JP5061435B2 - Heat-resistant resin precursor composition and semiconductor device using the same - Google Patents

Description

  The present invention relates to a precursor composition of a heat resistant resin used for an interlayer insulating film, a surface protective layer and the like in the semiconductor field, particularly a precursor of a heat resistant resin suitably used for an electrode made of a metal material and an insulating film in contact with a wiring. The present invention relates to a body composition and a semiconductor device using the same.

  Heat-resistant resins are used in the semiconductor field for interlayer insulation films, surface protective films (buffer coat films, alpha ray shielding films), etc. First, they are applied in the form of a heat-resistant resin precursor that is highly soluble in organic solvents. After the film is formed, a pattern processing is performed using a photoresist such as a novolac resin, and then the precursor is heated and cured to obtain an insoluble and infusible heat resistant resin. In recent years, the photoresist process has been simplified by using negative and positive photosensitive heat-resistant resin precursor compositions that can themselves be patterned.

  The negative photosensitive heat-resistant resin precursor composition in which the exposed part remains by development includes an organic group dimerized by actinic radiation or an amino compound containing a polymerizable carbon-carbon double bond, or a quaternization thereof. A salt added to a polyamic acid (for example, see Patent Document 1), a polyamic acid to which an acrylamide is added (for example, see Patent Document 2), and a carbon-carbon double bond group in the side chain or main chain of the polymer A polyimide precursor (see, for example, Patent Document 3) is disclosed.

  Moreover, as a positive type photosensitive heat-resistant resin precursor composition in which the exposed part is dissolved by development with an alkaline aqueous solution, a polyimide precursor in which an o-nitrobenzyl group is introduced into a polymer side chain by an ester bond (for example, Patent Document 4) Reference), a polyamic acid ester mixed with an o-quinonediazide compound, a polyamic acid having a phenolic hydroxyl group or a polyamic acid ester mixed with an o-quinonediazide compound (for example, see Non-Patent Document 1), and having a phenolic hydroxyl group The thing which mixed the o-quinonediazide compound with the polyimide (for example, refer nonpatent literature 2), the thing which mixed the o-quinonediazide compound with polyhydroxyamide (for example, refer patent document 5), etc. are disclosed.

  When the heat-resistant resin precursor composition is used for semiconductor applications, the mechanical properties of the heat-cured film are very important because the resin after heat-curing remains as a permanent film in the device.

  In order to ensure reliability in a semiconductor package, adhesion to silicon-based materials formed on the surface of a semiconductor chip such as silicon, silicon oxide, silicon nitride, and phosphorous silicate glass is important. In particular, when used for an insulating film between wiring layers of a wafer level package, in addition to the adhesiveness with the silicon-based material, the adhesiveness with a metal material used for electrodes, wirings, etc. is important.

  In general, a heat-resistant resin is considered not to have high adhesive strength with a metal material due to its rigid main chain structure, and in the case of a heat-resistant resin formed from the photosensitive precursor listed above, it constitutes a composition. Additives such as photosensitizers, sensitizers, acid generators and dissolution regulators remain after heating and curing, resulting in lower adhesion strength than those containing no additives There was a point. To solve this problem, improvements have been made by adding a silane coupling agent such as aminosilane to the composition. However, metal materials, particularly copper, gold, titanium-based metals (eg, titanium, titanium nitride, titanium tungsten) have been improved. Etc.) was not sufficiently improved.

As a method for solving this problem and improving the adhesion to a metal material, a heat resistant resin precursor composition using a specific amino compound or thiol derivative as an adhesion improver has been proposed (for example, Patent Document 6). reference). This improves the adhesion performance with the metal material, but there is a problem with the stability of the heat-resistant resin precursor composition at room temperature.
JP 11-30862 A (Claims 1 to 5) JP-A-3-170547 (Claim 1) JP-A-8-36264 (Claims 1 to 5) JP-A-62-145239 (Claims 1 and 2) JP 2002-229206 A (Claims 1 to 5) JP 2004-43779 A (Claims 1 to 5) “J. Appl. Polym. Sci.”, 58, 1535 (1995). “Reactive & Functional Polym.”, 30, 109 (1996).

  Materials used in the semiconductor industry are required to be stable under room temperature storage. The present invention improves the adhesion between a heat-cured film and a metal material, particularly copper, gold, and titanium-based metal, and uses a heat-resistant resin precursor composition that has little change in adhesion performance due to storage at room temperature and the same. An object is to provide a semiconductor device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a heat-resistant resin precursor composition that satisfies both adhesion to a metal material and room temperature storage stability by using a specific disulfide compound or thioether compound. It was found that a product was obtained.

That is, the present invention mainly comprises a) one or more structural units selected from the structural units represented by the following general formulas (4), (5), (5) ′, (5) ″, (6) and (7). a polymer as a component, b) a heat-resistant resin precursor composition comprising the following formula (b) to show that Ru of compound selected from those of the structure.

(R ¹⁵ is 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylhexafluoropropanetetra Selected from carboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid This is a residue obtained by removing four carboxyl groups from a tetracarboxylic acid compound.
R ¹⁶ is para-phenylenediamine, meta-phenylenediamine, methyl para-phenylenediamine, methyl m-phenylenediamine, dimethyl paraphenylene diamine, dimethyl meta-phenylenediamine, trimethyl paraphenylenediamine, trimethyl metaphenylene diamine, tetramethyl paraphenylenediamine, tetramethyl meta Phenylenediamine, trifluoromethylparaphenylenediamine, trifluoromethylmetaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methylmetaphenylenediamine, methoxyparaphenylenediamine, methoxymetaphenylenediamine, trifluoromethoxy Paraphenylenediamine, trifluoromethoxymetaphenylenediamine, fluoropa Laphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxycarbonylmetaphenylenediamine , Diaminodiphenylmethane, bis (aminomethylphenyl) methane, bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl) methane, bis (aminodiethylphenyl) ) Methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (aminotri Fluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (aminodimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) Hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) ) Hexafluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bi (Aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (aminoethyl) Phenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl) ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (Aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) methane and bis (amino It is a residue obtained by removing two amino groups from a diamine compound selected from (nophenoxyphenyl) sulfone, or a residue obtained by removing two amino groups from a hydrogenated compound of the diamine compound.
R ¹⁷ and R ¹⁸ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. R ¹⁷ and R ¹⁸ may be the same or different. m ₂ is an integer of 3 to 100,000.
R ¹⁹ is the compound listed as R ¹⁵ in the general formula (4). Ar ⁴ ′ and Ar ⁴ ″ have a structure as shown in the above formula.
R ²⁰ ′ is the compound listed as R ¹⁶ in the general formula (4). The following structural formulas (10) and (10) '' containing R ²⁰ and R ²⁰ ″ are diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, 1,3-diamino-4-hydroxybenzene, 1,3. -Diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) sulfone Bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexaful Ropropane, 1,5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, bis (3-amino-4-hydroxyphenyl) propane and bis (4-amino-3-hydroxy) A residue obtained by removing two amino groups from a hydroxy group-containing diamine compound selected from phenyl) propane or a structure represented by the following formula (11).
R ²¹ , R ^{21 ′} and R ^{21 ″} represent hydrogen or an organic group having 1 to 20 carbon atoms. m ₃ , m ₃ ′ and m ₃ ″ are integers from ₃ to 100,000, and s and s ″ are 1 or 2.
R ²² represents diphenyl ether-3,3′-dicarboxylic acid, diphenyl ether-3,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, isophthalic acid, benzophenone-3,3′-dicarboxylic acid, benzophenone-3. , 4′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, diphenylsulfone-3,3′-dicarboxylic acid, diphenylsulfone-3,4′-dicarboxylic acid and diphenylsulfone-4,4′-dicarboxylic acid A residue obtained by removing two carboxyl groups from a selected dicarboxylic acid compound.
R ²³ is di-amino-dihydroxypyrimidine, diaminodihydroxy pyridine, 3, 3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4- Hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 1, 5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3 ′ -Dihydroxydiphenyl ether and 3,4'-diamino-3,4'-dihydro From hydroxy group-containing diamine compound selected from shea ether is a residue obtained by removing two amino groups and two hydroxyl groups.
m4 represents an integer of ₃ to 100,000.
R ²⁴ is the compound listed as R ¹⁵ in the general formula (4).
R ²⁵ is 2, 5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diamino terephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, 4 A carboxyl group and two carboxyl groups from a carboxyl group-containing diamine compound selected from 4,4'-diamino 3,3'-dicarboxybiphenyl and 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl It is a residue excluding an amino group.
R ^{26 to} R ²⁸ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. R ^{26 to} R ²⁸ may be the same or different. u is 1 or 2, and R ²⁸ when u is 2 may be a single species or a mixture of two or more species. m5 represents an integer of ₃ to 100,000. )

