developability become good, and the chemical resistance becomes better. On the other hand, if it is 100,000 or less, developability and sensitivity are improved.

  (A-5) A resin having a structural unit represented by the following general formula (2) as a main component can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. It is also a heat resistant resin precursor whose heat resistance and solvent resistance are drastically improved by having an annular structure.

In the general formula (2), R ³¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ³² is a divalent to octavalent organic group having 2 or more carbon atoms, and R ³³ and R ³⁴ may be the same or different. It often represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. p and q are integers of 0 to 4, and r and s are integers of 0 to 2. However, p + q> 0.

  The general formula (2) represents a structural unit of a polyamic acid or a polyamic acid ester having a hydroxyl group, and the solubility in an alkaline aqueous solution is better than that of a polyamic acid or a polyamic acid ester having no hydroxyl group due to the hydroxyl group. become. In particular, from the viewpoint of solubility in an aqueous alkali solution, a phenolic hydroxyl group is more preferable among the hydroxyl groups. In addition, by having a fluorine atom in the structural unit represented by the general formula (2) at 10% by weight or more, when developing with an alkaline aqueous solution, water repellency appears moderately at the interface of the film. Etc. are suppressed. Furthermore, when the fluorine atom content is 20% by weight or less, the solubility in an alkaline aqueous solution is maintained, the organic solvent resistance of a polymer made into a cyclic structure by heat treatment is maintained, and the solubility in fuming nitric acid is maintained. It is preferable for doing. Accordingly, the fluorine atom is preferably contained in an amount of 10% by weight to 20% by weight.

R ³¹ contained in the general formula (2) represents a structural component of an acid and represents a divalent to octavalent organic group having 2 or more carbon atoms. R ³¹ is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms containing an aromatic ring or an aliphatic ring.

The specific acid constituting R ³¹ (OH) _p (COOR ³³ ) _r is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride when p = 0. 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-Dicarboxyphenyl) methane Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2 -Bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3 , 5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) pheny L) Aromatic tetracarboxylic dianhydrides such as hexafluoropropane dianhydride and 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride Or cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride, 5- (2,5- Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylicsan anhydride, and fats such as “TDA100, Rica Resin TMEG” (trade name, manufactured by Shin Nippon Rika Co., Ltd.) Mention may be made of the group tetracarboxylic dianhydrides. Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyfe Nyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (3,4 Dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl)- 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride is preferred. These are used alone or in combination of two or more.

  In the case of p ≧ 1, the following structures are exemplified, but the invention is not limited thereto. These are used alone or in combination of two or more.

R ^{32 in the} general formula (2) represents a divalent to octavalent organic group having 2 or more carbon atoms. R ³² is preferably an organic group having 6 to 30 carbon atoms containing an aromatic ring or an aliphatic ring. What has an aromatic ring is more preferable than the heat resistance of the polymer obtained. Specific examples of the diamine constituting R ³² (OH) _q (COOR ³⁴ ) _s include, when q = 0, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1 , 4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4- Aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis ( -Aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2, 2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3 3'-tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4 Examples include '-diaminobiphenyl, or compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, etc. But it is not limited. These are used alone or in combination of two or more.

  When s ≧ 1, 2,2-bis [4- (amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) having a fluorine atom Phenyl] hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine and “ABCH”, “ABPS” (trade name, Nippon Kayaku Co., Ltd.) )), “BAHF” (trade name, manufactured by JFE Chemical Co., Ltd.) and the like, and the structures shown below are exemplified, but are not limited thereto. These are used alone or in combination of two or more.

R ³³ and R ^{34 in} the general formula (2) represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. From the viewpoint of the stability of the resulting positive photosensitive resin solution, R ³³ and R ³⁴ are preferably hydrocarbon groups, but hydrogen atoms are preferred from the viewpoint of the solubility in an aqueous alkali solution. In the present invention, hydrogen atoms and hydrocarbon groups can be mixed. By adjusting the amounts of hydrogen atoms and hydrocarbon groups of R ³³ and R ^34, the dissolution rate with respect to the alkaline aqueous solution changes, so that a positive photosensitive resin composition having an appropriate dissolution rate is obtained by this adjustment. be able to. A preferred range is that 10 mol% to 90 mol% of R ³³ and R ³⁴ are hydrogen atoms. When the number of carbon atoms in R ³³ and R ³⁴ exceeds 20, the alkali solubility is lowered. From the above, R ³³ and R ³⁴ preferably contain one or more hydrocarbon groups having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  Polyhydroxyamide can also be used in place of polyamic acid as a heat-resistant polymer precursor similar to polyamic acid. Such polyhydroxyamide can be obtained by a condensation reaction of a bisaminophenol compound and a dicarboxylic acid. Specifically, a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid and a bisaminophenol compound is added thereto, or a dicarboxylic acid is added to a solution of a bisaminophenol compound such as pyridine and a tertiary amine. For example, a solution of dichloride is dropped.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ³¹ or R ³² in the general formula (2) within a range that does not decrease the heat resistance. Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  The preferred weight average molecular weight of the resin having the structural unit represented by the general formula (2) as a main component is preferably 2,000 or more, more preferably 3,000 or more, in terms of polystyrene using gel permeation chromatography. More preferably, it is 5,000 or more, preferably 100,000 or less, more preferably 70,000 or less, and further preferably 50,000 or less. When the weight average molecular weight is 2,000 or more, the pattern shape, post-development resolution, and developability become good, and the chemical resistance becomes better. On the other hand, if it is 100,000 or less, developability and sensitivity are improved.

