WO2011001493A1 - 有機溶媒に可溶な、pmda、dade、da、ビス(アミノ-4-ヒドロキシフェニル)スルホン成分を含むポリイミドおよびその製造方法 - Google Patents
有機溶媒に可溶な、pmda、dade、da、ビス(アミノ-4-ヒドロキシフェニル)スルホン成分を含むポリイミドおよびその製造方法 Download PDFInfo
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- 0 C*c(cc1)cc(C(N2*)=O)c1C2=O Chemical compound C*c(cc1)cc(C(N2*)=O)c1C2=O 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N Nc(cc1)ccc1Oc(cc1)ccc1N Chemical compound Nc(cc1)ccc1Oc(cc1)ccc1N HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- XWKLXPPQZPXMGF-UHFFFAOYSA-N [O-][NH+](c(c1c2)cc3c2[NH+]([O-])O[NH+]3[O-])O[NH+]1[O-] Chemical compound [O-][NH+](c(c1c2)cc3c2[NH+]([O-])O[NH+]3[O-])O[NH+]1[O-] XWKLXPPQZPXMGF-UHFFFAOYSA-N 0.000 description 1
- NBLLHFHMOBEMOH-UHFFFAOYSA-N [O-][NH+](c(c1c2)ccc2-c(cc23)ccc2[NH+]([O-])O[NH+]3[O-])O[NH+]1[O-] Chemical compound [O-][NH+](c(c1c2)ccc2-c(cc23)ccc2[NH+]([O-])O[NH+]3[O-])O[NH+]1[O-] NBLLHFHMOBEMOH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4461—Polyamides; Polyimides
Definitions
- the present invention relates to a polyimide soluble in an organic solvent and a method for producing the same. More specifically, the present invention relates to a super heat-resistant polyimide containing bis (3-amino-4-hydroxyphenyl) sulfone (hereinafter also referred to as “HOABSO 2 ”), PMDA, DADE, and DA components.
- HOABSO 2 bis (3-amino-4-hydroxyphenyl) sulfone
- KAPTON registered trademark
- Upilex registered trademark
- Kapton was first produced by DuPont in 1960 and synthesized from pyromellitic dianhydride (hereinafter also referred to as “PMDA”) and 1,4-diaminodiphenyl ether.
- This polyimide has characteristics such as a glass transition temperature (Tg) of 420 ° C. and a thermal decomposition start temperature (Tm) of 500 ° C. or more, and is a polymer excellent in electrical insulation, mechanical strength and chemical resistance. Widely used as materials for vehicles, electronic / electrical parts, semiconductor materials, etc. (Non-patent Document 1: Polyimides; D. Wilson, H. D. Steinberger, R. M. Morgenrother; 1990)).
- Upilex is a polyimide film manufactured by Ube Industries, Ltd. in 1980, and is synthesized from biphenyltetracarboxylic dianhydride (hereinafter also referred to as “BPDA”) and 1,4-diaminobenzene.
- BPDA biphenyltetracarboxylic dianhydride
- This polyimide has heat resistance of Tg> 500 ° C. and Tm> 550 ° C. (Non-patent Document 1).
- Kapton and Upilex are sparingly soluble in organic solvents, so tetracarboxylic dianhydride and aromatic amine are polycondensed in polar organic solvent to synthesize high molecular weight polyamic acid, then cast and heated ( 400 ° C. or higher) and an imidization reaction while removing the organic solvent. That is, a conventional polyimide has been obtained by forming a coating film from a polyamic acid solution and simultaneously performing an imidization reaction and film formation.
- polyamic acid is easily decomposed with water, and the quality is maintained for about 3 months even if it is stored frozen.
- polyamic acid easily undergoes an exchange reaction in the solution, when other components are added, it becomes a random copolymer by the exchange reaction. It is difficult to improve the performance of the random copolymer by modification.
- the method of removing the organic solvent from the polyamic acid solution and synthesizing the polyimide was not a method adequately suited for industrial production.
- Patent Document 1 International Publication No. 2008/120398 pamphlet
- Patent Document 2 International Publication No. 2008/155811 pamphlet
- BPDA biphenyltetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- DAT 2,4-diaminotoluene
- This polyimide is obtained by reacting DOD with both ends of BPDA to obtain an oligomer having amino groups at both ends, by reacting the oligomer with 2 molar equivalents of PMDA and 1 molar equivalent of DAT. , A second step of obtaining an oligomer having both ends of which are PMDA-derived acid anhydride groups, and a third step of polymerizing the oligomer by reacting with DAT.
- PMDA and BPDA which are acid anhydride components
- Patent Document 3 A. Berger, US Pat. No. 4,011,297 (1993), Patent Document 4: US Patent). No. 4,359,572 (1983)).
- Patent Document 4 a method using toluenesulfonic acid or phosphoric acid as a catalyst is known.
- the catalyst obtained in this way has a catalyst remaining in the solution, the catalyst may be deteriorated when formed into a film. Therefore, it is necessary to remove the catalyst from the solution.
- Patent Document 5 Y. Oie, H. Itatani, US Pat. No. 5502142 (1996). As shown below, this catalyst becomes an acid ion species and a base ion species in the presence of water, and causes an equilibrium reaction to become a lactone and a base when water is removed.
- Polyimides soluble in organic solvents are expected to be used for new applications such as high heat-resistant adhesives and coating agents.
- higher functionality is required for polyimide as represented by further improvement in heat resistance.
- the solubility of polyimide in an organic solvent may be reduced. That is, a polyimide having excellent heat resistance and soluble in an organic solvent is required, but such a polyimide has not yet existed.
- an object of the present invention is to provide a polyimide excellent in heat resistance and soluble in an organic solvent, and a method for producing the same.
- the present invention (1) pyromellitic dianhydride (PMDA), (2) Carboxylic acid dianhydrides (DA) including biphenyltetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), (3) Provided is a polyimide soluble in an organic solvent obtained by polymerizing diaminodiphenyl ether (DADE) and (4) bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ).
