JP6048257B2 - Heat resistant resin and precursor composition thereof - Google Patents

Description

  The present invention relates to a heat resistant resin and a precursor composition thereof. More specifically, a heat-resistant resin suitably used for an insulating film in contact with an electrode and a wiring made of a metal material, for example, a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and a precursor composition thereof About.

  Polyimide resins, polybenzoxazole resins, and polyamideimide resins that are excellent in heat resistance, mechanical properties, and the like are widely used for surface protective films and interlayer insulating films of semiconductor elements of electronic devices. Conventionally, after first forming a coating film in the state of a heat-resistant resin precursor having high solubility in an organic solvent, patterning is performed using a photoresist based on a novolak resin and the precursor is heated and cured. Thus, a method of making an insoluble and infusible heat resistant resin has been taken. In recent years, the photoresist process has been simplified by using negative and positive photosensitive resin compositions that can themselves be patterned.

  When the heat-resistant resin composition is used for applications such as semiconductors, the heat-cured resin remains as a permanent film in the device, so the physical properties of the heat-cured film are very important. In order to ensure reliability in semiconductor packages, adhesion with silicon-based materials formed on the surface of semiconductor chips such as silicon, silicon oxide, silicon nitride, and phosphorous silicate glass is important. When used as an insulating film or the like, in addition to the adhesiveness with the silicon-based material, the adhesiveness with a metal material used for electrodes and wirings is important.

  In general, a heat-resistant resin is said to have a low adhesive strength with a metal material due to its rigid main chain structure, and further constitutes a composition in the case of a cured resin film formed from a resin composition imparted with photosensitivity. Additives such as photosensitizers, sensitizers, acid generators and dissolution regulators remain in the cured film even after heat curing, resulting in lower adhesive strength than those containing no additives. . In order to improve adhesion with silicon-based materials, improvement has been achieved by adding a silane coupling agent such as aminosilane to the composition (for example, Patent Document 1). Adhesion was insufficient.

  As a method for improving the adhesion to a metal material, a heat resistant resin composition to which a specific amino compound or thiol derivative is added (for example, Patent Document 2), or a heat resistant resin to which a specific disulfide compound or thioether compound is added. Although a composition (for example, Patent Document 3) has been proposed, the effect of improving adhesiveness is not always sufficient, and a heat-resistant resin composition having high adhesiveness has been demanded even when fired at a low temperature.

JP 2008-83124 A (Claims 1 to 3) JP 2004-43779 A (Claims 1 to 5) JP 2007-39486 A (Claims 1 to 5)

  An object of this invention is to provide the heat resistant resin and its precursor composition which can obtain the cured film excellent in adhesiveness with a metal material, especially copper and gold | metal | money in view of the said problem.

  In order to solve the above problems, the heat-resistant resin and the precursor composition thereof according to the present invention have the following configurations. That is, (a) containing an alkali-soluble resin selected from polyimides, polyimide precursors and polybenzoxazole precursors or copolymers thereof, and (b) a compound represented by the following general formula (1). A heat-resistant resin and a precursor composition thereof.

In general formula (1), R ^{1 to} R ⁶ may be the same or different, and are a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxy group, a sulfonyl group, an amino group, or nitro. Indicates a group.

  The heat resistant resin and its precursor composition of the present invention can provide a cured film having excellent adhesion to metal materials, particularly copper and gold.

  The heat-resistant resin and its precursor composition according to the present invention include (a) an alkali-soluble resin selected from polyimide, polyimide precursor, and polybenzoxazole precursor, or a copolymer thereof, and (b) the following general formula. It contains the compound represented by (1).

  The heat-resistant resin and its precursor composition of the present invention contain (a) an alkali-soluble resin selected from polyimide, polyimide precursor, and polybenzoxazole precursor, or a copolymer thereof. In the present invention, alkali-soluble means that a solution in which a resin is dissolved in γ-butyrolactone 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 obtained from the decrease in film thickness when the membrane is immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ± 1 ° C. for 1 minute and then rinsed with pure water is 50 nm / min or more. Say.