  In the present invention, the alkali-soluble resin may be composed only of the structural unit represented by the general formula (2), or other structure mainly composed of the structural unit represented by the general formula (2). It may be a copolymer or a mixture with the unit. Here, the main component means that the structural unit represented by the general formula (2) is contained in an amount of 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more. . The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polyimide-based and / or polybenzoxazole-based polymers obtained by the final heat treatment.

  Moreover, terminal blocker can be made to react with the terminal of resin which has the structural unit represented by General formula (2) as a main component. As the end-capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used. It is preferable in that the molecular weight can be adjusted to a preferable range by reacting the terminal blocking agent. Moreover, various organic groups can be introduce | transduced as a terminal group by making terminal blocker react. Specifically, a resin having a structure represented by any one of the general formulas (3) to (6) is preferable.

In general formulas (3) to (6), R ³¹ represents a 2 to 8 valent organic group having 2 or more carbon atoms, and R ³² represents a 2 to 8 valent organic group having 2 or more carbon atoms. R ^{40 is, -CR 41 R 42 -, -} CH 2 O- and _-CH 2 SO ₂ - a divalent group from selected. R ⁴¹ and R ⁴² represent a monovalent group selected from a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. Among these, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrogen atom, a methyl group, or a t-butyl group is particularly preferable. n is in the range of 10 to 10,000, and r and s are integers of 0 to 2. m is an integer of 0 to 10, preferably an integer of 0 to 4.

—NH— (R ⁴⁰ ) _m —X in the general formulas (3) and (4) is a component derived from a primary monoamine which is a terminal blocking agent, and —CO in the general formulas (5) and (6) - (R ⁴⁰⁾ m _-Y are acid anhydrides are end capping agent is a component derived from a monocarboxylic acid, monoacid chloride compound or a mono active ester compound.

  Monoamines used for the end-capping agent include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene and 1-hydroxy. -6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino- 2-hydroxynaphthalene, 1-carboxy-8- Minonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy Carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-amino Naphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5 -Aminosalicylic acid, 6-aminosalicylic acid, -Amino-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3 -Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-amino Naphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto 2-aminonaphthalene, 1-amino-7-mercaptona Phthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino 2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphth 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl -3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl -1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-di Ethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, and the like, but not limited thereto.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline and the like are preferable.

  Acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds used as end-capping agents include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic acid Acid anhydrides such as anhydrides, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy 2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl -1-naphthoic acid, 3-e Nyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid Acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl Monocarboxylic acids such as 2-naphthoic acid and 8-ethynyl-2-naphthoic acid, monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3- Hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2, Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as 6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5-norbornene The active ester compound obtained by reaction with -2,3-dicarboximide is mentioned.

  Of these, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl benzoic acid Monocarboxylic acids, and monoacid chloride compounds in which these carboxyl groups are converted to an acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1 , 7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and the like monocarboxylic acid compounds in which only the monocarboxyl group of the dicarboxylic acid is converted to acid chloride, monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5- Active ester compounds obtained by reaction with norbornene-2,3-dicarboximide are preferred.

  The introduction ratio of the monoamine used for the end-capping agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 with respect to the diamine component. -90 mol%. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

The end-capping agent introduced into the resin can be easily detected by the following method. For example, by dissolving the resin introduced with the end-capping agent in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the polymer, this is measured by gas chromatography (GC) or NMR measurement, The end capping agent can be easily detected. In addition, the resin component into which the end-capping agent is introduced can be easily detected directly by pyrolysis gas chromatograph (PGC), infrared spectrum and C ¹³ NMR spectrum measurement.

  The resin having as a main component the structural unit represented by the general formula (2) used in the present invention is synthesized by the following method. In the case of polyamic acid or polyamic acid ester, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then in the presence of an amine and a condensing agent And a method in which a diester is obtained with tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorideed and reacted with an amine.

  Polyhydroxyamide can be obtained by a production method in which a bisaminophenol compound and a dicarboxylic acid are subjected to a condensation reaction. Specifically, a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid and a bisaminophenol compound is added thereto, or a dicarboxylic acid is added to a solution of a bisaminophenol compound such as pyridine and a tertiary amine. There is a method of dropping a solution of dichloride.

  Examples of the reaction solvent used in these known methods include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and γ-butyrolactone.

The positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound having an alkoxymethyl group. (B) By containing a quinonediazide compound having an alkoxymethyl group, compared to the case of using a quinonediazide compound having no alkoxymethyl group and a combination of a quinonediazide compound having no alkoxymethyl group and a thermal crosslinking agent. High sensitivity, high resolution after curing, and high chemical resistance. Since the quinonediazide compound having an alkoxymethyl group has high crosslinking reactivity in firing, the post-development resolution can be maintained without causing a reduction in resolution due to softening of the film during firing. Due to this crosslinking effect, the thermal decomposition of the quinonediazide compound itself is suppressed as compared with the conventional quinonediazide compound, so that deterioration of the cured film due to decomposition can be prevented, and the chemical resistance of the resulting cured film can be improved. When the alkyl group is not attached, that is, in the case of a methylol group, the standing stability after exposure is impaired, which is not preferable. Quinonediazide compound having an alkoxymethyl group, a phenol compound having an alkoxymethyl group, quinone diazide sulfonyl group in the phenolic hydroxyl group sites are compounds obtainable by esterification, a compound represented by the general formula (1).

In General Formula (1), R ¹ and R ² may be the same or different, and represent CH ₂ OR ³⁰ (R ³⁰ is an alkyl group having 1 to 6 carbon atoms). R ^{3 to} R ²⁹ represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Cl, Br, I, F, or a fluoro-substituted hydrocarbon group. Q represents a 5-naphthoquinonediazidosulfonyl group, a 4-naphthoquinonediazidesulfonyl group, or a hydrogen atom. However, not all of Q are hydrogen atoms. x represents an integer of 1 to 4, and y represents an integer of 1 to 8.

  In general formula (1), x is preferably 3 or 4. When x is 3 or 4, the quinonediazidosulfonyl group and the unsubstituted phenolic hydroxyl group are likely to coexist in the same molecule, and the number of alkoxymethyl groups is 6 to 8, so that the chemical resistance is further improved. And the photosensitive resin composition with few shrinkage | contraction at the time of baking can be obtained.

  Preferred specific examples of the compound represented by the general formula (1) are shown below.

  (B) The quinonediazide compound having an alkoxymethyl group is a compound in which a sulfonic acid of quinonediazide is ester-bonded to a hydroxyl group of a phenol compound having an alkoxymethyl group. Although all the hydroxyl groups of the phenol compound having an alkoxymethyl group may not be substituted with quinonediazide, it is preferable that 40 mol% or more of the total hydroxyl groups are substituted with quinonediazide. By using the quinonediazide compound substituted by 40 mol% or more, the affinity of the quinonediazide compound with respect to the aqueous alkali solution is lowered, and the solubility of the resin composition in the unexposed area in the aqueous alkaline solution is greatly reduced. Moreover, a quinonediazide sulfonyl group changes to indene carboxylic acid by exposure, and a large dissolution rate with respect to the alkaline aqueous solution of the resin composition in the exposed portion can be obtained. As a result, the dissolution rate ratio between the exposed area and the unexposed area of the photosensitive resin composition is increased, and a pattern with excellent resolution after development can be obtained.

  The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure, and the 5-naphthoquinone diazide sulfonyl ester compound has absorption extended to the g-line region of the mercury lamp. Suitable for exposure. In the present invention, both a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be preferably used, but depending on the wavelength of exposure, 4-naphthoquinone diazide sulfonyl ester, an ester compound, and 5-naphthoquinone diazide sulfonyl ester It is preferred to select a compound. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  In addition, the molecular weight of the (b) quinonediazide compound having an alkoxymethyl group is preferably 300 or more, and more preferably 350 or more, from the viewpoint of the effect of suppressing alkali solubility in the non-exposed area. Further, from the viewpoint of alkali solubility in the exposed area, it is preferably 2,000 or less, and more preferably 1700 or less.

  (B) A quinonediazide compound having an alkoxymethyl group is synthesized from a specific phenol compound by a known method. For example, there is a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a phenol compound having an alkoxymethyl group in the presence of triethylamine. As a method for synthesizing a phenol compound having an alkoxymethyl group, it can be obtained by reacting formaldehyde with a phenol compound and alkoxymethylating the methylol group of the obtained methylolphenol compound. As a synthesis method of a phenol compound, there is a method of reacting an α- (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.

  In the positive photosensitive resin composition of the present invention, the content of the (b) quinonediazide compound having an alkoxymethyl group is preferably 1 part by weight or more, more preferably, 100 parts by weight of the alkali-soluble resin. 3 parts by weight or more, preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

  Moreover, you may contain the compound which has a phenolic hydroxyl group as a solubility regulator in order to supplement the alkali developability of the photosensitive resin composition as needed. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ. Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP -PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26 -OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.). The compound having a phenolic hydroxyl group may be esterified with naphthoquinone diazide. By containing these compounds having a phenolic hydroxyl group, or compounds obtained by esterifying these with naphthoquinone diazide, the resulting resin composition hardly dissolves in an alkali developer before exposure, and easily develops when exposed to alkali. Since it dissolves in the liquid, film loss due to development is small, and development is facilitated in a short time. Therefore, the sensitivity is easily improved.

  The content of such a compound having a phenolic hydroxyl group or a compound obtained by esterifying these with naphthoquinone diazide is preferably 1 part by weight or more, more preferably 3 parts by weight, per 100 parts by weight of the (a) alkali-soluble resin. It is above, Preferably it is 50 weight part or less, More preferably, it is 40 weight part or less.