- PMDA pyromellitic dianhydride
- DA Carboxylic acid dianhydrides
- BPDA biphenyltetracarboxylic dianhydride
- BTDA benzophenone tetracarboxylic dianhydride
- a polyimide soluble in an organic solvent obtained by polymerizing diaminodiphenyl ether (DADE) and (4) bis (3-amino-4-hydroxyphenyl) sulf
- the polyimide preferably has a repeating unit represented by the general formula (I). ⁇ [PMDA]-[HOABSO 2 ]-[PMDA] ⁇ [DADE]-[DA]-[DADE] ⁇ [PMDA]-[HOABSO 2 ]-[PMDA] ⁇ U 1 ⁇ (I) ⁇
- [PMDA] is the pyromellitic dianhydride residue
- [HOABSO 2 ] is the bis (3-amino-4-hydroxyphenyl) sulfone residue
- [DADE] is the diaminodiphenyl ether residue
- [DA] is the carboxylic acid dianhydride residue
- U 1 is, X 1 or X 1, - a group represented by [DA] -X 1, (Where X 1 represents a phenylenediamine residue, an alkyl-substituted phenylenediamine residue, a diaminodiphenylsulfone residue, a bis (aminoph
- the polyimide may be a polyimide having a repeating unit represented by the general formula (III).
- [HOABSO 2 ] is the bis (3-amino-4-hydroxyphenyl) sulfone residue and [DA]
- X 3 is defined as above
- [DADE] and [DA] [DADE] and [PMDA]
- binding of X 3 and [PMDA] is an imide bond
- the bonds of [HOABSO 2 ] and [PMDA] are bonds represented by the general formula (i) or (ii).
- a preferred embodiment of the present invention is a polyimide containing a repeating unit represented by the general formula (1).
- Q is a single bond or a carbonyl group;
- R is independently a hydrogen atom or a carboxyl group, a to h represent the positions of carbon atoms, and when carbons a, c, e, and g are bonded to R, they represent that carbons b, d, f, and h are bonded to an oxazole group,
- Y 1 is a group represented by the general formulas (11) to (13),
- R 10 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- Ar 1 is independently a group represented by the general formulas (11) to (13), and Q is as defined above.
- Q represents as defined above.
- * Represents that a phenylene group and an imide group are bonded.
- Another preferred embodiment of the present invention is a polyimide containing a repeating unit represented by the general formula (2).
- Q is a single bond or a carbonyl group;
- R is independently a hydrogen atom or a carboxyl group, a to d represent the positions of carbon atoms, and when the carbons a and c are bonded to R, the carbons b and d are bonded to the oxazole group,
- Y 2 is a group represented by the general formula (21), (22) or (23),
- Ar 1 is a group represented by the general formulas (11) to (13),
- R 10 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- Another preferred embodiment of the present invention is a polyimide containing a repeating unit represented by the general formula (3-1).
- Q is a single bond or a carbonyl group;
- R is independently a hydrogen atom or a carboxyl group, a to d represent the positions of carbon atoms, and when the carbon atoms a and c are bonded to R, the carbon atoms b and d are bonded to the oxazole group,
- Ar 1 is independently a group represented by general formulas (11) to (13),
- Y 3 is a single bond or a group represented by the formula (31),
- R 1 independently represents a hydrogen atom or a carboxyl group
- Q is defined as above, and e to h are defined in the same manner as a to d).
- * Represents that a phenylene group and an imide group are bonded.
- Another preferred embodiment of the present invention is a polyimide containing a repeating unit represented by the general formula (3-2).
- Q is a single bond or a carbonyl group;
- R is independently a hydrogen atom or a carboxyl group, a to d represent the positions of carbon atoms, and when the carbons a and c are bonded to R, the carbons b and d are bonded to the oxazole group,
- Ar 1 is independently a group represented by general formulas (11) to (13),
- (A1) 1 molar equivalent of carboxylic acid dianhydride (DA) including biphenyltetracarboxylic dianhydride (BPDA) or benzophenonetetracarboxylic dianhydride (BTDA) and 2 molar equivalents of diamino
- DA carboxylic acid dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- BTDA benzophenonetetracarboxylic dianhydride
- DADE diphenyl ether
- the oligomer obtained in the step A1 is reacted with 4 molar equivalents of pyromellitic dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ).
- PMDA pyromellitic dian
- BPDA biphenyltetracarboxylic dianhydride
- a method for producing polyimide comprising a step of reacting 1 molar equivalent of carboxylic acid dianhydride (DA) including benzophenone tetracarboxylic dianhydride (BTDA) with 2 molar equivalent of aromatic diamine to obtain a polymer.
- DA carboxylic acid dianhydride
- BTDA benzophenone tetracarboxylic dianhydride
- (B1) reacting 2 molar equivalents of pyromellitic dianhydride (PMDA) with 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ), Obtaining an oligomer whose both ends are PMDA-derived acid anhydride groups; (B2) Carboxylic acid dianhydride (DA) 2 molar equivalents and 4 molar equivalents including the oligomer obtained in step B1 and biphenyltetracarboxylic dianhydride (BPDA) or benzophenonetetracarboxylic dianhydride (BTDA) And (B3) the oligomer obtained in step B2 and biphenyltetracarboxylic dianhydride (BPDA) or benzophenone.
- PMDA pyromellitic dianhydride
- BTDA bis (3-amino-4-hydroxyphenyl) sulfone
- a method for producing a polyimide includes a step of obtaining a polymer.
- (C1) 1 molar equivalent of carboxylic acid dianhydride (DA) including biphenyltetracarboxylic dianhydride (BPDA) or benzophenonetetracarboxylic dianhydride (BTDA), and 2 molar equivalents of A step of reacting diaminodiphenyl ether (DADE) to obtain an oligomer in which both ends are amino groups derived from DADE, (C2) An oligomer obtained by reacting the oligomer obtained in Step C1, 4 molar equivalents of pyromellitic dianhydride (PMDA) and 2 molar equivalents of an aromatic diamine, and both terminals are acid anhydride groups derived from PMDA.