  The alkali-soluble resin or copolymer thereof selected from (a) a polyimide, a polyimide precursor, and a polybenzoxazole precursor used in the present invention imparts the above-mentioned alkali solubility. Or it is preferable to have an acidic group at the end of the main chain. Examples of the acidic group include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Moreover, it is preferable to have a fluorine atom, and when developing with an alkaline aqueous solution, water repellency can be imparted to the interface between the film and the substrate, and the penetration of the alkaline aqueous solution into the interface can be suppressed. The fluorine atom content in the alkali-soluble resin is preferably 5% by weight or more from the viewpoint of the effect of preventing the penetration of the alkaline aqueous solution into the interface, and preferably 20% by weight or less from the viewpoint of solubility in the alkaline aqueous solution.

  The polyimide described above has a structural unit represented by the following general formula (2), and the polyimide precursor and the polybenzoxazole precursor have a structural unit represented by the following general formula (3). Two or more of these may be contained, or a resin obtained by copolymerizing the structural unit represented by the general formula (2) and the structural unit represented by the general formula (3) may be used.

In the general formula (2), R ⁷ represents a 4 to 10 valent organic group, and R ⁸ represents a 2 to 8 valent organic group. R ⁹ and R ¹⁰ represent a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, or a thiol group, and each may be a single group or different groups. p and q represent the integer of 0-6.

In General Formula (3), R ¹¹ represents a divalent to octavalent organic group, and R ¹² represents a divalent to octavalent organic group. R ¹³ and R ¹⁴ represent a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or COOR ¹⁵ , and each may be a single one or different ones. R ¹⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r and s represent the integer of 0-6. However, r + s> 0.

  In the present invention, the alkali-soluble resin or copolymer thereof selected from (a) polyimide, polyimide precursor, and polybenzoxazole precursor has 5 structural units represented by the general formula (2) or (3). It is preferable to have ~ 100,000. Further, in addition to the structural unit represented by the general formula (2) or (3), another structural unit may be included. In this case, it is preferable that the structural unit represented by the general formula (2) or (3) has 50 mol% or more in all the structural units.

In said general formula (2), R <^7> -(R < ⁹ _> ) _p represents the residue of an acid dianhydride. R ⁷ is a 4- to 10-valent organic group, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic 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-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic 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, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, acid dianhydride having the structure shown below, etc. Examples include aliphatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and the like. it can. Two or more of these may be used.

R ¹⁶ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ¹⁷ and R ¹⁸ each represent a hydrogen atom, a hydroxyl group or a thiol group.

In the general formula (3), R ^11- (R ¹³ ) _r represents an acid residue. R ¹¹ is a divalent to octavalent organic group, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Examples of the acid component include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tetracarboxylic acids such as acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyl Tetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2 ′, 3,3′-benzophenonetetracarboxylic acid, 2 , 2-bis (3,4-dical Xylphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3- Dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxy) Phenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10 -Perylenetetracarboxylic acid and aromatic tetracarboxylic acid having the structure shown below, butanetetracarboxylic acid, 1,2,3,4-cyclopenta , And the like aliphatic tetracarboxylic acids such as tetracarboxylic acid. Two or more of these may be used.

R ¹⁶ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , respectively. R ¹⁷ and R ¹⁸ each represent a hydrogen atom, a hydroxyl group or a thiol group.

Among these, in tricarboxylic acid and tetracarboxylic acid, one or two carboxy groups correspond to the R ¹³ group in the general formula (3). Further, dicarboxylic acids exemplified above, tricarboxylic acid, a hydrogen atom of the tetracarboxylic acid of the general formula (3) in R ¹³ groups, preferably those 1-4 substituted by a hydroxyl group or a sulfonic acid group, a thiol group More preferred. These acids can be used as they are, or as acid anhydrides and active esters.

^R 12 of ^(R _{10) q} and the general formula (3) ^{- - R} 8 in the general formula ^{₍₂₎ (R} 14) _s represents the residue of a diamine. R ⁸ and R ¹² are divalent to octavalent organic groups, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of diamines include 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, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4 -(4-aminophenoxy) phenyl} -Ter, 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′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid or compounds in which at least a part of hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, or aliphatic cyclohexyldi Min and diamines of the structure shown in methylene bis cyclohexylamine and are given below. Two or more of these may be used.