The positive photosensitive resin composition of the present invention may contain a photoacid generator salt for the purpose of appropriately stabilizing the acid component generated by exposure in the exposed portion. The photoacid generator salt is preferably a sulfonium salt, a phosphonium salt, or a diazonium salt . Since it is necessary to consider the environmental viewpoint and the color tone of the film obtained from the positive photosensitive resin composition, a sulfonium salt is preferably used among them.

  If necessary, for the purpose of improving the wettability between the photosensitive resin composition and the substrate, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl Ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be contained. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  Further, in order to enhance the adhesion to a substrate such as a silicon wafer, the varnish of the photosensitive resin composition contains a silane coupling agent, a titanium chelating agent, etc. Can also be preprocessed.

  When contained in varnish, it is obtained by reacting a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent, an aluminum chelating agent, an aromatic amine compound and an alkoxy group-containing silicon compound. It is preferable to contain 0.5-10 weight% of adhesion improving agents, such as a compound, with respect to the (a) alkali-soluble resin in the varnish.

  When treating the substrate, the adhesion improver described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. in an amount of 0.5-20. It is preferable to surface-treat the solution in which the weight percentage is dissolved by spin coating, dipping, spray coating, steam treatment or the like. In some cases, the reaction between the substrate and the coupling agent may be advanced by applying a temperature from 50 ° C. to 300 ° C. thereafter.

  The positive photosensitive resin composition of the present invention preferably contains a solvent. Solvents are polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl Esters such as acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene, etc. Aromatic hydrocarbons and the like may be used alone, or two or more. The content of the solvent is preferably 50 to 2,000 parts by weight and more preferably 100 to 1,500 parts by weight with respect to 100 parts by weight of the resin of component (a).

  Next, a method for forming a heat-resistant resin pattern using the positive photosensitive resin composition of the present invention will be described.

The photosensitive resin composition of the present invention is applied on a substrate and dried to obtain a photosensitive resin composition film. Examples of the material of the substrate include all materials that can be provided with the electrode metal on the surface, such as metal, glass, semiconductor, metal oxide insulating film, silicon nitride, and polymer film. Preferably glass is used. The material of the glass is not particularly limited, but alkali zinc borosilicate glass, sodium borosilicate glass, soda lime glass, low alkali borosilicate glass, barium borosilicate glass, borosilicate glass, aluminosilicate glass, molten Quartz glass, synthetic quartz glass, and the like are used, and soda-lime glass with a barrier coating such as non-alkali glass or SiO ₂ that usually has few ions eluted from the glass is used. As the material of the polymer film, polyethylene terephthalate, polyethersulfone, and materials having a similar chemical structure can be used. From the viewpoint of maintaining mechanical strength, the thickness is 0.1 mm or more, preferably 0.2 mm or more if the material is inorganic, and 0.05 mm or more, preferably 0.1 mm or more if the material is organic. . The size of the substrate is not particularly limited, but a rectangular or square rectangular substrate having a side of 150 mm or more and a round substrate is generally used having a diameter of 6 inches or more. The coating method includes a slit coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, and the like, and these methods may be used in combination. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying becomes 0.1 to 100 μm. If the material is a polymer film and one side is 300 mm or more and it is difficult to maintain the mechanical strength even if the thickness is adjusted, the polymer film is attached to a glass substrate or the like to maintain the mechanical strength, The coating method can be used.

For drying, a hot plate, oven, infrared ray, vacuum chamber or the like is usually used. When a hot plate is used, the object to be heated is heated by holding it directly on the plate or on a jig such as a proxy pin installed on the plate. As a material of the proxy pin, there is a metal material such as aluminum or stellenless, or a synthetic resin such as polyimide resin or Teflon (registered trademark), and any proxy pin may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, etc. For example, a resin layer coated on a 400 × 500 × 0.7 mm ³ glass substrate is used. When heating, the height of the proxy pin is preferably about 2 to 12 mm. The heating temperature varies depending on the type and purpose of the object to be heated, and it is preferably performed in the range of room temperature to 180 ° C. for 1 minute to several hours.

  Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In order to form a pattern of a heat-resistant resin from the photosensitive resin composition film, after the exposure, development is performed to remove the exposed portion using a developer. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Contains alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of several kinds Good. After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, heat treatment at 130 ° C. to 400 ° C. is performed to convert to a heat resistant resin pattern. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and increasing the temperature stepwise or by selecting a certain temperature range and continuously increasing the temperature. As an example, a method of performing heat treatment at 130 ° C., 150 ° C., 200 ° C., 350 ° C. for 30 minutes or 60 minutes, or raising the temperature linearly from room temperature to 230 ° C. over 1 hour may be mentioned.

  The heat resistant resin pattern formed from the photosensitive resin composition according to the present invention includes a surface protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, an insulating layer or a spacer layer for an organic electroluminescence element, and a flat surface for a thin film transistor substrate. It is suitably used for applications such as chemical film.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples. In addition, evaluation of the photosensitive resin composition in an Example is the following method.

(1) Pattern processability evaluation Production of photosensitive resin film A 6-inch silicon wafer was coated with a photosensitive resin composition (hereinafter referred to as varnish) so that the film thickness after pre-baking was 7 μm and 1.5 μm, Subsequently, a photosensitive resin film was obtained by pre-baking at 120 ° C. for 3 minutes using a hot plate (a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Ltd.).