- DA carboxylic acid dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- BTDA benzophenonetetracarboxylic dianhydride
- C2 An oligomer obtained by reacting the oligomer obtained in Step C1,
- step C3 the oligomer obtained in step C2 and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ), or biphenyltetracarboxylic dianhydride (BPDA) or 1 molar equivalent of carboxylic dianhydride (DA) including benzophenone tetracarboxylic dianhydride (BTDA), 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ), and 1 molar equivalent
- a method for producing polyimide which comprises a step of reacting the aromatic diamine to obtain a polymer.
- the reaction in the above polyimide production method is preferably carried out in the presence of ⁇ -valerolactone and pyridine, or ⁇ -valerolactone and N-methylmorpholine.
- a composite material including a film obtained from the polyimide of the present invention can be provided.
- the present invention also provides an electrodeposition paint containing the polyimide of the present invention.
- a step of preparing a solution containing the polyimide of the present invention and an organic solvent comprising the steps of casting or applying the solution on a substrate to form a film, and drying the film.
- the drying step in the method for producing the composite material is preferably performed at 300 ° C. or lower.
- a polyimide excellent in heat resistance and soluble in an organic solvent and a method for producing the same can be provided.
- Polyimide of the present invention The polyimide of the present invention (1) pyromellitic dianhydride (PMDA), (2) Carboxylic acid dianhydrides (DA) including biphenyltetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), It is obtained by polymerizing (3) diaminodiphenyl ether (DADE) and (4) bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ).
- PMDA Pyromellitic dianhydride is a compound represented by the chemical formula (m1).
- DA Biphenyltetracarboxylic dianhydride is a compound in which two acid anhydride groups are bonded to biphenyl.
- a compound represented by the chemical formula (m2-1) is preferable from the viewpoint of availability.
- Benzophenone tetracarboxylic dianhydride is a compound in which two acid anhydride groups are bonded to benzophenone.
- a compound represented by the chemical formula (m2-2) is preferable from the viewpoint of availability.
- the polyimide of the present invention is made from carboxylic acid dianhydride (DA) containing biphenyltetracarboxylic dianhydride (BPDA) or benzophenonetetracarboxylic dianhydride (BTDA), but BPDA can be used alone. preferable. This is because polyimide containing a component derived from BPDA has a higher glass transition temperature (Tg).
- DADE Diaminodiphenyl ether (DADE) is a compound in which amino groups are bonded to the benzene ring of diphenyl ether one by one. Examples include 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether. In the present invention, 4,4′-diaminodiphenyl ether is preferred. This is because polyimide made from this material is superior in heat resistance.
- 4,4′-Diaminodiphenyl ether is represented by the chemical formula (m3).
- HOABSO 2 Bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ) is a compound represented by the chemical formula (m4). This compound is dihydroxydiamine having a sulfonyl group, two amino groups, and two hydroxyl groups in the molecule.
- the polyimide of the present invention may use an aromatic diamine other than the above as a raw material.
- An aromatic diamine is a compound in which two amino groups are bonded to an aromatic group. Preferred examples thereof include phenylene diamine, alkyl-substituted phenylene diamine, diaminodiphenyl sulfone, and 1,3-bis (4-aminophenoxy) benzene. Preferred examples of the alkyl-substituted phenylene diamine include toluene diamine.
- These aromatic diamines include isomers such as p-form, m-form, 4,4′-form, and 3,4′-form.
- the polyimide of the present invention is soluble in an organic solvent, preferably a polar organic solvent.
- polar organic solvents include N-methylpyrrolidone, N, N′-dimethylacetamide, and N, N′-dimethylformamide.
- the amount of the polyimide dissolved in the organic solvent is preferably 10 to 15 parts by mass with respect to 100 parts by mass of the organic solvent.
- the symbol “ ⁇ ” includes values at both ends thereof. This is because such a soluble polyimide is excellent in handleability when used as a polyimide solution.
- the organic solvent may be appropriately selected depending on the solubility of the polyimide.
- the polyimide of the present invention is excellent in heat resistance.
- the heat resistance is evaluated by a decomposition start temperature (Tm) and a glass transition temperature (Tg).
- Tm decomposition start temperature
- Tg glass transition temperature
- the polyimide of the present invention has a high Tm. This is considered because it has an oxazole group in the molecule, as will be described later.
- the Tm of the polyimide of the present invention is preferably 500 to 560 ° C, more preferably 540 to 560 ° C.
- the Tg of the polyimide of the present invention is preferably 300 to 400 ° C. Polyimide having such a range of Tm and Tg can be applied to uses that require extremely high heat resistance.
- the polyimide of the present invention is derived from (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ) and has an oxazole group or a carboxyl group which is a polar group in the main chain. For this reason, the polyimide of this invention is excellent in adhesiveness with another material.
- the polyimide of the present invention has a photosensitive property that when irradiated with light, the —N ⁇ C— bond of the oxazoline ring is cleaved and the molecular chain at that portion is cleaved (Patent Document 6).
- the polyimide of this invention also has an electrodeposition characteristic by ionizing a carboxyl group.
- the polyimide of the present invention preferably has a repeating unit of the following general formula (I), (II) or (III).
- [HOABSO 2 ] is the bis (3-amino-4-hydroxyphenyl) sulfone residue.
- [DADE] is the diaminodiphenyl ether residue.
- [DA] is the carboxylic acid dianhydride residue.
- a residue is a partial structure in a polymer and refers to a structure other than a chemical bond.
- [DADE] that is, the diaminodiphenyl ether residue is a divalent diphenyl ether group.
- U 1 is, X 1 or X 1, - is a group represented by [DA] -X 1.
- X 1 is a phenylenediamine residue, an alkyl-substituted phenylenediamine residue, a diaminodiphenylsulfone residue, a bis (aminophenoxy) benzene residue, or a bis (3-amino-4-hydroxyphenyl) sulfone residue.
- phenylenediamine residue or diamine residue is preferable. This is because such a polyimide has high solubility in an organic solvent.
- the bond between [DADE] and [DA], and [DADE] and [PMDA] is an imide bond. That is, the bond is an imide bond formed by the reaction of an amino group derived from diaminodiphenyl ether (DADE) and an acid anhydride group derived from acid dianhydride.
- DADE diaminodiphenyl ether
- the bond between [HOABSO 2 ] and [PMDA] is a bond represented by the general formula (i) or (ii).