R ¹⁶ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , respectively. R ^{17 to} R ²⁰ each represent a hydrogen atom, a hydroxyl group, or a thiol group.

  These diamines can be used as diamines or as corresponding diisocyanate compounds, trimethylsilylated diamines.

  Moreover, the resin which has an acidic group at the principal chain terminal can be obtained by sealing the terminal of these resins with the above-mentioned monoamine, acid anhydride, acid chloride, and monocarboxylic acid having an acidic group.

  Preferred examples of such monoamines include 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-aminosa Tyric 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 and the like can be mentioned. Two or more of these may be used.

  Preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include acids such as phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride. Anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxy Monocarboxylic acids such as naphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like Monoacid chloride compounds in which the ruxoxy group is 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 other monocarboxylic acid compounds in which only one carboxy group is converted to an acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-di Examples include active ester compounds obtained by reaction with carboximide. Two or more of these may be used.

  The content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid described above is preferably 2 to 25 mol% with respect to 100 mol% of the total acid and amine components constituting the resin.

  The end-capping agent introduced into the resin can be easily detected by the following method. For example, a resin having a terminal blocking agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid component, which are constituent units of the resin, and this is measured by gas chromatography (GC) or NMR measurement. The end capping agent can be easily detected. Apart from this, it is possible to detect the resin into which the end-capping agent has been introduced by directly measuring by pyrolysis gas chromatography (PGC), infrared spectrum and 13C-NMR spectrum.

  The alkali-soluble resin of the present invention is synthesized by a known method. For example, a method of producing a polyamic acid or a polyamic acid ester is 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 an amine and a condensing agent are present. Examples thereof include a method of reacting under reduced pressure, a method of obtaining a diester with tetracarboxylic dianhydride and an alcohol, then converting the remaining dicarboxylic acid into an acid chloride and reacting with an amine.

  In the case of a polybenzoxazole precursor, the production method can be obtained by subjecting a bisaminophenol compound and a dicarboxylic acid to a condensation reaction. Specifically, a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a solution of a bisaminophenol compound added with a tertiary amine such as pyridine is added to a dicarboxylic acid. There is a method of dropping a solution of dichloride.

  In the case of polyimide, it can be obtained by dehydrating and ring-closing the polyamic acid or polyamic acid ester obtained by the aforementioned method by heating or chemical treatment such as acid or base.

  The alkali-soluble resin of the present invention is preferably polyimide because it can be fired at a low temperature. In order to cyclize from the precursor structure, the polyimide precursor needs to be baked at 250 ° C. or higher, and the polybenzoxazole precursor has to be baked at 300 ° C. or higher. On the other hand, since polyimide may have a closed ring structure, sufficient heat resistance and mechanical properties can be obtained even when firing at 200 ° C. or lower.

  The heat resistant resin and its precursor composition of the present invention contain (b) a compound represented by the following general formula (1).

In general formula (1), R ^{1 to} R ⁶ may be the same or different, and are a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxy group, a sulfonyl group, an amino group, or nitro. Indicates a group.

  Specific examples of the structure represented by the general formula (1) include 4,4′-dipyridyl disulfide, 2,2′-dipyridyl disulfide, bis (5-nitro-2-pyridyl) disulfide, 6,6′-dithiobis ( 3-pyridinecarboxylic acid) and the like, but is not limited thereto.

  The amount of component (b) added is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of resin (a). When the content is 0.1 parts by weight or more, the adhesiveness between the heat-cured film and the metal becomes good, and when it is 30 parts by weight or less, the heat resistance and mechanical properties of the heat-cured film become good.

  The alkali-soluble resin of component (a) of the present invention can impart positive photosensitivity by adding (c) a photoacid generator.

  The photoacid generator is a compound that generates an acid in response to radiation such as ultraviolet rays, far ultraviolet rays, and X-rays, and specifically, onium compounds such as diaryliodonium salts, triarylsulfonium salts, phenyldiazonium salts, Examples thereof include quinonediazide compounds, imide sulfonate derivatives, tosylate compounds, carbonate compounds of benzyl derivatives, and halogen compounds of triazine derivatives. Among these, quinonediazide compounds that are sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of mercury lamps, which are general ultraviolet rays, are preferred from the viewpoint of versatility.