Film thickness measurement method Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film after pre-baking and development is measured at a refractive index of 1.629, and the cured film is measured at a refractive index of 1.773. did.

Exposure The reticle from which the pattern was cut was set in an exposure machine (i-line stepper DSW-8000 manufactured by GCA), and the photosensitive resin film was exposed to i-line by changing the exposure time at an intensity of 365 nm.

Development Using a developing device of Mark-7 manufactured by Tokyo Electron Ltd., a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed on the exposed film for 10 seconds at 50 revolutions. Then, it was allowed to stand for 60 seconds at 0 rotation, rinsed with water at 400 rotation, and shaken and dried for 10 seconds at 3000 rotation.

Calculation of Sensitivity After exposure and development, an exposure time for forming a 50 μm line and space pattern (1L / 1S) in a one-to-one width (hereinafter referred to as an optimal exposure time) was determined.

Calculation of post-development resolution The minimum pattern size formed in the optimum exposure time was defined as post-development resolution.

Cure Using the inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., the cured photosensitive resin film was heated at 140 ° C. for 30 minutes and then to 350 ° C. in 1 hour under nitrogen flow (oxygen concentration 20 ppm or less). Heated and heat treated at 350 ° C. for 1 hour to produce a cured film (heat resistant resin film). A cured film having a thickness of about 5 μm and a thickness of about 1 μm after curing was obtained from the photosensitive resin films having a thickness of 7 μm and 1.5 μm after pre-baking, respectively.

Calculation of post-cure resolution After baking, the minimum pattern size formed in the optimum exposure time was taken as post-cure resolution.

Calculation of shrinkage rate After producing a cured film, the shrinkage rate was calculated according to the following equation.
Shrinkage rate (%) = (film thickness after pre-baking−film thickness after curing) / film thickness after pre-baking × 100.
(2) Evaluation of chemical resistance A cured film having a post-cure film thickness of about 5 μm and about 1 μm prepared by the above method is immersed in a stripping solution 106 manufactured by Tokyo Ohka Kogyo Co., Ltd. for 10 minutes at 70 ° C. The film thickness before and after was measured, and the amount of film reduction due to the immersion treatment was determined.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride Under a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 34.2 g of allyl glycidyl ether were used. (0.3 mol) was dissolved in 100 g of gamma butyrolactone and cooled to -15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 liter of toluene to obtain a hydroxyl group-containing acid anhydride (a) represented by the following formula.

Synthesis Example 2 Synthesis of Hydroxyl Group-Containing Diamine Compound (b) Under a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 100 ml of acetone and propylene. It was dissolved in 17.4 g (0.3 mol) of oxide and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound (c) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 ml) and propylene oxide (30 g, 0.34 mol) at -15 ° C. Cooled to. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic acid chloride in 60 ml of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

  This precipitate was dissolved in 200 ml of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto for recrystallization to obtain a hydroxyl group-containing diamine compound (c) represented by the following formula.

Synthesis Example 4 Synthesis of quinonediazide compound (d) having an alkoxymethyl group 4,4 ′, 4′-ethylidene tris [2,6-bis (methoxymethyl) phenol] (produced by Honshu Chemical Industry Co., Ltd.) under a dry nitrogen stream 28.5 g (0.05 mol) and 2-naphthoquinone diazide sulfonyl chloride 24.2 g (0.09 mol) were dissolved in 1000 g of acetone and brought to room temperature. To this, 9.1 g of triethylamine mixed with 100 g of acetone was added dropwise so that the temperature inside the system would not exceed 25 ° C. It stirred at 20 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (d) having an alkoxymethyl group represented by the following formula.

Synthesis Example 5 Synthesis of quinonediazide compound (e) having an alkoxymethyl group 4,4 ′-(1-methyl-2-ethylidene) bis (3,5-dimethoxymethylphenol) (Honshu Chemical Industry Co., Ltd.) under a dry nitrogen stream 20.2 g (0.05 mol) and 4-naphthoquinone diazide sulfonyl chloride 21.4 g (0.08 mol) were dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 8.1 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 30 ° C. or higher. It stirred at 30 degreeC after dripping for 1 hour. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (e) having an alkoxymethyl group represented by the following formula.

Synthesis Example 6 Synthesis of quinonediazide compound (f) having an alkoxymethyl group 2,2-bis [4,4-cyclohexylidenebis (4-hydroxy-3,5-dimethoxymethylphenyl)] propane (in a dry nitrogen stream) 18.5 g (0.02 mol) of Honshu Chemical Industry Co., Ltd., 5.4 g (0.02 mol) of 5-naphthoquinone diazide sulfonyl chloride, 10.7 g (0.04 mol) of 4-naphthoquinone diazide sulfonyl chloride ) Was dissolved in 950 g of 1,4-dioxane and brought to room temperature. Here, 6.1 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 45 ° C. or higher. It stirred at 40 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (f) having an alkoxymethyl group represented by the following formula.