- the bond represented by the general formula (i) is a bond through an oxazole group, and is also referred to as “oxazole bond” in the present invention.
- R is a hydrogen atom or a carboxyl group.
- ⁇ represents a part of [PMDA], and ⁇ represents a part of [HOABSO 2 ].
- the oxazole bond is formed by reacting the amino group and hydroxyl group of HOABSO 2 which is dihydroxydiamine with an acid anhydride group derived from PMDA or the like (Scheme 1).
- R in the formula (i) is a hydrogen atom or a carboxyl group.
- the bond represented by the general formula (ii) is an imide bond in which a hydroxyl group is present in the vicinity of the imide group.
- the polyimide of the present invention includes a structure in which [PMDA] and [DADE] are bonded, it is excellent in heat resistance and water resistance.
- a polyimide containing a structure in which three or more [PMDA] and [DADE] are bonded such as [PMDA]-[DADE]-[PMDA]
- the structure is because of the high density of imide groups.
- the polyimide of the present invention includes a unique structure such as [HOABSO 2 ] while controlling the bond between [PMDA] and [DADE], it has excellent heat resistance and water resistance and has various functions.
- the adhesion to other materials is particularly excellent.
- the polyimide of the present invention has an L-2 or L-3 structure at the bonding portion, that is, when it has an oxazole group and a carboxyl group, it has excellent adhesiveness and heat resistance.
- the heat resistance is extremely excellent.
- the polyimide of the present invention can exhibit various functions by appropriately selecting the structure of the bond between HOABSO 2 that is dihydroxydiamine and an acid anhydride.
- the bond is preferably a bond represented by L-2 or L-3. This is because such polyimide is excellent in heat resistance.
- repeating unit (I) in the polyimide of the present invention is preferably represented by the general formula (1).
- This repeating structure is characterized in that HOABSO 2 is bonded to an acid dianhydride and an oxazole.
- * represents that a phenylene group and an imide group are bonded.
- Q is a single bond or a carbonyl group.
- BPDA biphenyltetracarboxylic dianhydride
- BTDA benzophenonetetracarboxylic dianhydride
- a single bond means that benzene rings are directly bonded to form a biphenyl skeleton.
- Q is preferably a single bond. This is because the polyimide in which Q is a single bond is more excellent in heat resistance.
- Y 1 corresponds to U 1 in the general formula (I) and is a group represented by the general formula (11), (12), (13), or (14).
- the general formulas (11) to (13) are specific structures when U 1 in the general formula (I) is represented by X 1 and are aromatic diamine residues.
- R 10 in the general formula (11) is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. This is because such a polyimide has higher solubility in an organic solvent.
- U 1 of the general formula (I) is X 1 - is a specific structure which may be represented by [DA] -X 1.
- Ar 1 in the general formula (14) is independently a group represented by the general formulas (11) to (13).
- Q is a single bond or a carbonyl group, but as described above, Q is preferably a single bond.
- Y 1 is preferably a group represented by the general formula (11). This is because such polyimide is more excellent in heat resistance.
- This repeating structure is characterized in that HOABSO 2 can form an oxazole bond with an acid dianhydride.
- U 2 is a group represented by [DA] or [DA] -X 2- [DA].
- X 2 represents a phenylenediamine residue, an alkyl-substituted phenylenediamine residue, a diaminodiphenylsulfone residue, 1,3-bis (4-aminophenoxy) benzene, or the bis (3-amino-4-hydroxyphenyl) sulfone residue. It is a group. Among these, a phenylenediamine residue or a toluenediamine residue is preferable. This is because such a polyimide has high solubility in an organic solvent.
- the oxazole bond in the polyimide of the present invention is preferably a bond represented by L-2 or L-3. Therefore, the repeating unit (II) in the polyimide of the present invention is preferably represented by the general formula (2). Repeat unit of (2)
- Q is a single bond or a carbonyl group.
- Q is preferably a single bond. This is because the polyimide in which Q is a single bond is more excellent in heat resistance.
- Y 2 is a group corresponding to U 2 in the general formula (II). Y 2 is represented by the general formula (21), (22), or (23).
- General formula (21) is a specific structure when U 2 in general formula (II) is represented by X 2 , and is a carboxylic acid dianhydride residue.
- General formulas (22) and (23) are specific structures when U 2 in general formula (II) is represented by [DA] -X 2- [DA].
- the general formula (23) is a structure when X 2 is HOABSO 2
- the general formula (22) is a structure when X 2 is an aromatic diamine other than HOABSO 2 .
- Q is defined as described above, and a single bond is preferable as described above.
- Ar 1 is the general formulas (11) to (13) described above, and the group of the general formula (11) is preferable as described above.
- R, ad, and * are defined in the same manner as general formula (1).
- Y 2 is preferably a group represented by the general formula (22). This is because such polyimide is more excellent in heat resistance.
- [PMDA] and the like are as described in the formulas (I) and (II).
- X 3 is a phenylenediamine residue, an alkyl-substituted phenylenediamine residue, a diaminodiphenylsulfone residue, or a bis (aminophenoxy) benzene residue.
- X 3 is preferably a phenylenediamine residue or a toluenediamine residue. This is because such a polyimide is excellent in solubility in an organic solvent.
- U 3 is [HOABSO 2 ], [HOABSO 2 ]-[DA]-[HOABSO 2 ], [HOABSO 2 ]-[DA] -X 3 , or X 3- [DA]-[HOABSO 2 ].
- bonds of [HOABSO 2 ] and [PMDA], and [HOABSO 2 ] and [DA] are bonds represented by the general formula (i) or (ii) described above.
- the oxazole bond in the polyimide of the present invention is preferably a bond represented by L-2 or L-3. Therefore, the repeating unit (III) in the polyimide of the present invention is preferably represented by the general formula (3-1) or (3-2). (3-1) repeating unit
- Q is a single bond or a carbonyl group, but as described above, a single bond is preferable.
- Ar 1 corresponds to the aromatic diamine residue X 3 of the general formula (III) and is represented by the general formula (11), (12), or (13).
- Y 3 is a group derived from U 3 in the general formula (III), and is a single bond or a group represented by the formula (31).