  The quinonediazide compound is preferably a compound in which a sulfonic acid of naphthoquinonediazide is bonded with an ester to a compound having a phenolic hydroxyl group. Examples of the compound having a phenolic hydroxyl group used here include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP. -PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-3 XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, 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, 46DMOC, 46DMOEP, TM-BIP-A Manufactured by Asahi Organic Materials Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetra Hydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bispheno And BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like, and those obtained by introducing 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid into these compounds through an ester bond are preferable. Although other compounds may be mentioned, other compounds may be used.

  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 up 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. Depending on the wavelength to be exposed, a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound may be used. It is preferable to select. 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.

  The naphthoquinonediazide compound can be synthesized by a known method by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazidesulfonic acid compound.

  By using these naphthoquinonediazide compounds, resolution, sensitivity, and remaining film ratio are improved. Further, when the molecular weight of the naphthoquinone diazide compound is 1500 or more, the naphthoquinone diazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the obtained film is lowered, the mechanical properties are lowered, and the adhesiveness is lowered. May cause problems. From such a viewpoint, the molecular weight of a preferable naphthoquinone diazide compound is 300-1500. More preferably, it is 350-1200.

  The amount of component (c) added is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of resin (a). Furthermore, you may add a sensitizer etc. as needed.

  By adding the component (c), the film loss in the unexposed area after development is significantly reduced, and a good pattern can be obtained in a short development time.

  The photosensitive resin composition of the present invention may contain a compound having at least two alkoxymethyl groups or methylol groups for the purpose of easily obtaining a cured film. By having two or more of these groups, it is possible to obtain a crosslinked structure by condensation reaction with the resin and the same kind of molecules by heat treatment.

  Preferred examples of such a compound include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML- PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM- MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM- BPA, TMOM-BPAF, TM M-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKACALAC MX -270, NIKALAC MX-279, NIKACALAC MW-100LM, NIKACALAC MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more of these may be contained.

  The content of the compound having at least two alkoxymethyl groups or methylol groups is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, further preferably 100 parts by weight of the resin (a). 5 parts by weight or more, preferably 300 parts by weight or less, more preferably 200 parts by weight or less.

  Moreover, you may contain the compound which has a phenolic hydroxyl group in the range which does not make the shrinkage | contraction residual film ratio after hardening small as needed. Thereby, development time can be adjusted and scum can be improved. Examples of these compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.), novolak resin, polyhydroxystyrene, and the like. Two or more of these may be contained.

  It is preferable that the heat resistant resin and its precursor composition of the present invention contain a solvent. Thereby, it can be set as a varnish state and applicability | paintability can be improved.

  The solvent is a polar aprotic solvent such as γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , Propylene glycol mono-n-butyl ether, dipropy Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, dioxane, and other ethers , Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Propylene glycol monomer Esters such as tilether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl pro Pionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate I-propyl butyrate, Other esters such as n-butyl acid, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate, aromatic hydrocarbons such as toluene and xylene, Solvents such as N-methylpyrrolidone, N, N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like can be used alone or in combination. Among these, γ-butyrolactone is preferable because it can dissolve other components well and form a coating film with good flatness.

  Although the usage-amount of the said solvent is not specifically limited, 50-2000 weight part is preferable with respect to 100 weight part of resin of (a) component, and 100-1500 weight part is especially preferable.

  The heat resistant resin and its precursor composition of the present invention may contain a surfactant for the purpose of improving the wettability with the substrate, if necessary. As the surfactant, commercially available compounds can be used. Specifically, as the silicon surfactant, SH series, SD series, ST series of Toray Dow Corning Silicone, BYK series of BYK Japan, Shin-Etsu Silicone The KP series from Nippon Oil & Fats, the TSF series from TOSHIBA Silicone Co., Ltd., etc. are included. As the fluorosurfactants, the “MegaFac (registered trademark)” series from Dainippon Ink Industries, Ltd., Sumitomo 3M Asahi Glass's "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series, Shin-Akita Kasei's EF series, Omninova Solution's Polyfox series, etc. From methacrylic and / or methacrylic polymers The that surfactants, Kyoeisha Chemical Co. Poly flow series, manufactured by Kusumoto Chemicals, Inc. "DISPARLON (R)", but the series and the like, without limitation.