Synthesis Example 7 Synthesis of quinonediazide compound (g) having alkoxymethyl group 23.8 g (0. 0) of 4-tert-butyl-2,6-bis-methoxymethylphenol (Honshu Chemical Industry Co., Ltd.) under a dry nitrogen stream. 1 mol) and 1-3.4 g (0.05 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 5.1 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 30 ° C. or higher. It stirred at 30 degreeC after dripping for 1 hour. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (g) having an alkoxymethyl group represented by the following formula.

Synthesis Example 8 Synthesis of quinonediazide compound (h) In a dry nitrogen stream, 16.10 g (0.05 mol) of BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86 g of 5-naphthoquinonediazidesulfonyl acid chloride (0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (h) represented by the following formula.

Synthesis Example 9 Synthesis of quinonediazide compound (i) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40. 28 g (0.10 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (i) represented by the following formula was obtained in the same manner as in Synthesis Example 5 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

Example 1
Under a dry nitrogen stream, 5.01 g (0.025 mol) of 4,4′-diaminophenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to N—. It was dissolved in 50 g of methyl-2-pyrrolidone (NMP). To this, 21.4 g (0.03 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added together with 14 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. . Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dripping, it stirred at 50 degreeC for 3 hours, and obtained the polyamic-acid solution which is (a-5) component.

  Varnish A was obtained by adding 3.2 g of the quinonediazide compound (d) having an alkoxymethyl group obtained in Synthesis Example 4 to 40 g of the obtained polyamic acid solution. Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 2
Under a dry nitrogen stream, 15.1 g (0.02 mol) of the hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 and 0.62 g (0.02 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were obtained. 0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 7.8 g (0.025 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was added thereto and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. 4-Ethynylaniline 0.59g (0.005mol) was added here as terminal blocker, and also it was made to react at 60 degreeC for 2 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polyamic acid as component (a-5).

  10 g of the obtained polyamic acid solid was measured, 4.0 g of the quinonediazide compound (e) having an alkoxymethyl group obtained in Synthesis Example 5 and 0.2 g of vinyltrimethoxysilane were dissolved in 30 g of gamma butyrolactone to obtain varnish B. Obtained. Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 3
Except for changing 4.0 g of the quinonediazide compound (e) having an alkoxymethyl group of Example 2 to 4.0 g of the quinonediazide compound (d) having an alkoxymethyl group obtained in Synthesis Example 4, the same procedure as in Example 2 was performed. Varnish C was obtained. Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 4
Except for changing 4.0 g of the quinonediazide compound (e) having an alkoxymethyl group in Example 2 to 4.0 g of the quinonediazide compound (f) having an alkoxymethyl group obtained in Synthesis Example 6, the same procedure as in Example 2 was performed. Varnish D was obtained. Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 5
Example 2 A varnish was prepared in the same manner as in Example 2 except that 4.0 g of the quinonediazide compound (e) having an alkoxymethyl group was replaced with 4.0 g of the quinonediazide compound (g) having an alkoxymethyl group obtained in Synthesis Example 7. E was obtained. Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 6
Under a dry nitrogen stream, 15.1 g (0.025 mol) of the hydroxyl group-containing diamine compound (b) obtained in Synthesis Example 2, 2 g (0.01 mol) of 4,4′-diaminodiphenyl ether, and 1,3-bis 0.62 g (0.0025 mol) of (3-aminopropyl) tetramethyldisiloxane was dissolved in 100 g of GBL. To this, 16.1 g (0.050 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added together with 33 g of GBL at room temperature, and allowed to react at room temperature for 1 hour and then at 50 ° C. for 4 hours. . To this was added 2.7 g (0.025 mol) of 3-aminophenol as a terminal blocking agent, and the mixture was further reacted at 60 ° C. for 2 hours to obtain a polyamic acid solution as component (a-5).

  To 30 g of the obtained polyamic acid solution, 2.5 g of the quinonediazide compound (f) having an alkoxymethyl group obtained in Synthesis Example 6 and 1 g of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a dissolution regulator. Dissolved to obtain Varnish F. Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 7
In a dry nitrogen stream, 4.13 g (0.016 mol) of diphenyl ether-4,4′-dicarboxylic acid and 4.32 g (0.032 mol) of 1-hydroxy-1,2,3-benzotriazole were reacted. A mixture (0.016 mol) of the obtained dicarboxylic acid derivative and 7.33 g (0.020 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were added to N-methyl- 2-7.0 g of 2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 1.31 g (0.008 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 7 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was put into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum (a-5). The component polyamic acid was obtained.

  10 g of the obtained polyamic acid solid was weighed, and 4 g of the quinonediazide compound (d) having an alkoxymethyl group obtained in Synthesis Example 4 and 0.2 g of vinyltrimethoxysilane were dissolved in 30 g of gamma butyrolactone to obtain varnish G. . Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 8
Under a dry nitrogen stream, 15.1 g (0.02 mol) of the hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 and 0.62 g (0.02 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were obtained. 0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). To this, 7.8 g (0.025 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was added and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. To this was added 0.55 g (0.005 mol) of 3-aminophenol as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 48 hours to obtain polyamic acid as component (a-5).