- This repeating unit has a specific structure in the case where U 3 is [HOABSO 2 ]-[DA] -X 3 in the general formula (III).
- polyimide repeating structure of the present invention may be the following structure.
- pyromellitic dianhydride has two acid anhydride groups in one benzene ring. That is, since the proximity of the acid anhydride groups present in one molecule differs depending on the structure of the acid dianhydride, the reactivity of the imidization reaction also varies greatly.
- the molecular weight of the polymer decreases with the passage of reaction time. That is, when the molecular weight of the polymer produced is plotted with time as the horizontal axis, a parabolic curve is obtained.
- BPDA biphenyltetracarboxylic dianhydride
- the molecular weight of the polymer produced increases with time, unlike this. That is, a hyperbolic curve is obtained by plotting the molecular weight of the polymer produced with time as the horizontal axis.
- a gel-like material is generated, and the solubility of polyimide in an organic solvent is lowered.
- the rapid increase in molecular weight is thought to be due to the intermolecular crosslinking reaction of the polyamic acid produced as a precursor (Scheme 3).
- PMDA and DA are used in combination as an acid dianhydride and a polyimide soluble in an organic solvent is synthesized. Therefore, the difference in reactivity between PMDA and DA, control of molecular weight, and determination of the end point of the reaction are important.
- the polyimide of this invention is manufactured by the method characterized by the following points. 1) A three-stage sequential polymerization method is employed in which sequential polymerization is performed in three stages. 2) In the first and second steps, an oligomer having amino groups at both ends or an oligomer having acid anhydride groups at both ends is obtained. 3) In the third step, the oligomer obtained in the previous step is polymerized to obtain a high molecular weight polyimide.
- DADE diaminodiphenyl ether
- PMDA pyromellitic dianhydride
- the polyimide of the present invention is preferably produced by the following method A, B or C.
- Manufacturing method A is (A1) 1 mol equivalent of carboxylic acid dianhydride (DA) containing biphenyltetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA) is reacted with 2 mol equivalent of diaminodiphenyl ether (DADE). And obtaining an oligomer whose both ends are amino groups derived from DADE, (A2) The oligomer obtained in step A1 is reacted with 4 molar equivalents of pyromellitic dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ) at both ends.
- DA carboxylic acid dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- BTDA benzophenone tetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- DA carboxylic acid dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- BTDA benzophenone tetracarboxylic dianhydride
- the aromatic diamine in the present production method is not limited as long as it is a compound in which two amino groups are bonded to an aromatic group.
- phenylenediamine, toluenediamine, diaminodiphenylsulfone, bis (4-aminophenoxy) benzene, or bis (3-amino-4-hydroxyphenyl) sulfone are preferred. This is because these aromatic amines are easily available and can provide a polyimide having excellent solubility.
- These aromatic amines also include their isomers. Among these, a phenylenediamine residue or a toluenediamine residue is preferable. This is because such a polyimide has higher solubility in an organic solvent.
- BPDA biphenyltetracarboxylic dianhydride
- DAT 2,4′-diaminotoluene
- A3 The case where 1 molar equivalent of BPDA and 2 molar equivalents of DAT are reacted in the step will be described. This reaction is shown in Scheme A below.
- Step A1 In this step, one acid anhydride group of BPDA reacts with one amino group of DADE, and the other acid anhydride group of BPDA reacts with one amino group of DADE of another molecule. To do. As a result, an oligomer (a1) whose terminal is an amino group is produced. Since this oligomer is stable and soluble in an organic solvent, the oligomer does not precipitate in the reaction solution.
- This step is preferably performed in a polar organic solvent under an inert gas stream.
- inert gases include nitrogen and argon.
- polar organic solvents include NMP, DMAc, and DMF.
- ⁇ -valerolactone and pyridine are preferably used as the catalyst.
- Gamma-valerolactone is preferably 10 to 15 mmol equivalent
- pyridine or N-methylmorpholine is preferably 20 to 30 mmol equivalent.
- a solvent such as toluene that can be azeotroped with water together.
- the reaction temperature may be determined in consideration of the balance between the reaction rate and the deterioration of the raw material.
- the reaction temperature is preferably about 150 to 200 ° C.
- reaction time may be appropriately determined depending on the progress of the reaction.
- Step A2 In this step, 4 molar equivalents of pyromellitic dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ) were added. It is made to react with the obtained oligomer. Although the reaction mechanism is not limited, it is guessed as follows.
- PMDA pyromellitic dianhydride
- HOABSO 2 bis (3-amino-4-hydroxyphenyl) sulfone
- A2 process is performed under inert gas stream similarly to A1 process.
- the reaction temperature and reaction time may be the same as in step A1.
- Step A3 In this step, 1 molar equivalent of biphenyltetracarboxylic dianhydride (BPDA) and 2 molar equivalents of 2,4′-diaminotoluene (DAT) were added, the oligomer obtained in the previous step, 1 molar equivalent of BPDA and 2 molar equivalents of DAT are reacted to obtain a polymer.
- BPDA biphenyltetracarboxylic dianhydride
- DAT 2,4′-diaminotoluene
- This reaction mechanism is not limited, but is presumed as follows.
- this oligomer Since this oligomer has an amino group at one end and an acid anhydride group at the other end, it polymerizes to produce a high molecular weight polyimide (a3).
- This polyimide is a polyimide having a repeating unit of the general formula (1). Even in this step, an oligomer represented by [PMDA]-[DADE]-[PMDA] or [DADE] -PMDA]-[DADE], which is hardly soluble in an organic solvent, is not generated. Therefore, no component is precipitated in the reaction system during the process, and the obtained polyimide (a3) is also soluble in the organic solvent.
- the A3 step is performed under an inert gas stream as in the A1 step.
- the reaction temperature and reaction time may be the same as in step A1. Since the viscosity of the system increases as the polymer increases in molecular weight, it is preferable to add a solvent. The additional amount of the solvent may be appropriately adjusted, but it is preferable to adjust the reaction solution so that the reaction solution contains about 10 to 20% by mass of the polymer in consideration of the handling property of the reaction solution.