  The content of the surfactant is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the resin (a).

  Moreover, the heat resistant resin and its precursor composition of the present invention may contain inorganic particles. Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like. The primary particle diameter of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

  The content of the inorganic particles is preferably 10 to 500 parts by weight with respect to 100 parts by weight of the resin (a).

  Further, in order to enhance the adhesion to the silicon substrate, trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol are added to the resin composition of the present invention as long as the storage stability is not impaired. A silane coupling agent such as propylsilane may be contained. A preferable content is 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin of component (a).

  Next, a method for forming a pattern using the heat resistant resin of the present invention and its precursor composition will be described.

  The heat resistant resin of the present invention and its precursor composition are applied onto a substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide, or the like on which copper, gold, or titanium-based metal is formed as an electrode or wiring is used, but is not limited thereto. Examples of the application method include spin coating using a spinner, spray coating, and roll coating. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the substrate coated with the heat resistant resin and its precursor composition is dried to obtain a resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at a temperature of 50 ° C. to 150 ° C. for 1 minute to several hours. If necessary, it can be dried in two or more stages, such as drying at 80 ° C. for 2 minutes and then drying at 120 ° C. for 2 minutes.

  Next, the film is irradiated with 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-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. . When photosensitivity is not imparted to the heat resistant resin and its precursor composition, it is necessary to form another layer of a photoresist film on the resin film. For this photoresist, a general novolak resist such as OFPR-800 (manufactured by Tokyo Ohka Co., Ltd.) is preferably used. The formation of the photoresist film is performed by the same method as the formation of the heat resistant resin film.

  In the case where the resolution of the pattern at the time of development is improved or the allowable range of development conditions is increased, a step of performing a baking process before development may be incorporated. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-150 degreeC is especially more preferable. The time is preferably 10 seconds to several hours. If it is out of this range, care must be taken because the reaction may not proceed or the entire region may not dissolve.

  Development processing is performed to form a pattern of the heat resistant resin and its precursor composition. When the heat-resistant resin and its precursor composition are negative photosensitive, the relief pattern can be obtained by removing the unexposed portion with a developer, and when positive photosensitive, removing the exposed portion with a developer. Is obtained.

  The developer can be selected according to the structure of the polymer, but ammonia, tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine An aqueous solution of an alkaline compound such as methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine can be preferably used.

  Further, as a developer, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, which are solvents for the resin and composition of the present invention, Hexamethylphosphotriamide alone or the like, or the solvent of the resin and composition of the present invention and methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene A poor solvent for the resin and composition of the present invention such as glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl acetate or the like alone or Several combinations Mixture can also be preferably used.

  The development can be performed by a method such as irradiating the developer on the coating film as it is or in the form of a mist, immersing in the developer, or applying ultrasonic waves while immersing.

  Then, it is preferable to wash the relief pattern formed by development with a rinse solution. As the rinse solution, water can be preferably used when an alkaline aqueous solution is used as the developer. At this time, an rinsing treatment may be performed by adding an ester such as ethanol, isopropyl alcohol or propylene glycol monomethyl ether acetate, an acid such as carbon dioxide, hydrochloric acid or acetic acid to water.

  When rinsing with an organic solvent, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxy, which are miscible with the developer Propionate, 2-heptanone, ethyl acetate and the like are preferably used.

  When photosensitivity is not imparted to the heat resistant resin, the photoresist film formed on the resin film after development must be removed. This removal is often performed by dry etching or wet etching with a stripping solvent. As the peeling solvent, organic solvents such as acetone, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, An aqueous solution of sodium hydroxide or potassium hydroxide is used, but not limited thereto.

  After the development, by applying a temperature of 150 ° C. to 500 ° C., when the resin is a precursor, the ring-opening portion is closed, and when the resin contains a thermal crosslinking component, the crosslinking reaction proceeds, and the resulting resin film has heat resistance. And chemical resistance are improved. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 180 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 300 ° C. over 2 hours can be mentioned. In the present invention, the curing condition is preferably 150 ° C. or higher and 350 ° C. or lower. However, since the present invention provides a cured film having excellent adhesion to a metal material even at low temperature firing, 150 ° C. or higher and 280 ° C. More preferably, it is 150 ° C. or higher and 250 ° C. or lower.