  According to the present invention, a heat-resistant resin precursor composition excellent in adhesion to a metal material such as copper, gold, titanium-based metal, etc. of the film after heat curing, and excellent in room temperature storage stability, and the same are used. A semiconductor device can be provided.

  Hereinafter, the present invention will be described in detail. As a result of diligent studies to solve the above-mentioned problems, the present invention is based on a heat-resistant resin precursor composition containing a specific disulfide compound or a specific thioether compound, and a heat-cured film and a metal material, particularly copper, gold, and titanium. It has been found that the adhesion to metal is dramatically improved, and that even when this heat-resistant resin precursor composition is stored at room temperature, the adhesion performance does not deteriorate.

The heat resistance in the present invention means that it can withstand continuous use at a high temperature of 250 ° C. or higher. Examples of the heat resistant resin precursor composition of the present invention include polyamic acid which is a precursor of polyimide, polyhydroxyamide which is a precursor of polybenzoxazole, polythiohydroxyamide which is a precursor of polybenzothiazole, and polybenzimidazole. Examples of such a precursor include polyaminoamide, which can be converted into a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst, but is not limited thereto. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved .

The main component in the present invention means one or more structural units selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7). It means containing 70 mol% or more. More preferably, it is 80 mol% or more, and most 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 polymer obtained by the final heat treatment.

In the present invention, the main component is one or more structural units selected from the structural units represented by the following general formulas (4), (5), (5) ′, (5) ″, (6) and (7). A polymer is used.

R ¹⁵ is 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylhexafluoropropanetetracarboxylic acid 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid tetra A residue obtained by removing four carboxyl groups from a carboxylic acid compound.
R ¹⁶ is para-phenylenediamine, meta-phenylenediamine, methyl para-phenylenediamine, methyl m-phenylenediamine, dimethyl paraphenylene diamine, dimethyl meta-phenylenediamine, trimethyl paraphenylenediamine, trimethyl metaphenylene diamine, tetramethyl paraphenylenediamine, tetramethyl meta Phenylenediamine, trifluoromethylparaphenylenediamine, trifluoromethylmetaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methylmetaphenylenediamine, methoxyparaphenylenediamine, methoxymetaphenylenediamine, trifluoromethoxy Paraphenylenediamine, trifluoromethoxymetaphenylenediamine, fluoropa Laphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxycarbonylmetaphenylenediamine , Diaminodiphenylmethane, bis (aminomethylphenyl) methane, bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl) methane, bis (aminodiethylphenyl) ) Methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (aminotri Fluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (aminodimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) Hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) ) Hexafluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bi (Aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (aminoethyl) Phenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl) ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (Aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) methane and bis (amino It is a residue obtained by removing two amino groups from a diamine compound selected from (nophenoxyphenyl) sulfone, or a residue obtained by removing two amino groups from a hydrogenated compound of the diamine compound.
R ¹⁷ and R ¹⁸ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. R ¹⁷ and R ¹⁸ may be the same or different. m ₂ is an integer of 3 to 100,000.

R ¹⁹ is the compound listed as R ¹⁵ in the general formula (4) . Ar ⁴ ′ and Ar ⁴ ″ have a structure as shown in the above formula. R ²⁰ ′ is the compound listed as R ¹⁶ in the general formula (4) . The following structural formulas (10) and (10) '' containing R ²⁰ and R ²⁰ ″ are diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, 1,3-diamino-4-hydroxybenzene, 1,3. -Diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) sulfone Bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexaful Ropropane, 1,5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, bis (3-amino-4-hydroxyphenyl) propane and bis (4-amino-3-hydroxy) A residue obtained by removing two amino groups from a hydroxy group-containing diamine compound selected from phenyl) propane or a structure represented by the following formula (11).
R ²¹ , R ^{21 ′} and R ^{21 ″} represent hydrogen or an organic group having 1 to 20 carbon atoms. m ₃ , m ₃ ′ and m ₃ ″ are integers of ₃ to 100,000, and s and s ″ are 1 or 2.

R ²² represents diphenyl ether-3,3′-dicarboxylic acid, diphenyl ether-3,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, isophthalic acid, benzophenone-3,3′-dicarboxylic acid, benzophenone-3. , 4′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, diphenylsulfone-3,3′-dicarboxylic acid, diphenylsulfone-3,4′-dicarboxylic acid and diphenylsulfone-4,4′-dicarboxylic acid A residue obtained by removing two carboxyl groups from a selected dicarboxylic acid compound.
R ²³ is di-amino-dihydroxypyrimidine, diaminodihydroxy pyridine, 3, 3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4- Hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 1, 5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3 ′ -Dihydroxydiphenyl ether and 3,4'-diamino-3,4'-dihydro Hydroxy group-containing diamine compound selected from shea ether is a residue obtained by removing two amino groups and two hydroxyl groups.
m4 represents an integer of ₃ to 100,000.

R ²⁴ is the compound listed as R ¹⁵ in the general formula (4).
R ²⁵ is 2, 5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diamino terephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, 4 A carboxyl group and two carboxyl groups from a carboxyl group-containing diamine compound selected from 4,4'-diamino 3,3'-dicarboxybiphenyl and 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl It is a residue excluding an amino group.
R ^{26 to} R ²⁸ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. R ^{26 to} R ²⁸ may be the same or different. u is 1 or 2, and R ²⁸ when u is 2 may be a single species or a mixture of two or more species. m5 represents an integer of ₃ to 100,000.

In the above general formula (4), R ¹⁵ is 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4 ′. -Diphenylhexafluoropropanetetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid and cyclo It is a residue obtained by removing four carboxyl groups from a tetracarboxylic acid compound selected from pentanetetracarboxylic acid . Further, R ¹⁵ is may be composed of one of these, it may be a copolymer composed of two or more.