- a three-step sequential polymerization method is employed, 2) an oligomer having an amino group at both ends is obtained in the first step, and an oligomer having both ends at an acid anhydride group is obtained in the second step. 3) A high molecular weight polyimide is obtained in the third step. 4) The production method having the characteristics of not producing an oligomer represented by [PMDA]-[DADE]-[PMDA] is soluble in a solvent. A polyimide is obtained.
- the bond between PMDA and DADE and the bond between DADE and BPDA indicated by V are imide bonds.
- the imide bond is preferably generated in the steps A1 and A2. That is, in the A1 step, it is preferable that an imide bond is generated between DADE and BPDA instead of an amide bond, and similarly, in the A2 step, an imide bond is generated between PMDA and DADE. This is because if DADE and BPDA remain in an unstable amide bond, an exchange reaction may proceed in the solution. Since the polyimide of the present invention is soluble in an organic solvent even when an imide bond is formed, there is an advantage that an exchange reaction hardly occurs in a solution.
- the steps A1 to A3 of the present invention are preferably carried out at 150 to 200 ° C. and the reaction in the step A3 is preferably carried out for about 3 to 6 hours, the W portion is a bond mainly via an oxazole group, It is considered that a carboxyl group exists in the vicinity of the oxazole group (the structure of L-2 described above). Therefore, in the step A3, if the polyimide is heated at 400 ° C.
- the W portion is a bond through an oxazole group, and a carboxyl group is present in the vicinity of the oxazole group. Is considered to be a bond that does not exist (the structure of L-3 described above).
- heating a reaction system containing a solvent to 400 ° C. to 500 ° C. is accompanied by decomposition of the solvent, which may impair the physical properties of the polyimide. Therefore, the A3 step may be performed at 150 to 200 ° C., and after this step, a step of removing the solvent and heating the polyimide at 400 to 500 ° C. may be provided.
- Manufacturing method B is (B1) 2 molar equivalents of pyromellitic dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO 2 ) are reacted to form an acid anhydride derived from PMDA at both ends.
- PMDA pyromellitic dianhydride
- HOABSO 2 bis (3-amino-4-hydroxyphenyl) sulfone
- step B2 The oligomer obtained in step B1, 2 molar equivalents of carboxylic acid dianhydride (DA) containing biphenyltetracarboxylic dianhydride (BPDA) or benzophenonetetracarboxylic dianhydride (BTDA), and diaminodiphenyl ether ( (DADE) reacting with 4 molar equivalents to obtain an oligomer whose both ends are amino groups derived from DADE, and (B3) the oligomer obtained in step B3 and biphenyltetracarboxylic dianhydride (BPDA) or benzophenone 1 molar equivalent of carboxylic dianhydride (DA) including tetracarboxylic dianhydride (BTDA), or
- the method includes a step of reacting the oligomer obtained in step B3 with 2 molar equivalents of the carboxylic acid dianhydride (DA) and 1 molar equivalent of an aromatic diamine to obtain
- the aromatic diamine is preferably a compound as described in Production Method A.
- an oligomer (b1) whose terminal is an acid anhydride group is generated. Since this oligomer is soluble in an organic solvent, the oligomer does not precipitate in the reaction solution.
- step B2 2 molar equivalents of BPDA and 4 molar equivalents of DADE are added and reacted with the oligomer obtained in the previous step.
- the oligomer produced by this reaction contains a skeleton derived from HOABSO 2 in the molecule, and the terminal is an amino group. This oligomer is soluble and does not precipitate in the reaction solution.
- a high molecular weight polyimide (b3).
- This polyimide has a repeating unit of the general formula (2) and is soluble in an organic solvent.
- the conditions for each step may be the same as in manufacturing method A. Further, after the step B3, a step of heating the polyimide at 400 to 500 ° C., preferably 410 to 450 ° C. may be provided. Further, the reaction mechanism of this method can be inferred in the same manner as in production method A.
- Manufacturing method C is (C1) Reaction of 1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyltetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA) with 2 molar equivalents of diaminodiphenyl ether (DADE) A process for obtaining an oligomer having both ends of an amino group derived from DADE, (C2) The oligomer obtained in the previous step is reacted with 4 molar equivalents of pyromellitic dianhydride (PMDA) and 2 molar equivalents of an aromatic diamine, and an oligomer having both ends of which are PMDA-derived acid anhydride groups.
- DA carboxylic acid dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- BTDA benzophenone tetracarboxylic dianhydride
- DADE diaminodiphenyl
- the aromatic diamine in this method is preferably an aromatic diamine other than HOABSO 2 , more preferably phenylene diamine, toluene diamine, diaminodiphenyl sulfone, or 1,3-bis (4-aminophenoxy) benzene.
- aromatic diamines are easily available and can provide a polyimide having excellent solubility.
- a phenylenediamine residue or a toluenediamine residue is preferable.
- Such polyimide is more soluble in organic solvents.
- BPDA biphenyltetracarboxylic dianhydride
- DAT 2,4′-diaminotoluene
- an oligomer (c1) having an amino group at the end is generated. Since this oligomer is soluble in an organic solvent, the oligomer does not precipitate in the reaction solution.
- step C2 4 molar equivalents of pyromellitic dianhydride (PMDA) and 2 molar equivalents of aromatic diamine are added and reacted with the oligomer obtained in the previous step.
- the oligomer produced by this reaction is terminated with an acid anhydride group (c2).
- Step C3 consists of 1 molar equivalent of biphenyltetracarboxylic dianhydride (BPDA), 1 molar equivalent of 2,4′-diaminotoluene (DAT), and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl).
- Sulfone (HOABSO 2 ) is reacted with the oligomer obtained in step C2 to obtain a polymer (c3).
- This polyimide is soluble in an organic solvent and has a repeating unit of the general formula (3-2).
- the conditions for each step may be the same as in manufacturing method A. Further, after the step C3, a step of heating the polyimide at 400 to 500 ° C., preferably 410 to 450 ° C. may be provided. The reaction mechanism of this method can be inferred in the same manner as in production method A.
- a composite material obtained by laminating a film obtained from the polyimide of the present invention on a substrate is preferable.