  The heat-resistant cured film formed of the heat-resistant resin and the precursor composition of the present invention includes a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for multilayer wiring for high-density mounting, and an insulation for an organic electroluminescent element. It is suitably used for applications such as layers.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, evaluation of the resin in a synthesis example, the heat resistant resin in an Example, and its precursor composition was performed with the following method.

(1) Adhesion test An adhesion test with a metal material was performed by the following method.

Preparation of Cure Film A substrate (copper sputter substrate, gold sputter substrate) was prepared by sputtering copper or gold on a silicon wafer and having a metal material layer formed with a thickness of 200 to 500 nm on the surface. On this substrate, varnish was applied by spin coating using a spinner (Mikasa Co., Ltd.) and then baked at 120 ° C. for 3 minutes using a hot plate (D-SPIN manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a pre-baked film having a thickness of 8 μm was produced. Using a clean oven (CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.), this membrane was heated at 140 ° C. for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less), then further heated to 1 at a predetermined temperature. Time curing was performed to obtain a polyimide cured film.

The adhesive property evaluation substrate was divided into two, and a single-edged blade was used for the cured film for each substrate, and 10 rows and 10 columns of grid-like cuts were made at intervals of 2 mm. Of these, one sample substrate was used to count how many of the 100 cells were peeled by peeling with cello tape (registered trademark), and the adhesion characteristics between the metal material / resin cured film were evaluated. The other sample substrate was subjected to a PCT treatment for 200 hours under a saturated condition of 121 ° C. and 2 atm using a pressure cooker test (PCT) apparatus (HAST CHAMBER EHS-212MD manufactured by Tabais Peeck Co., Ltd.). Thereafter, the above-described peeling test was performed. In any of the substrates, the number of peeled off in the peeling test was determined to be less than 20, and 20 or more was determined to be defective.

Film thickness measurement method Dainippon Screen Mfg. Co., Ltd. Lambda Ace STM-602 was used, and after pre-baking, the developed film was measured with a refractive index of 1.629, and the cured film was measured with a refractive index of 1.773. .

(2) Sensitivity evaluation Production of developed film Using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Ltd.), varnish is applied on an 8-inch silicon wafer by spin coating, and hot plate is used at 120 ° C for 3 minutes. Was baked to prepare a pre-baked film having an average film thickness of 10 μm. Thereafter, it exposed with 10 mJ / cm ² steps by the exposure amount of 0~500mJ / cm ² using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation). After exposure, using the Mark-7 developing device, a 2.38 wt% tetramethylammonium aqueous solution (hereinafter TMAH, manufactured by Tama Chemical Industry Co., Ltd.) reduces the film thickness during development to 1.5 μm. After developing with time, the substrate was rinsed with distilled water and then shaken off and dried to obtain a pattern.

Method for Measuring Film Thickness Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film after pre-baking and development was measured with a refractive index of 1.629.

Calculation of sensitivity The pattern of the developed film obtained by the above method is observed at a magnification of 20 using an FDP microscope MX61 (manufactured by Olympus Corporation), and the minimum necessary exposure amount for opening a pattern with a mask size of 5 μm This was taken as the sensitivity.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was added to 100 mL of acetone and 17 of propylene oxide. It was dissolved in 0.4 g (0.3 mol) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-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 catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 2 Synthesis of Alkali-Soluble Resin (A-1) BAHF 29.3 g (0.08 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005) under a dry nitrogen stream Mol), 3.27 g (0.03 mol) of 3-aminophenol was dissolved in 150 g of N-methyl-2-pyrrolidone (NMP) as a terminal blocking agent. Here, 31.0 g (0.1 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (manac Co., Ltd., ODPA) was added with 50 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour. Then, the mixture was stirred at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried with an 80 ° C. vacuum dryer for 24 hours to obtain polyimide (A-1) which is an alkali-soluble resin.