  10 g of the obtained polyamic acid solid was weighed, 2.3 g of the quinonediazide compound (d) having an alkoxymethyl group obtained in Synthesis Example 4, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a dissolution regulator. ) Varnish H was obtained by dissolving 0.9 g in a mixed solvent of 20 g of gamma butyrolactone and 10 g of ethyl lactate. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 9
In a 0.3 liter flask equipped with a stirrer and a thermometer, 24.82 g (0.08 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 11.86 g of n-butyl alcohol (0.16 mol), 0.4 g (0.004 mol) of triethylamine and 110 g of N-methylpyrrolidone (NMP) were stirred and reacted at room temperature for 8 hours to obtain 3,3 ′, 4,4′-diphenyl ether. An NMP solution (α) of tetracarboxylic acid di-n-butyl ester was obtained. Then, after cooling the flask to 0 ° C., 17.13 g (0.144 mol) of thionyl chloride was added dropwise to react for 1 hour, and di-n-butyl 3,3 ′, 4,4′-diphenyl ether tetracarboxylate. A solution (β) of ester dichloride was obtained. Next, 105 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 26.37 g (0.072 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After adding and dissolving with stirring, 22.78 g (0.288 mol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., di-n-butyl 3,3 ′, 4,4′-diphenyl ether tetracarboxylate After the ester dichloride solution (β) was added dropwise over 20 minutes, the temperature was raised to 30 ° C. and stirring was continued for 1 hour. The solution was poured into 3 liters of water, and the precipitate was collected and washed, and then dried under reduced pressure to obtain polyamic acid as component (a-5).

  10 g of the resulting polyamic acid solid was measured, and 3.2 g of the quinonediazide compound (e) having an alkoxymethyl group obtained in Synthesis Example 5 was dissolved in a mixed solvent of 20 g of gamma butyrolactone and 10 g of ethyl lactate to obtain varnish I. It was. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 10
Under a dry nitrogen stream, 15.1 g (0.025 mol) of the hydroxyl group-containing diamine compound (b) obtained in Synthesis Example 2 was dissolved in 50 g of NMP. 17.5 g (0.025 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 20 hours to obtain polyamic acid as component (a-5).

  10 g of the obtained polyamic acid solid was measured, and 2.8 g of the quinonediazide compound (f) having an alkoxymethyl group obtained in Synthesis Example 6 was dissolved in a mixed solvent of 15 g of gamma butyrolactone, 10 g of ethyl lactate and 5 g of propylene glycol monomethyl ether. And varnish J was obtained. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 11
Metacresol 57 g (0.6 mol), paracresol 38 g (0.4 mol), 37 wt% aqueous formaldehyde solution 75.5 g (formaldehyde 0.93 mol), Shusan dihydrate 0.63 g (0.005 mol) Was dissolved in 264 g of methyl isobutyl ketone, and polycondensation was performed for 4 hours with stirring while the reaction solution was refluxed. Then, the temperature was raised over 3 hours, and then the pressure in the flask was reduced to 4000 to 6666 Pa to remove volatile components, and the molten resin was cooled to room temperature and recovered. This resin was dissolved in ethyl acetate so that the resin component would be 30%, then 1.3 times the amount of methanol and 0.9 times the amount of water were added and left stirring. Subsequently, the lower layer separated into two layers was taken out, concentrated and dried to obtain a novolak resin as component (a-1).

  10 g of the obtained novolak resin solid was measured, and 3.2 g of the quinonediazide compound (d) having an alkoxymethyl group obtained in Synthesis Example 4 was dissolved in a mixed solvent of 15 g of gamma butyrolactone, 10 g of ethyl lactate, and 5 g of propylene glycol monomethyl ether. And varnish K was obtained. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 12
A solution prepared by dissolving 7 g of 2,2′-azobis (2,4-dimethylvaleronitrile) in 200 g of propylene glycol monomethyl ether acetate was charged with 10 g of styrene, 20 g of methacrylic acid, 45 g of glycidyl methacrylate and 25 g of dicyclopentanyl methacrylate. After the replacement, stirring was started gently. The temperature of the solution was maintained for 5 hours to obtain an acrylic resin solution as component (a-2).

  20 g of the obtained acrylic resin solution was weighed, and 3.2 g of the quinonediazide compound (d) having an alkoxymethyl group obtained in Synthesis Example 4 was dissolved to obtain varnish L. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 13
Under a dry nitrogen stream, 29.30 g (0.08 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane 24 g (0.005 mol), 3.27 g (0.03 mol) of 3-aminophenol was dissolved in 80 g of N-methyl-2-pyrrolidone as a terminal blocking agent. To this, 31.2 g (0.1 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. It was. Then, it stirred at 180 degreeC for 5 hours. After completion of stirring, the solution was poured into 3 l of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. When the obtained polymer solid was measured by infrared absorption spectrum, an absorption peak of an imide structure caused by polyimide was detected in the vicinity of 1780 cm ⁻¹ and 1377 cm ⁻¹ to obtain a polyimide which is a component (a-3). It was.