- the polyimide of the present invention since the polyimide of the present invention has excellent heat resistance and adhesiveness, a composite material having high heat resistance and high strength can be obtained.
- Such composite materials can be used as aerospace materials, transportation vehicle materials, and semiconductor materials.
- Such composite materials are 1) A step of preparing a solution containing the polyimide of the present invention and an organic solvent, It is preferable that the solution is produced by a method including a step of casting or coating the solution on a substrate to form a film, and 3) a step of drying the film.
- the polyimide of the present invention is soluble in an organic solvent, a solution can be easily prepared.
- the solution may be prepared in a known manner, and a known polar solvent may be used as the organic solvent.
- polar solvents include NMP, DMAc, DMF and the like.
- the concentration of the solution is not limited, but is preferably 10 to 20% by mass because it is excellent in handleability and the like.
- the step of casting or coating this solution on a substrate to form a film may also be performed as known.
- this step may be performed using an apparatus such as a spin coater, a knife coater, or a roll coater.
- Known materials may be used as the substrate, but examples thereof include glass, metal, preferably copper plate, and ceramic.
- the membrane is dried, but this condition may be determined according to the characteristics to be obtained.
- the film is preferably dried at 300 ° C. or lower, more preferably at 200 to 300 ° C.
- polar groups such as carboxyl groups are present in the molecule, so that high adhesion can be obtained.
- the film is preferably dried at 400 to 500 ° C., particularly 410 to 450 ° C. When the film is dried at such a temperature, the carboxyl group is eliminated, so that extremely high heat resistance can be obtained.
- the polyimide of this invention has an oxazole group in a molecule
- a positive resist can draw an extremely fine pattern and can be used as a next-generation semiconductor material.
- the polyimide of the present invention is soluble in an organic solvent, and its solution is stable and excellent in adhesiveness. Therefore, it can be used as a coating agent, paint, or adhesive. . In particular, it can be used for medical materials, building materials, household high heat resistant materials (iron bottoms, pan lining materials), flame retardant curtains, coating agents as a substitute for polytetrafluoroethylene. Furthermore, when the polyimide of this invention has a carboxyl group in a molecule
- the coating agent, paint, or adhesive may be prepared by a known method.
- the most important step in the polyimide production method of the present invention is the second step.
- the reagent is usually simply added to the reaction system, but the order of adding the reagent and the time for adding the reagent may be limited. Therefore, the second step can be performed by changing as necessary. In this way, changing the second step as appropriate is effective for the first experiment.
- 1) a container different from the reaction vessel is prepared, and the reagent added in the second step is heated as necessary to dissolve it in advance. 2)
- the homogeneous solution thus obtained is added to the reaction vessel. It is good as a process added to. Moreover, you may add such a change to a 3rd process as needed.
- Tm Thermal decomposition start temperature
- Tg glass transition temperature
- Example 2 (BPDA + 2DADE) (4 PMDA+2HOABSO 2 ) (BPDA + DAT + mTPE)
- BPDA + DAT + mTPE A 10% by mass polyimide solution was obtained in the same manner as in Example 1 except for the following changes.
- step 1) 1.0 g of ⁇ -valerolactone was used.
- the amount of NMP added in the step 2) was 140 g.
- the raw materials added in the step 3) were 2.94 g (10 mmol) of BPDA, 1.22 g (10 mmol) of DAT, and 2.92 g of 1,3-bis (4-aminophenoxy) benzene (mTPE). The amount was 80 g.
- the reaction time was 6 hours. Table 1 shows the molecular weight and heat resistance of the obtained polyimide.
- Example 3 (BPDA + 2DADE) (4 PMDA+2HOABSO 2 ) (BTDA + DAT + HOABSO 2 )
- a polyimide solution was obtained in the same manner as in Example 1 except for the following changes.
- 1.0 g of ⁇ -valerolactone was used.
- the amount of NMP added in the step 2) was 140 g.
- the raw materials to be added in the step 3) are benzophenone tetracarboxylic dianhydride (BTDA) 3.22 g (10 mmol), DAT 1.22 g (10 mmol), and 4,4′-diaminodiphenylsulfone 2.48 g (10 mmol).
- the reaction time was 6.5 hours. Table 1 shows the molecular weight and heat resistance of the obtained polyimide.
- Example 4 (BPDA + 2DADE) (3 PMDA+HOABSO 2 ) (BTDA + 2DAT) A polyimide solution was obtained in the same manner as in Example 1 except for the following changes.
- step 1) 1.2 g of pyridine was used.
- the raw materials added in the step 2) were PMDA 6.64 g (30 mmol) and HOABSO 2 2.80 g (10 mmol), and the amount of NMP added was 60 g.
- the amount of NMP added in the step 3) was 80 g, and the reaction time was 4.75 hours.
- Table 1 shows the molecular weight and heat resistance of the obtained polyimide.
- Example 5 (2 PMDA+HOABSO 2 ) (2BPDA + 4DADE) (2BPDA + mPD) A flask similar to that in Example 1 was prepared and immersed in a silicon bath.
- Example 6 (2 PMDA+HOABSO 2 ) (2BPDA + 4DADE) (2BPDA + HOABSO 2 )
- a polyimide solution was obtained in the same manner as in Example 5 except for the following changes.
- step 1) 2.4 g of pyridine and 80 g of NMP were used, and the reaction time was 50 minutes.
- the starting material to be added in the step 3) was BPDA 5.88 g (20 mmol), followed by HOABSO 2 2.80 g (10 mmol), the amount of NMP added was 60 g, and the reaction time was 2.75 hours.
- 100 g of NMP was further added to the reaction mixture to obtain a 10% by mass polyimide solution. Table 1 shows the molecular weight and heat resistance of the obtained polyimide.
- Example 7 (2 PMDA+HOABSO 2 ) (2BPDA + 4DADE) (2BTDA + HOABSO 2 )
- the raw materials added in the step 3) were 6.46 g (20 mmol) of BTDA and 2.80 g (10 mmol) of HOABSO 2 , and the reaction time was 4 hours.
- 60 g of NMP was added when the reaction had passed for 2 hours.
- 40 g of NMP was further added to the reaction mixture to obtain a 10% by mass polyimide solution.