Synthesis Example 3 Synthesis of Alkali-Soluble Resin (A-2) 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of NMP under a dry nitrogen stream. Here, 9.07 g (0.015 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 0.25 g (0.001 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to 25 g of NMP. And reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.87 g (0.008 mol) of 4-aminophenol as an end-capping agent was added together with 5 g of NMP, and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the stirring, the solution was cooled to room temperature and then poured into 1 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 24 hours in a vacuum dryer at 80 ° C. to obtain a polyimide precursor (A-2) which was the target alkali-soluble resin.

Synthesis Example 4 Synthesis of Alkali-Soluble Resin (A-3) Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was adjusted. Cooled to -15 ° C. Here, 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) ) A solution dissolved in 25 g 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 for 24 hours in a vacuum dryer at 80 ° C. to obtain a target polybenzoxazole precursor (A-3), which is an alkali-soluble resin.

Synthesis Example 5 Synthesis of quinonediazide compound (C-1) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 33 .58 g (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 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 (C-1) represented by the following formula.

Synthesis Example 6 Synthesis of quinonediazide compound (C-2) Under a dry nitrogen stream, 24.1 g (0.05 mol) of TrisOCR-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 4-naphthoquinonediazidesulfonyl acid chloride 13 .43 g (0.05 mol) and 20.15 g (0.075 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 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 (C-2) represented by the following formula.

The sulfide compounds used in each example and comparative example are shown below.
(B-1): 4,4′-dipyridyl disulfide (B-2): 2,2′-dipyridyl disulfide (B-3): bis (5-nitro-2-pyridyl) disulfide (B-4): 6 , 6'-dithiobis (3-pyridinecarboxylic acid)
(Β-1): 4,4′-Diacetylaminodiphenyl disulfide (β-2): Bis [3- (triethoxysilyl) propyl] tetrasulfide (β-3): Dibenzothiazyl disulfide Example 1
After dissolving 10.0 g of the alkali-soluble resin (A-1) obtained in Synthesis Example 2 and 0.5 g of (B-1) in 15.0 g of γ-butyrolactone, a 1 μm polytetrafluoroethylene filter ( Varnish A was obtained by filtration through Sumitomo Electric Industries, Ltd. Using the obtained varnish A, an adhesion test was performed at 180 ° C. by the above method.

Example 2
Varnish B was obtained in the same manner as in Example 1 except that (B-2) was used instead of (B-1) as the component (b). Using the obtained varnish B, an adhesion test was performed at 180 ° C. by the above method.

Example 3
Varnish C was obtained in the same manner as in Example 1 except that (B-3) was used instead of (B-1) as the component (b). Using the obtained varnish C, an adhesion test was performed at 180 ° C. by the above method.

Example 4
Varnish D was obtained in the same manner as in Example 1 except that (B-4) was used instead of (B-1) as the component (b). Using the obtained varnish D, an adhesion test was performed at 180 ° C. by the above method.

Example 5
Varnish E was obtained in the same manner as in Example 1 except that (A-2) was used instead of (A-1) as the alkali-soluble resin. Using the obtained varnish E, an adhesion test was performed at 280 ° C. by the above method.

Example 6
Using the varnish E obtained in Example 5, the adhesion test was performed at 180 ° C. by the above method.

Example 7
Varnish F was obtained in the same manner as in Example 1 except that (A-3) was used instead of (A-1) as the alkali-soluble resin. Using the obtained varnish F, an adhesion test was performed at 320 ° C. by the above method.

Example 8
Using the varnish F obtained in Example 7, an adhesion test was performed at 180 ° C. by the above method.

Comparative Example 1
Varnish G was obtained in the same manner as in Example 1 except that component (B-1) (b) was not added. Using the obtained varnish G, an adhesion test was performed at 180 ° C. by the above method.

Comparative Example 2
Varnish H was obtained in the same manner as in Example 1 except that (β-1) was used instead of (B-1) as the component (b). Using the obtained varnish H, an adhesion test was performed at 180 ° C. by the above method.

Comparative Example 3
Varnish I was obtained in the same manner as in Example 1 except that (β-2) was used instead of (B-1) as the component (b). Using the obtained varnish I, an adhesion test was performed at 180 ° C. by the above method.