In the general formula (4), R ¹⁶ represents paraphenylene diamine, metaphenylene diamine, methyl paraphenylene diamine, methyl metaphenylene diamine, dimethyl paraphenylene diamine, dimethyl metaphenylene diamine, trimethyl paraphenylene diamine, trimethyl metaphenylene diamine, tetramethyl para Phenylenediamine, tetramethylmetaphenylenediamine, trifluoromethylparaphenylenediamine, trifluoromethylmetaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methylmetaphenylenediamine, methoxyparaphenylenediamine, methoxymeta Phenylenediamine, trifluoromethoxyparaphenylenediamine, trifluoromethoxymetaphenylene Diamine, fluoroparaphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxycarbonyl Metaphenylenediamine, diaminodiphenylmethane, bis (aminomethylphenyl) methane, bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl) methane, bis ( Aminodiethylphenyl) methane, diaminodiphenylpropane, bis (aminomethylphenyl) propa , Bis (aminotrifluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (aminodimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis ( Aminomethylphenyl) hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (Aminodiethylphenyl) hexafluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) Nyl) sulfone, bis (aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether Bis (aminoethylphenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl) ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxy) Phenyl) propane, bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) me A residue obtained by removing two amino groups from a diamine compound selected from tan and bis (aminophenoxyphenyl) sulfone, or a residue obtained by removing two amino groups from a hydrogenated compound of the diamine compound . Further, R ¹⁶ is may be composed of one of these, it may be a copolymer composed of two or more.

In the general formula (4), R ¹⁷ and R ¹⁸ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. The organic group having 1 to 20 carbon atoms is preferably an aliphatic organic group, and examples thereof include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. Specific examples of preferable organic group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, butyl group, t-butyl group, ethyl methacrylate group, ethyl acrylate group, propyl methacrylate group, and propyl acrylate. Groups, ethyl methacrylamide groups, propyl methacrylamide groups, ethyl acrylamide groups, propyl acrylamide groups, and the like, but are not limited thereto. In order to suppress copper migration, it is preferable that 50 mol% or more of R ¹⁷ and R ¹⁸ is an organic group having 1 to 20 carbon atoms, and 70 mol% or more is an organic group having 1 to 20 carbon atoms. More preferably. Moreover, it is more preferable that it is a C1-C4 organic group. R ¹⁷ and R ¹⁸ may be a single species or a mixture of two or more species. Further, R ¹⁷ and R ¹⁸ may be the same or different.

The polymer having the structural unit represented by the general formula (4) as a main component is synthesized by a known method. That is, when R ¹⁷ and R ¹⁸ are hydrogen, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N— It is synthesized by a known method such as a reaction in a polar solvent containing dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide or the like as a main component or a solvent containing γ-butyrolactone as a main component.

In the case where R ¹⁷ and R ¹⁸ are alkyl groups, after reacting tetracarboxylic dianhydride with an alcohol compound, synthesizing an acid chloride using thionyl chloride or the like, and then selectively combining with an appropriate diamine Or selectively combined with a diamine using a suitable dehydrating agent such as dicyclohexylcarbodiimide, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexa It is synthesized by a known method such as reacting in a polar solvent containing methylphosphorotriamide or the like as a main component or in a solvent containing γ-butyrolactone as a main component.

^{If, R 19} in the general formula (5) are the compounds listed in ^{R 1 5} in the general formula (4). In general formula (5) In the case of 'general formula (5)'', Ar ^4', Ar ⁴ '' it has a structure as shown in the following formula.

Formula (5) ^{'R 20'} of the compounds listed in ^{R 16} in the general formula (4). The following structural formulas (10 ) and (10) '' including R ²⁰ and R ²⁰ ″ in the general formulas (5) and (5) ″ are diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, 1 , 3-Diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl Bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ) Ether, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydride) Kishifeniru) hexafluoropropane, 1,5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, bis (3-amino-4-hydroxyphenyl) propane and bis (4-amino 3-hydroxyphenyl) those excluding residues or formula two amino groups from hydroxy group-containing diamine compound selected from propane (11) shown in to structures.

  The said acid compound or diamine compound is used individually or in combination of 2 or more types. At this time, it is preferable that the acid compound containing a hydroxyl group is 70 mol% or more of the total acid compound, or the diamine compound containing a hydroxyl group is 70 mol% or more of the total diamine compound. When the ratio of the compound containing a hydroxyl group is in the above range, there is an advantage that the solubility in an alkali developer is increased and the sensitivity is improved.

R ²¹ in the general formulas (5) , (5) ′ and (5) ″ represents hydrogen or an organic group having 1 to 20 carbon atoms. More preferably, it is a C1-C10 organic group. When the carbon number of R ²¹ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the stability of the resulting photosensitive resin solution, R ²¹ is preferably an organic group having 1 to 20 carbon atoms, but hydrogen is preferable from the viewpoint of solubility in an aqueous alkali solution. That is, it is not preferable that all R ²¹ are hydrogen or all organic groups. By controlling the amount of hydrogen and organic group of R ^21, the dissolution rate with respect to the aqueous alkali solution is changed, so that a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. Considering suppression of copper migration, 50 mol% or more of R ²¹ is more preferably an organic group having 1 to 20 carbon atoms, and 70 mol% or more is an organic group having 1 to 20 carbon atoms. Further preferred. Moreover, it is especially preferable that it is a C1-C4 organic group .

  It is also possible to adjust the amount of the remaining carboxyl group by imidizing a part of the carboxyl group. As an imidization method, a known method may be used as long as imidization is possible. The imidation ratio at this time is preferably 1% or more and 50% or less. More preferably, it is 1% or more and 20% or less. By suppressing the imidization rate to 50% or less, there is an advantage that the absorption of the polymer with respect to the actinic radiation used for exposure is reduced and the sensitivity is improved.

The polymer having the structural unit represented by the general formula (5) , (5) ′, (5) ″ as a main component is synthesized by a known method. That is, tetracarboxylic dianhydride and diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, etc. After reacting in a polar solvent containing γ-butyrolactone as a main component, a side chain carboxyl group may be imidized by heat treatment or an alkyl ester using an esterifying reagent, etc. And is synthesized by a known method.

In the general formula (6), R ²² represents diphenyl ether-3,3′-dicarboxylic acid, diphenyl ether-3,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, isophthalic acid, benzophenone-3,3′-. Dicarboxylic acid, benzophenone-3,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, diphenylsulfone-3,3'-dicarboxylic acid, diphenylsulfone-3,4'-dicarboxylic acid and diphenylsulfone-4, A residue obtained by removing two carboxyl groups from a dicarboxylic acid compound selected from 4'-dicarboxylic acids . R ²² may be composed of one of these, or may be a copolymer composed of two or more.

^{R 23} in the general formula (6), diamino-dihydroxypyrimidine, diaminodihydroxy pyridine, 3, 3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis ( 3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) Hexafluoropropane, 1,5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′- Diamino-3,3'-dihydroxydiphenyl ether and 3,4'-diamy 3,4' a residue obtained by removing two amino groups from hydroxy group-containing diamine compound and two hydroxyl groups selected from the dihydroxydiphenyl ether. Further, R ²³ is may be composed of one of these, it may be a copolymer composed of two or more.

  The polybenzoxazole precursor represented by the general formula (6) is synthesized by a known method. That is, it can be obtained by a method such as condensation of dihydroxydiamine and halogenated dicarboxylic acid, or condensation of dihydroxydiamine and dicarboxylic acid in the presence of a dehydration condensing agent such as dicyclohexylcarbodiimide.