  A varnish M was obtained by measuring 10 g of the obtained polyimide solid and dissolving the quinonediazide compound (d) 3.2 having an alkoxymethyl group obtained in Synthesis Example 4 in a mixed solvent of 15 g of gamma butyrolactone and 15 g of ethyl lactate. . Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Example 14
In a dry nitrogen stream, 14.6 g (0.04 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1.5 g (0.01 mol) of diaminobenzoic acid were added to 50 g of NMP and glycidylmethyl. It was dissolved in 26.4 g (0.3 mol) of ether, and the temperature of the solution was cooled to −15 ° C. A solution prepared by dissolving 14.7 g (0.050 mol) of diphenyl ether dicarboxylic acid dichloride in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyhydroxyamide polymer. Next, 25 g of this polyhydroxyamide polymer was dissolved in 300 g of propylene glycol monomethyl ether acetate, and 14.2 g (0.05 mol) of phosphoric anhydride was added and reacted at 150 ° C. for 8 hours. After filtering the reaction solution, the filtrate was put into 2 L of a mixed solvent of 1: 1 water and methanol, and the precipitate was collected. This precipitate was collected by filtration, washed 3 times with water, and then dried for 24 hours in a vacuum dryer at 80 ° C. to obtain polybenzoxazole as component (a-4).

  10 g of the obtained polybenzoxazole solid was measured, and 3.2 g of the quinonediazide compound (d) having an alkoxymethyl group obtained in Synthesis Example 4 was dissolved in a mixed solvent of 15 g of gamma butyrolactone and 15 g of ethyl lactate to obtain varnish N. Obtained. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Comparative Example 1
To 40 g of the polymer solution obtained in Example 1, 2 g of the quinonediazide compound (h) obtained in Synthesis Example 8 and the thermally crosslinkable compound “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 2 g was added to obtain Varnish O. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Comparative Example 2
10 g of the polyamic acid solid (a-5) obtained in Example 2 was added to 2 g of the quinonediazide compound (i) obtained in Synthesis Example 9 and 4,4 ′, 4′-ethylidene tris as a thermally crosslinkable compound. Varnish P was obtained by adding 2 g of [2,6-bis (methoxymethyl) phenol] (Honshu Chemical Industry Co., Ltd.). Using the obtained varnish, the varnish sensitivity and post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Comparative Example 3
Tris (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazide-5-sulfonyl chloride in a molar ratio of 1/3 were added to 10 g of the polyamic acid solid (a-5) obtained in Example 9. 1.40 g of reacted orthoquinonediazide compound, 1.20 g of 2,2′-methylenebis (4-methylphenol), 0.50 g of dimethylolurea, 0.10 g of diphenyliodonium nitrate, 50% methanol solution of ureapropyltriethoxysilane 0.60 g was stirred and dissolved in 17.78 g of N-methylpyrrolidone to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

Comparative Example 4
To 10 g of the polymer obtained in Example 10, 2 g of the quinonediazide compound (i) obtained in Synthesis Example 9, 0.1 g of WPAG-505 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), thermally crosslinkable compound TMOM- 2 g of BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 1.5 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 0.2 g of m-aminophenyltrimethoxysilane are dissolved in 30 g of gamma butyrolactone. Varnish R was obtained. Using the obtained varnish, the sensitivity of the varnish and the post-development resolution were evaluated as described above. Thereafter, curing was performed to evaluate shrinkage, post-curing resolution, and chemical resistance.

  Table 1 shows the evaluation results of Examples 1 to 14 and Comparative Examples 1 to 4.

Claims (4)

A positive photosensitive resin containing (a) an alkali-soluble resin and (b) a quinonediazide compound having an alkoxymethyl group , wherein (b) the quinonediazide compound having an alkoxymethyl group is represented by the following general formula (1) Composition.

(In the general formula (1), R ¹ and R ² may be the same or different, and represent CH ₂ OR ³⁰ (R ³⁰ is an alkyl group having 1 to 6 carbon atoms). R ^{3 to} R ²⁹ are hydrogen. An atom, a hydrocarbon group having 1 to 20 carbon atoms, Cl, Br, I, F or a fluoro-substituted hydrocarbon group, Q represents a 5-naphthoquinonediazidosulfonyl group, a 4-naphthoquinonediazidesulfonyl group or a hydrogen atom. , Q does not become a hydrogen atom, x is an integer of 1 to 4, and y is an integer of 1 to 8.) (A) an alkali-soluble resin is (a-1) a phenol resin, (a-2) a polymer obtained from a radical polymerizable monomer having an alkali-soluble group, (a-3) an alkali-soluble polyimide, or (a-4) the positive photosensitive resin composition according to claim 1 Symbol placement containing an alkali-soluble polybenzoxazole. (A) an alkali-soluble resin, (a-5) represented by the following general formula (2) containing a structural unit less than 50 mol% represented by claim 1 Symbol placement of the positive photosensitive resin composition.

(In the general formula (2), R ³¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ³² is a divalent to octavalent organic group having 2 or more carbon atoms, and R ³³ and R ³⁴ are the same or different. And represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, p and q are integers of 0 to 4, and r and s are integers of 0 to 2, provided that p + q> 0. It claims 1-3 in any step of applying a positive photosensitive resin composition according to the substrate drying, exposing, method for producing a pattern comprising the steps of process and heat treatment developed using an alkaline developer .