Comparative Example 4
Varnish J was obtained in the same manner as in Example 1 except that (β-3) was used instead of (B-1) as the component (b). Using the obtained varnish J, an adhesion test was performed at 180 ° C. by the above method.

  The composition of the evaluation varnish is shown in Table 1, and the adhesion test results are shown in Table 2.

Example 9
After dissolving 10.0 g of the alkali-soluble resin (A-1) obtained in Synthesis Example 2 and 0.5 g of (B-1) and 1.5 g of the quinonediazide compound (C-1) in 18.0 g of γ-butyrolactone. A varnish K was obtained by filtration through a 1 μm filter made of polytetrafluoroethylene (manufactured by Sumitomo Electric Industries, Ltd.). Using the obtained varnish K, an adhesion test was performed at 180 ° C. by the above-described method, and further a photosensitivity evaluation was performed.

Example 10
Varnish L was obtained in the same manner as in Example 9 except that (B-2) was used instead of (B-1) as the component (b). Using the obtained varnish L, an adhesion test was performed at 180 ° C. by the above-described method, and the photosensitivity was evaluated.

Example 11
Varnish M was obtained in the same manner as in Example 9 except that (B-3) was used instead of (B-1) as the component (b). Using the obtained varnish M, an adhesion test was performed at 180 ° C. by the above-described method, and further a photosensitivity evaluation was performed.

Example 12
Varnish N was obtained in the same manner as in Example 9 except that (B-4) was used instead of (B-1) as the component (b). Using the obtained varnish N, an adhesion test was performed at 180 ° C. by the above-described method, and the photosensitivity was evaluated.

Example 13
Varnish O was obtained in the same manner as in Example 9 except that (A-2) was used instead of (A-1) as the alkali-soluble resin. Using the obtained varnish O, an adhesion test was performed at 280 ° C. by the above-described method, and further a photosensitivity evaluation was performed.

Example 14
Varnish P was obtained in the same manner as in Example 9 except that (A-3) was used instead of (A-1) as the alkali-soluble resin. Using the obtained varnish P, an adhesion test was performed at 320 ° C. by the above-described method, and further a photosensitivity evaluation was performed.

Example 15
Varnish Q was obtained in the same manner as in Example 9 except that (C-2) was used instead of (C-1) as the component (c). Using the obtained varnish Q, an adhesion test was performed at 180 ° C. by the above-described method, and further photosensitivity was evaluated.

Comparative Example 5
Varnish R was obtained in the same manner as Example 9 except that (B-1) component (b) was not added. Using the obtained varnish R, an adhesion test was performed at 180 ° C. by the above-described method, and further a photosensitivity evaluation was performed.

Comparative Example 6
Varnish S was obtained in the same manner as in Example 9 except that (β-1) was used instead of (B-1) as the component (b). Using the obtained varnish S, an adhesion test was performed at 180 ° C. by the above-described method, and further a photosensitivity evaluation was performed.

Comparative Example 7
Varnish T was obtained in the same manner as in Example 9 except that (β-2) was used instead of (B-1) as the component (b). Using the obtained varnish T, an adhesion test was performed at 180 ° C. by the above-described method, and the photosensitivity was evaluated.

Comparative Example 8
Varnish U was obtained in the same manner as in Example 9 except that (β-3) was used instead of (B-1) as the component (b). Using the obtained varnish U, an adhesion test was performed at 180 ° C. by the above-described method, and further photosensitivity was evaluated.

  The composition of the evaluation varnish is shown in Table 3, and the adhesion test results are shown in Table 4.

Claims (4)

(A) An alkali-soluble resin selected from polyimide, polyimide precursor, and polybenzoxazole precursor or a copolymer thereof, (b) containing a compound represented by the following general formula (1) Heat resistant resin and precursor composition thereof.

In general formula (1), R ^{1 to} R ⁶ may be the same or different, and are a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, a carboxy group, a sulfonyl group, an amino group, or nitro. Indicates a group. The heat-resistant resin and its precursor composition according to claim 1, further comprising (c) a photoacid generator. (C) The photoacid generator is a quinonediazide compound, The heat-resistant resin and its precursor composition according to claim 2. The resin of (a) component is a polyimide, The heat resistant resin and its precursor composition in any one of Claims 1-3 characterized by the above-mentioned.