R ²⁴ in the general formula (7) are compounds listed in the R ¹⁵ in the general formula (4).

^{R 25} in the general formula (7), 2, 5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diamino terephthalic acid, bis (4-amino-3- Carboxyphenyl) methylene, 4,4′-diamino 3,3′-dicarboxybiphenyl and carboxyl group-containing diamine compound selected from 4,4′-diamino-5,5′-dicarboxy-2,2′-dimethylbiphenyl Is a residue obtained by removing a carboxyl group and two amino groups from These may be used alone or in combination of two or more.

  In addition, it is preferable to contain 10 mol% or more of diamine compounds which have a carbonyl group in a side chain among these diamine compounds with respect to the total number of moles of a diamine compound. More preferably, it is 30 mol% or more. By containing 10 mol% or more of a diamine having a carbonyl group in the side chain, there is an advantage that the solubility in an alkali developer is increased and the sensitivity is improved.

In the general formula (7), R ²⁶ and R ²⁷ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. The organic group having 1 to 20 carbon atoms is preferably an aliphatic organic group, and examples thereof include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. Specific examples include methyl, ethyl, isopropyl, butyl, t-butyl, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, ethyl methacrylamide, propyl methacrylamide. Groups, ethylacrylamide groups, propylacrylamide groups, and the like, but are not limited thereto. In particular, the use of one having 5 or less carbon atoms has the advantage that the ester portion is rapidly removed during thermal curing, and dehydration ring closure proceeds completely to obtain a polyimide resin film having good characteristics. Particularly preferred are methyl group, ethyl group, isopropyl group, butyl group and t-butyl group.

In the general formula (7), R ²⁸ represents hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. In view of solubility in an alkali developer, R ²⁸ is preferably hydrogen, an alkali metal ion or an ammonium ion, and most preferably hydrogen.

The polymer having the structural unit represented by the general formula (7) as a main component is synthesized by a known method. That is, when R ²⁶ and R ²⁷ are hydrogen, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N— It is synthesized by a known method such as a reaction in a polar solvent containing dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide or the like as a main component or a solvent containing γ-butyrolactone as a main component.

In the case where R ²⁶ and R ²⁷ are alkyl groups, after reacting tetracarboxylic dianhydride with an alcohol compound, synthesizing an acid chloride using thionyl chloride or the like, and then selectively combining with an appropriate diamine Or selectively combined with a diamine using a suitable dehydrating agent such as dicyclohexylcarbodiimide, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexa It is synthesized by a known method such as reacting in a polar solvent containing methylphosphorotriamide or the like as a main component or in a solvent containing γ-butyrolactone as a main component.

A polymer mainly composed of one or more structural units selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7) It may be used, and may be a copolymer or a mixture.

Further, in order to improve the adhesion property with the metal material, 1 selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7) It is preferable that at least one of both ends of the polymer having the structural unit as a main component contains at least one organic group selected from a phenol group and a thiophenol group. Specific examples of the organic group include, but are not limited to, the structures shown below.

Furthermore, the polymer whose main component is one or more structural units selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7) , More preferably, the polymer is precipitated and then washed and dried after precipitation in a poor solvent for the polymer such as methanol or water. By re-precipitation, the by-product by the esterification agent, condensing agent and acid chloride used during polymer polymerization, and low molecular weight components of the polymer can be removed, greatly improving the mechanical properties of the composition after heat curing. To improve.

Heat-resistant resin precursor composition of the present invention b) as essential components selected Ru of compounds from a structure represented by the following formula (b).

  The heat-resistant resin precursor composition of the present invention preferably contains 0.001 to 30 parts by weight of the above compound with respect to 100 parts by weight of the polymer. More preferably, it is 0.005-20 weight part, More preferably, it is 0.01-15 weight part, More preferably, it is 0.05-10 weight part. If it is 0.001 part by weight or more, the adhesive performance will be able to withstand long-term storage, and if it is 30 parts by weight or less, there is an advantage that the mechanical properties of the film after thermosetting are improved.

In order to impart negative photosensitivity to the polymer whose main component is the structural unit represented by the general formula (4), (5) , (5) ′, (5) ″ , (7), R ¹⁷ , R ¹⁸ , R ²¹ , R ²¹ ′, R ²¹ ″, R ²⁶ and R ²⁷ components include ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, ethyl methacrylamide, propyl methacryl It is also possible to use an amide group, an ethylacrylamide group, a propylacrylamide group, and / or a compound represented by the general formula (12) newly containing an ethylenically unsaturated double bond and an amino group. is there.

In the general formula (12), R ²⁹ , R ³⁰ and R ³¹ represent an organic group having 1 to 30 carbon atoms. The organic group is preferably an aliphatic organic group, and examples thereof include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. Furthermore, it is preferable that at least one of R ²⁹ , R ³⁰ and R ³¹ contains an ethylenically unsaturated double bond in order to improve the photosensitive performance.

  Preferred specific examples of the compound represented by the general formula (12) include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethyl Examples include aminopropyl acrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl methacrylamide, dimethylaminoethyl acrylamide, and diethylaminoethyl acrylamide. But it is not limited to. The compound represented by the general formula (12) may be a single species or a mixture of two or more species.

  A preferable content of the compound represented by the general formula (12) is 20 to 500 mol%, preferably 50 to 300 mol%, and more preferably 70 to 250 mol% with respect to the carboxyl group of the polymer. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting.

Further, the polymer having a main component of one or more structural units selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7) is negative. When imparting photosensitivity of the mold, it is possible to use a photoinitiator and / or a photosensitizer.

  Suitable photoinitiators for the present invention include aromatic amines such as N-phenyldiethanolamine and N-phenylglycine, aromatic ketones such as Michler's ketone, and cyclic oxime compounds represented by 3-phenyl-5-isoxazolone. , Chain oxime compounds represented by 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime, benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzylketone, fluorenone, thioxanthone, 2-methylthioxanthone And thioxanthone derivatives such as 2-isopropylthioxanthone, but are not limited thereto.

  Examples of photosensitizers suitable for the present invention include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, aminocoumarins such as 7-diethylaminobenzoylcoumarin, 3,3′-carbonylbis (diethylaminocoumarin), and benzanthrone. And aromatic ketones such as phenanthrenequinone, which are generally used for photocurable resins. In addition, it may be preferably used as long as it is used as a charge transfer agent for an electrophotographic photoreceptor.

  The photoinitiator or photosensitizer is preferably contained in an amount of 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer in the present invention. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting. These photoinitiators and sensitizers can be used alone or in admixture of two or more.

  In order to improve the photosensitive performance of the composition of the present invention, a photoreactive monomer can be appropriately used. Photoreactive monomers include 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate ethylene glycol dimethacrylate, diethylene glycol dimethacrylate triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, methylene Examples include, but are not limited to, bismethacrylamide and methylenebisacrylamide. The photoreactive monomer is preferably contained in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the polymer. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting. These photoreactive monomers can be used alone or in admixture of two or more.

The polymer having as a main component one or more structural units selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7) is exposed. It should be as transparent as possible to actinic radiation. Therefore, the absorbance at 365 nm of a pre-baked film produced using a polymer γ-butyrolactone solution (polymer concentration 40%) is preferably 0.1 or less per 1 μm of film thickness. More preferably, it is 0.08 or less. If it is 0.1 or less, the absorption of the composition with respect to 365 nm actinic radiation becomes small, and there is an advantage that the sensitivity when exposed to this actinic radiation is improved. The pre-baked film referred to here is a thickness of 3 to 4 minutes after the solution was applied to a Pyrex (registered trademark) glass substrate and baked on a hot plate at 120 ° C. (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). It is a 10 μm film.

A polymer mainly composed of one or more structural units selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7) is a photoacid. Positive photosensitivity can be imparted by adding a generator. In particular, it is preferably used in a polymer having as a main component a structural unit represented by general formula (5 ), general formula (5) ′, general formula (5) ″ , general formula (6), or general formula (7). .

  Examples of the photoacid generator include a quinonediazide compound and a sulfonic acid onium salt compound, but a quinonediazide compound is preferable, and an o-quinonediazide compound is particularly preferable. The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone. Examples include amide-bonded ones. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. When 50 mol% or more is substituted with quinonediazide, there is an advantage that the solubility in an alkali developer is improved and a fine pattern having a high contrast with the unexposed portion can be obtained. By using such a quinonediazide compound, a positive photosensitive resin precursor composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to.

  Polyhydroxy compounds 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-35XL, TML-BP, TML-HQ TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPPHAP (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 (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Manufactured by Manabu Kogyo Co.) and the like, but not limited to.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Although sulfide etc. are mentioned, it is not limited to these.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. 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.

  Moreover, the molecular weight of a preferable quinonediazide compound is 300-1500. More preferably, it is 350-1200. When it is 300 or more, the exposure sensitivity is high, and when it is 1500 or less, there is an advantage that the mechanical properties of the film after thermosetting are improved.

  In addition, the content of the quinonediazide compound is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  The heat resistant resin precursor composition of the present invention may contain a dissolution regulator. As the dissolution regulator, any compound can be preferably used as long as it is a compound generally used as a solubility regulator in a positive resist, such as a polyhydroxy compound, a sulfonamide compound, and a urea compound. In particular, a polyhydroxy compound which is a raw material for synthesizing a quinonediazide compound is preferably used. Preferred polyhydroxy compounds include, for example, 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, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, and the like. Among these, particularly preferred polyhydroxy compounds are, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F It is. By containing the compound having a phenolic hydroxyl group, the obtained resin composition is hardly dissolved in an alkali developer before exposure, and is easily dissolved in an alkali developer upon exposure. Development is easy in a short time.

The dissolution regulator is mainly composed of one or more structural units selected from the structural units represented by the general formulas (4), (5), (5) ′, (5) ″, (6) and (7). Preferably it is 1-100 weight part with respect to 100 weight part of polymers, More preferably, it mix | blends in the range of 5-40 weight part. When the amount is 1 part by weight or more, there are advantages that development can be performed in a shorter time and exposure sensitivity is high. Moreover, there exists an advantage that the heat resistance of the film | membrane after thermosetting improves that it is 100 weight part or less.

  The heat resistant resin precursor composition of the present invention may contain a thermal crosslinking agent. As the thermal crosslinking agent, any compound such as a methylol compound, a methoxymethylol compound, or a urea compound can be preferably used. In particular, a methoxymethylol compound is preferably used from the standpoint of stability after exposure.

  Specific examples thereof include, but are not limited to, the following compounds.

  By containing these thermal crosslinking agents, the resulting photosensitive resin precursor composition hardly dissolves in the alkali developer before exposure, and easily dissolves in the alkali developer upon exposure. There is little reduction and development can be performed in a short time, and in addition, the shrinkage after curing is reduced.

  The content of the thermal crosslinking agent is preferably 0.5 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

  Solvents used in the present invention include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, etc. Ethers, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, etc., esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, aromatic hydrocarbons such as toluene, xylene, etc., alone or in combination. Can be used.

  In order to improve the adhesion to silicon-based materials such as silicon, silicon nitride, silicon oxide, and phosphorus silicate glass, a silane coupling agent, a titanium chelating agent, or the like can be used in combination. It is preferable to contain 0.5 to 10 parts by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent, and an aluminum chelating agent with respect to 100 parts by weight of the polymer.

In addition, as a method for improving the adhesiveness with the silicon-based material, R ¹⁶ , R ²⁰ , and General Formulas (4), (5), (5) ′, (5) ″, (6), and (7) It is also preferably used to copolymerize 1 to 10 mol% of R ²⁰ ′, R ²⁰ ″, R ²³ and R ²⁵ with a residue of a diamine compound having a siloxane bond. Specific examples of the diamine compound having a siloxane bond include, but are not limited to, bis (3-aminopropyl) tetramethyldisiloxane .
In addition, it is possible to further improve the adhesion by pre-treating the surface of the silicon-based material in advance. Examples of the pretreatment method include the following methods. A solution obtained by dissolving 0.5 to 20 parts by weight of the coupling agent described above in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. In some cases, the reaction between the surface of the silicon-based material and the coupling agent is allowed to proceed by applying a temperature of 50 to 300 ° C. thereafter.

  Further, if necessary, a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate for the purpose of improving the wettability between the heat-resistant resin precursor composition of the present invention and the substrate to which the composition is applied. , Alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be contained in the composition. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  The heat-resistant resin precursor composition of the present invention is obtained by stirring and mixing the above-described polymer, the compound represented by the general formula (2) or (3), and if necessary, a photoacid generator, a solvent, and other additives. be able to. The conditions for stirring and mixing are not particularly limited.

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

  The heat resistant resin precursor composition of the present invention is applied onto a substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide or the like, or a substrate on which an electrode and / or wiring made of a metal material such as copper, gold, or titanium-based metal is used is used. It is not limited. 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 becomes 0.1 to 150 μm.

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

  Next, the 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-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. . When photosensitivity is not given to the heat resistant resin precursor composition, it is necessary to form another layer of photoresist film on the heat resistant resin precursor 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 precursor film.

  If the resolution of the pattern at the time of development is improved or the allowable range of development conditions is increased, a baking process may be incorporated before development. 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. Within this range, there are advantages that the reaction proceeds satisfactorily and the development time can be shortened.

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

  A suitable developer can be selected according to the structure of the polymer. 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, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl, which are solvents for the heat-resistant resin precursor composition of the present invention, are used as a developer. Sulfoxide, hexamethylphosphotriamide, etc., methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypro Preferable is also a mixture of a poor solvent of the heat-resistant resin precursor composition of the present invention such as pionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, or a combination of several kinds thereof. To do Kill.

  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 given to the heat resistant resin precursor, the photoresist film formed on the heat resistant resin precursor 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.

  In order to convert the heat resistant resin precursor into a heat resistant resin, a temperature of 200 to 500 ° C. is applied. 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., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned.

  Thus, the photosensitive heat-resistant resin precursor composition in the present invention is preferably used for a semiconductor device as a surface protective film (passivation film, buffer coat film, α-ray shielding film), an interlayer insulating film, or the like.

  Hereinafter, in order to describe the present invention in detail, examples will be described.

Synthesis example 1
Under a dry nitrogen stream, 19 g (0.095 mol) of 4,4′-diaminodiphenyl ether and 1.2 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to a 1 l four-necked flask. ) Was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). To this was added 10.8 g (0.05 mol) of pyromellitic anhydride and 15 g (0.047 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and the mixture was stirred at room temperature for 6 hours. Thus, polyamic acid was obtained. This solution was heated to 40 ° C., 23.8 g (0.20 mol) of dimethylformamide dimethylacetal was added, and the mixture was stirred for 2 hours, and then cooled to room temperature. After the temperature was lowered, 60 g (1 mol) of acetic acid was added and stirred for 1 hour, and then poured into pure water for reprecipitation, and the precipitate was filtered off. The precipitate separated by filtration was dried at 70 ° C. for 120 hours to obtain the desired polymer. 30 g of this polymer was dissolved in 100 g of NMP to obtain a heat-resistant resin precursor stock solution A.

Synthesis example 2
Under a dry air stream, 10.9 g (0.05 mol) of pyromellitic anhydride was dispersed in 100 g of γ-butyrolactone (GBL) in a 500 ml four-necked flask. To this, 13 g (0.1 mol) of 2-hydroxyethyl methacrylate and 7 g of pyridine were added and stirred at 50 ° C. for 2 hours. This solution was ice-cooled, and a solution obtained by dissolving 21 g (0.1 mol) of dicyclohexylcarbodiimide in 25 g of γ-butyrolactone was added dropwise over 15 minutes. Furthermore, a solution in which 10 g (0.05 mol) of 4,4′-diaminodiphenyl ether was dispersed in 25 g of γ-butyrolactone was added dropwise over 10 minutes. This solution was reacted for 3 hours under ice-cooling, and then stirred at 50 ° C. for 1 hour. After completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 3 l of water to form a polyamic acid ester precipitate. This precipitate was collected, washed with water and methanol, and then dried in a vacuum dryer at 50 ° C. for 24 hours. 15 g of this polyamic acid ester powder, 0.75 g of mercaptobenzimidazole, 1 g of trimethylolpropane triacrylate, 2 g of ethylene glycol dimethacrylate, 0.5 g of pt-butylcatechol, 0.5 g of Michler's ketone, 3-methacryloxypropyldimethoxy 0.5 g of silane and 0.5 g of 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime were added to obtain a heat-resistant resin precursor stock solution B imparted with negative photosensitivity.

Synthesis example 3
Instead of 10 g (0.05 mol) of 4,4′-diaminodiphenyl ether, 3.8 g (0.025 mol) of 3,5-diaminobenzoic acid and 5 g (0.025 mol) of 4,4′-diaminodiphenyl ether were used. Except having used, it carried out similarly to the synthesis example 2, and obtained the heat resistant resin precursor stock solution C provided with negative photosensitivity.

Synthesis Example 4 Synthesis of hydroxyl group-containing acid anhydride In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl glycidyl ether 34.2 g (0.3 mol) was dissolved in 100 g of ethyl acetate and cooled to −15 ° C. Thereto was added dropwise 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of ethyl acetate so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 4 hours.

  This solution was concentrated with a rotary evaporator and charged into 1 liter of toluene to obtain an acid anhydride. This is shown below. The material obtained did not have a clear melting point up to 350 ° C.

Synthesis Example 5 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, 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 stirred at −15 ° C. for 4 hours and then returned to room temperature. The solution was concentrated on a rotary evaporator, and the resulting solid was recrystallized with a solution of tetrahydrofuran and ethanol.

  The solid collected by recrystallization was dissolved in 100 ml of ethanol and 300 ml of tetrahydrofuran, 2 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 4 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the reaction was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a diamine compound. This is shown below. The obtained solid was used for the reaction as it was.

Synthesis Example 6
Under a dry nitrogen stream, 36.6 g (0.1 mol) of BAHF was dissolved in 100 ml of N, N-dimethylacetamide and cooled to −5 ° C. To this was added 26.4 g (0.3 mol) of glycidyl methyl ether, and 29.5 g (0.1 mol) of diphenyl ether dicarboxylic acid chloride was dissolved in 50 g of acetone. The temperature of the reaction solution exceeded 0 ° C. It was dripped so that there was no. After completion of the dropwise addition, the temperature of the solution was raised to 10 ° C. and stirring was continued for 1 hour, and then stirring was continued at 20 ° C. for 6 hours. After completion of the stirring, the solution was poured into 10 l of water to obtain a polyhydroxyamide precipitate. This precipitate was collected by filtration and then dried in a vacuum dryer at 60 ° C. for 20 hours.

  10 g of this dried polyhydroxyamide acid (polybenzoxazole precursor) solid and orthonaphthoquinonediazide sulfonic acid ester as 4NT-300 (1,3,4 per 1 mol of 2,3,4,4′-tetrahydroxybenzophenone) -Ester obtained by reacting 3 mol of naphthoquinone-2-diazide-5-sulfonyl chloride: manufactured by Toyo Gosei Kogyo Co., Ltd. 2 g was dissolved in 20 g of GBL (boiling point at 1 atm is 206 ° C.), and heat resistant resin A precursor stock solution D was obtained.

Synthesis example 7
18.3 g (0.05 mol) of BAHF was dissolved in 150 ml of ethanol and cooled to 5 ° C. To this, 11.2 g (0.1 mol) of potassium-t-butoxide was gradually added. Further, 21.8 g (0.1 mol) of dicarbonate-t-butyl was gradually added and stirring was continued for 2 hours to obtain a diamine compound in which the hydroxyl group of BAHF was protected with a t-butoxycarbonyl group. This solution was poured into 1 l of water to obtain a precipitate. This precipitate was collected by filtration and dried in a vacuum dryer at 30 ° C. for 20 hours.

  Under a dry nitrogen stream, 27.5 g (0.075 mol) of BAHF and 13.4 g (0.25 mol) of a diamine in which the hydroxyl group of BAHF synthesized above was protected with a t-butoxycarbonyl group in 150 ml of N, N-dimethylacetamide And cooled to -5 ° C. A solution in which 52.8 g (0.6 mol) of glycidyl methyl ether was added and 20.3 g (0.1 mol) of isophthalic acid dichloride was dissolved in 100 g of acetone, the temperature of the reaction solution did not exceed 0 ° C. Was dropped. After completion of the dropwise addition, the temperature of the solution was raised to 10 ° C. and stirring was continued for 1 hour, and then stirred at 20 ° C. for 6 hours. After completion of the stirring, the solution was poured into 10 l of water to obtain a polyhydroxyamidamic acid precipitate. This precipitate was collected by filtration and then dried in a vacuum dryer at 60 ° C. for 20 hours. 10 g of this dried polyhydroxyamide acid (polybenzoxazole precursor) solid and 1 g of NAI-105 (manufactured by Midori Chemical Co., Ltd.) as a photoacid generator are dissolved in 20 g of GBL, and a heat-resistant resin precursor stock solution E is obtained. Obtained.

Synthesis Example 8
Under a dry nitrogen stream, 20 g (0.1 mol) of 4,4′-diaminodiphenyl ether was dissolved in 350 g of GBL in a 1 l four-necked flask. Thereto was added 71.4 g (0.1 mol) of a hydroxyl group-containing acid anhydride synthesized in Synthesis Example 4 together with 40 g of GBL, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 40 ° C. for 2 hours. Further, 23.8 g (0.2 mol) of N, N-dimethylformamide dimethylacetal was added, stirred at 40 ° C. for 2 hours, and cooled to room temperature. Thereafter, 60 g (1 mol) of acetic acid was added and stirred at room temperature for 1 hour. This was poured into 10 L of water, and the precipitate was filtered off and dried at 70 ° C. for 120 hours to obtain the desired polymer. 35 g of the obtained polymer was dissolved in 65 g of GBL, and 5.5 g of o-quinonediazide compound 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) was added thereto to obtain a heat resistant resin precursor stock solution F.

Synthesis Example 9
Under a dry nitrogen stream, 24.2 g (0.04 mol) of the hydroxyl group-containing diamine compound synthesized in Synthesis Example 5 was dissolved in 100 g of NMP in a 1 l four-necked flask, and 3,3 ′, 4,4′-diphenyl ether tetra Carboxylic dianhydride 12.4g (0.04mol) was added and it stirred at 80 degreeC for 3 hours. Further, 8.8 g (0.06 mol) of N, N-dimethylformamide diethyl acetal was added, stirred at 40 ° C. for 2 hours, and cooled to room temperature. Thereafter, 24 g (0.4 mol) of acetic acid was added and stirred at room temperature for 1 hour. This was poured into 5 L of water, the precipitate was filtered off, and dried at 70 ° C. for 120 hours to obtain the desired polymer. 35 g of the obtained polymer was dissolved in 65 g of GBL, and 3.5 g of o-quinonediazide compound 4NT-300 was mixed therewith to obtain a heat resistant resin precursor stock solution G.

Synthesis Example 10
Under a dry nitrogen stream, 24.8 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 59.3 g of n-butyl alcohol were placed in a 500 ml four-necked flask and reacted at 95 ° C. for 5 hours. It was. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester. Next, 95.2 g of thionyl chloride and 70 g of toluene were placed in a 300 ml four-necked flask under a dry nitrogen stream and stirred at 40 ° C. for 3 hours. Excess thionyl chloride was removed azeotropically with toluene by reduced pressure. 186 g of NMP was added to obtain a solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di n-butyl ester dichloride.

  Next, 95 g of NMP, 8.5 g of 3,5-diaminobenzoic acid, and 4.8 g of 4,4'-diaminodiphenyl ether were placed in a 500 ml four-necked flask under a dry nitrogen stream and dissolved by stirring. Thereafter, 12.7 g of pyridine was added, and while keeping the temperature at 0 to 5 ° C., a solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour, Stirring was continued for 1 hour. The obtained solution was poured into 5 l of water, and the precipitate was collected and washed, and then dried under reduced pressure to obtain polyamic acid n-butyl ester.

  30 g of polyamic acid n-butyl ester, 7.5 g of a compound obtained by reacting 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3; 2 g of p-nitrobenzyl) -9,10-diethoxyanthracene-2-sulfonate was dissolved in 45 g of NMP with stirring to obtain a heat-resistant resin precursor stock solution H.

Synthesis Example 11
Instead of 19 g (0.095 mol) of 4,4′-diaminodiphenyl ether, 16 g (0.08 mol) of 4,4′-diaminodiphenyl ether and 2.2 g (0.02 mol) of 3-aminophenol were used. In the same manner as in Synthesis Example 1, a heat resistant resin precursor stock solution I was obtained.

Synthesis Example 12
Instead of using 20 g (0.1 mol) of 4,4′-diaminodiphenyl ether, 16 g (0.08 mol) of 4,4′-diaminodiphenyl ether and 2.2 g (0.02 mol) of 3-aminophenol were used. In the same manner as in Synthesis Example 8, a heat resistant resin precursor stock solution J was obtained.

Synthesis Example 13
Instead of 24.2 g (0.04 mol) of the hydroxyl group-containing diamine compound synthesized in Synthesis Example 5, 19.3 g (0.032 mol) of the hydroxyl group-containing diamine compound synthesized in Synthesis Example 5 and bis (3-amino Propyl) tetramethyldisiloxane 0.5 g (0.002 mol) and 3-aminophenol 2.2 g (0.02 mol) were used in the same manner as in Synthesis Example 9 to obtain a heat-resistant resin precursor stock solution K. .

Synthesis Example 14 Synthesis of Adhesion Improving Agent (4SS) 500 g of ethyl acetate was placed in a 1000 ml flask, and 24.84 g (0.1 mol) of 4,4′-dithiodianiline was added thereto. Then, 20.42 g (0.2 mol) of acetic anhydride was added, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the precipitate was filtered off, washed repeatedly with ethyl acetate, and then dried under reduced pressure at 40 ° C. to obtain the desired compound. This is shown in the following formula (15). This is hereinafter referred to as 4SS.

Synthesis Example 15 Synthesis of Adhesion Improving Agent (2SS) 500 g of N-methyl-2-pyrrolidone was placed in a 1000 ml flask, and 24.84 g (0.1 mol) of 2,2′-dithiodianiline was added thereto. Then, 20.42 g (0.2 mol) of acetic anhydride was added, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the liquid was poured into 5 L of pure water, and the precipitate was separated by filtration. This was dried under reduced pressure at 40 ° C. to obtain the desired compound. This is shown in the following formula (16). This is hereinafter referred to as 2SS.

Synthesis Example 16 Synthesis of adhesion improver (4MTE) 500 g of N-methyl-2-pyrrolidone was placed in a 1000 ml flask, and 13.92 g (0.1 mol) of 4 (methylthio) aniline was added thereto. Then, 20.42 g (0.2 mol) of acetic anhydride was added, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the liquid was poured into 5 L of pure water, and the precipitate was separated by filtration. This was dried under reduced pressure at 40 ° C. to obtain the desired compound. This is shown in the following formula (17). This is hereinafter referred to as 4MTE.

Synthesis Example 17 Synthesis of Adhesion Improving Agent (2MTE) 500 g of N-methyl-2-pyrrolidone was placed in a 1000 ml flask, and 13.92 g (0.1 mol) of 2 (methylthio) aniline was added thereto. Then, 20.42 g (0.2 mol) of acetic anhydride was added, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the liquid was poured into 5 L of pure water, and the precipitate was separated by filtration. This was dried under reduced pressure at 40 ° C. to obtain the desired compound. This is shown in the following formula (18). This is hereinafter referred to as 2MTE.

Examples 1-26 and Comparative Examples 1-14
Hereinafter, in Examples 1 to 14, the heat resistant resin precursor stock solution shown in Table 1 and the compound represented by the general formula (2) or (3) are mixed to produce a heat resistant resin precursor composition. did. Content of Table 1 shows the quantity of the compound represented by General formula (2) or (3) in a heat resistant resin precursor composition. In Comparative Examples 1 to 11, a heat resistant resin precursor composition shown in Table 2 was mixed with an adhesion improver to prepare a heat resistant resin precursor composition. In Comparative Examples 12 to 14, no adhesion improver was added. About the obtained heat resistant resin precursor composition, the adhesiveness with a metal material and room temperature stability were evaluated using the following method. The evaluation results are shown in Tables 1 and 2.

1) Adhesiveness Adhesiveness with a metal material was evaluated by the following method. First, a substrate (copper sputter substrate, gold sputter substrate, titanium sputter substrate) having a metal material layer formed on a surface by sputtering copper, gold, and titanium on a silicon wafer and having a thickness of 200 to 500 nm was prepared. A heat resistant resin precursor composition is spin-coated on this substrate, then baked for 3 minutes on a hot plate at 120 ° C. (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), and finally a prebake having a thickness of 8 μm. A membrane was prepared. This film was put into an oven and cured at 170 ° C. for 30 minutes and then at 320 ° C. for 1 hour to obtain a polyimide film. Cure was performed in nitrogen (oxygen concentration of 100 ppm or less). The cured film was cut into 10 rows and 10 columns at 2 mm intervals, and the adhesive properties between the metal material and the heat-resistant resin were determined according to how many squares were peeled off with cello tape (registered trademark). Evaluation was performed. For the gold sputtered substrate, a peeling test was performed immediately after curing, and those with a peeled number of less than 10 passed and those with 10 or more were rejected. For copper sputtered substrates and titanium sputtered substrates, the film after curing was subjected to a 400 hour pressure cooker test (PCT) treatment and then subjected to a peeling test. Passed. The PCT treatment was performed under a saturation condition of 121 ° C. and 2 atm.

2) Room temperature stability The heat resistant resin precursor composition was stored at room temperature (23 ° C) for 2 weeks, and then the adhesiveness was evaluated in the same manner as described above. The criteria for passing and failing were the same as those before standing at room temperature.

Table 1 and the results in Table 2, b) it can be seen that it is possible to achieve both adhesion properties and room temperature stability of the metal material by which Ru of compound selected from those of the structure shown in formula (b).

Claims (6)

a) a polymer mainly composed of one or more structural units selected from the structural units represented by the following general formulas (4), (5), (5) ′, (5) ″, (6) and (7) , b) heat-resistant resin precursor composition comprising the following formula (b) to show that Ru of compound selected from those of the structure.

(R ¹⁵ is 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylhexafluoropropanetetra Selected from carboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid This is a residue obtained by removing four carboxyl groups from a tetracarboxylic acid compound.
R ¹⁶ is para-phenylenediamine, meta-phenylenediamine, methyl para-phenylenediamine, methyl m-phenylenediamine, dimethyl paraphenylene diamine, dimethyl meta-phenylenediamine, trimethyl paraphenylenediamine, trimethyl metaphenylene diamine, tetramethyl paraphenylenediamine, tetramethyl meta Phenylenediamine, trifluoromethylparaphenylenediamine, trifluoromethylmetaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methylmetaphenylenediamine, methoxyparaphenylenediamine, methoxymetaphenylenediamine, trifluoromethoxy Paraphenylenediamine, trifluoromethoxymetaphenylenediamine, fluoropa Laphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxycarbonylmetaphenylenediamine , Diaminodiphenylmethane, bis (aminomethylphenyl) methane, bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl) methane, bis (aminodiethylphenyl) ) Methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (aminotri Fluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (aminodimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) Hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) ) Hexafluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bi (Aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (aminoethyl) Phenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl) ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (Aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) methane and bis (amino It is a residue obtained by removing two amino groups from a diamine compound selected from (nophenoxyphenyl) sulfone, or a residue obtained by removing two amino groups from a hydrogenated compound of the diamine compound.
R ¹⁷ and R ¹⁸ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. R ¹⁷ and R ¹⁸ may be the same or different. m ₂ is an integer of 3 to 100,000.
R ¹⁹ is 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylhexafluoropropanetetracarboxylic acid. Selected from acids, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid A residue obtained by removing four carboxyl groups from a tetracarboxylic acid compound. Ar ⁴ ′ and Ar ⁴ ″ have a structure as shown in the above formula.
R ²⁰ ′ is paraphenylenediamine, metaphenylenediamine, methylparaphenylenediamine, methylmetaphenylenediamine, dimethylparaphenylenediamine, dimethylmetaphenylenediamine, trimethylparaphenylenediamine, trimethylmetaphenylenediamine, tetramethylparaphenylenediamine, tetramethyl Metaphenylenediamine, trifluoromethylparaphenylenediamine, trifluoromethylmetaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methylmetaphenylenediamine, methoxyparaphenylenediamine, methoxymetaphenylenediamine, trifluoro Methoxyparaphenylenediamine, trifluoromethoxymetaphenylenediamine, fluoro Laphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxycarbonylmetaphenylenediamine , Diaminodiphenylmethane, bis (aminomethylphenyl) methane, bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl) methane, bis (aminodiethylphenyl) ) Methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (aminoto Fluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (aminodimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) hexa Fluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) Hexafluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, Sus (aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (amino Ethylphenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl) ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, Bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) methane and bis (a Roh phenoxyphenyl) is a residue obtained by removing two amino groups from hydrogenated compound residue excluding two amino groups from a diamine compound selected from the sulfone or the diamine compound. The following structural formulas (10) and (10) '' containing R ²⁰ and R ²⁰ ″ are diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, 1,3-diamino-4-hydroxybenzene, 1,3. -Diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) sulfone Bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexaful Ropropane, 1,5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, bis (3-amino-4-hydroxyphenyl) propane and bis (4-amino-3-hydroxy) A residue obtained by removing two amino groups from a hydroxy group-containing diamine compound selected from phenyl) propane or a structure represented by the following formula (11).
R ²¹ , R ^{21 ′} and R ^{21 ″} represent hydrogen or an organic group having 1 to 20 carbon atoms. m ₃ , m ₃ ′ and m ₃ ″ are integers from ₃ to 100,000, and s and s ″ are 1 or 2.
R ²² represents diphenyl ether-3,3′-dicarboxylic acid, diphenyl ether-3,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, isophthalic acid, benzophenone-3,3′-dicarboxylic acid, benzophenone-3. , 4′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, diphenylsulfone-3,3′-dicarboxylic acid, diphenylsulfone-3,4′-dicarboxylic acid and diphenylsulfone-4,4′-dicarboxylic acid A residue obtained by removing two carboxyl groups from a selected dicarboxylic acid compound.
R ²³ is di-amino-dihydroxypyrimidine, diaminodihydroxy pyridine, 3, 3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4- Hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 1, 5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3 ′ -Dihydroxydiphenyl ether and 3,4'-diamino-3,4'-dihydro From hydroxy group-containing diamine compound selected from shea ether is a residue obtained by removing two amino groups and two hydroxyl groups.
m4 represents an integer of ₃ to 100,000.
R ²⁴ is 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylhexafluoropropanetetracarboxylic acid. Selected from acids, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid A residue obtained by removing four carboxyl groups from a tetracarboxylic acid compound.
R ²⁵ is 2, 5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diamino terephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, 4 A carboxyl group and two carboxyl groups from a carboxyl group-containing diamine compound selected from 4,4'-diamino 3,3'-dicarboxybiphenyl and 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl It is a residue excluding an amino group.
R ^{26 to} R ²⁸ represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 20 carbon atoms. R ^{26 to} R ²⁸ may be the same or different. u is 1 or 2, and R ²⁸ when u is 2 may be a single species or a mixture of two or more species. m5 represents an integer of ₃ to 100,000. )

The heat-resistant resin precursor composition according to claim 1, further comprising a photoacid generator. The heat-resistant resin precursor composition according to claim 2, wherein the photoacid generator is an o-quinonediazide compound. The heat-resistant resin precursor composition according to claim 1, wherein at least one of both ends of the polymer contains at least one selected from a phenol group and a thiophenol group. The heat-resistant resin precursor composition according to claim 1, wherein the polymer is obtained by reprecipitation. A semiconductor device having an electrode and / or wiring made of a metal material and an insulating film, wherein the insulating film contains the heat-resistant resin precursor composition according to any one of claims 1 to 5, and A semiconductor device which is in contact with at least one metal material selected from copper, gold, titanium, titanium nitride, titanium tungsten, and nickel.