- the obtained polyimide solution was applied to the surface of the glass plate, and dried at 150 ° C. for 30 minutes under aeration. The dried coating film was released from the glass plate and attached to a metal frame. In this state, it was further heated at 250 ° C. for 1 hour to obtain a polyimide film.
- Table 1 shows the molecular weight and heat resistance of the obtained polyimide.
- Example 8 (2 PMDA+HOABSO 2 ) (2BPDA + 4mDADE) (2BTDA + mTPE)
- the raw materials added in the step 2) were 8.00 g (40 mmol) of 3,4'-diaminodiphenyl ether (mDADE) and 5.88 g (20 mmol) of BPDA.
- the raw materials to be added in the step 3) were BTDA 6.46 g (20 mmol), 1,3-bis (4-aminophenoxy) benzene (mTPE) 2.92 g (10 mmol), and the amount of NMP added was 50 g. .
- Example 9 (BPDA + 2DADE) (4 PMDA+2DAT) (BPDA + DAT + HOABSO 2 ) A flask similar to that in Example 1 was prepared and immersed in a silicon bath.
- the obtained polyimide was evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 10 (BPDA + 2DADE) (4 PMDA+2DAT) (BTDA + DAT + HOABSO 2 )
- a polyimide solution was obtained in the same manner as in Example 9 except for the following changes. 1) The reaction time in the step was 40 minutes, and the subsequent air cooling time was 40 minutes. 2) The amount of NMP added in the step was 70 g. 3) The raw materials added in the step were BTDA 4.51 g (14 mmol), DAT 1.71 g (14 mmol), HOABSO 2 3.93 g (14 mmol), and the amount of NMP added was 58 g. The reaction time in this step was 5 hours. In this way, a 14% by mass polyimide solution was obtained. The obtained polyimide was evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 11 (BPDA + 2DADE) (4 PMDA+2DAT) (HOABSO 2 )
- the raw materials added in the step 1) were BPDA 2.94 g (10 mmol), DADE 4.00 g (20 mmol), ⁇ -valerolactone 0.9 g, pyridine 1.8 g, NMP 100 g, and toluene 35 g.
- the reaction time was 1 hour, and the subsequent air cooling time was 15 minutes.
- the raw materials added in the step 2) were 8.72 g (40 mmol) of PMDA and 2.44 g (20 mmol) of DAT, and the amount of NMP added was 44 g.
- the air cooling time after the reaction was 30 minutes.
- the raw material added in the step 3) was 2.80 g (10 mmol) of HOABSO 2 and the amount of NMP added was 44 g.
- the reaction time in this step was 3.5 hours. In this way, a 10% by mass polyimide solution was obtained.
- the obtained polyimide was evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 12 (BPDA + 2DADE) (3PMDA) (2DAT + HOABSO 2 + BPDA) A polyimide solution was obtained in the same manner as in Example 9 except for the following changes.
- the cooling time after the reaction in step 1) was 50 minutes.
- the raw material added in the step 2) was PMDA 9.15 g (42 mmol), and the amount of NMP added was 50 g.
- the air cooling time after the reaction was 25 minutes.
- step 3 3.42 g (28 mmol) of DAT and 3.93 g (14 mmol) of HOABSO 2 were added in advance, and after stirring, 4.12 g (14 mmol) of BPDA and 80 g of NMP were added.
- the obtained polyimide was evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 13 (BPDA + 2DADE) (3 PMDA+DAT) (BTDA + HOABSO 2 + SO 2 AB)
- the raw materials added in the step 2) were PMDA 9.15 g (42 mmol) and DAT 1.71 g (14 mmol), and the amount of NMP added was 60 g.
- the raw materials added in the step 3) were 3.93 g (14 mmol) of HOABSO 2 and 3.48 g (14 mmol) of SO 2 AB, and the amount of NMP added was 80 g.
- the reaction in this step was carried out at room temperature for 20 minutes, and further took 11 hours and 45 minutes at 180 ° C. In this way, a 10% by mass polyimide solution was obtained.
- the obtained polyimide was evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 14 (BPDA + 2DADE) (3 PMDA+BPDA+mPD) (HOABSO 2 ) A polyimide solution was obtained in the same manner as in Example 9 except for the following changes.
- the raw materials added in step 1) were BPDA 2.94 g (10 mmol), DADE 4.00 g (20 mmol), ⁇ -valerolactone 1.2 g, pyridine 2.0 g, NMP 80 g, and toluene 25 g.
- the raw materials added in the step 2) were PMDA 4.36 g (20 mmol), BPDA 2.94 g (10 mmol), and mPD 1.00 g (10 mmol), and the amount of NMP added was 60 g.
- Example 1 (BPDA + 2DADE) (4 PMDA+2DAT) (BPDA + 2DAT) An apparatus similar to that of Example 1 was prepared. BPDA 5.88 g (20 mmol), DADE 8.01 g (40 mmol), ⁇ -valerolactone 1.5 g (15 mmol), pyridine 3.5 g (44 mmol), NMP 150 g, toluene 45 g were charged into the apparatus. did. While passing through nitrogen, the mixture was heated and stirred at a silicon bath temperature of 180 ° C. and a rotation speed of 180 rpm for 1 hour. 20 ml of water-toluene fraction was removed. Air-cooled and stirred at 180 rpm for 1 hour.
- Example 2 A part of the reaction solution was diluted with dimethylformamide, and the molecular weight was measured in the same manner as in Example 1. A part of the dried polyimide film was taken, and the thermal decomposition starting temperature (Tm) was measured with a thermal analyzer Thermo Plus Tg 8120 manufactured by Rigaku Corporation. The conditions were a temperature increase rate of 10 ° C./1 minute and a temperature increase of 600 ° C. Tm was 512.5 ° C. The glass transition temperature (Tg) was measured using a Perkin Elmer Pyrid Diameter DSC. The condition was that the temperature was raised to 400 ° C. at a rate of temperature increase of 10 ° C./1 minute, then air-cooled and again raised to 430 ° C. at 10 ° C./1 minute. Tg was not observed.
- the polyimide of the present invention has extremely high heat resistance with a thermal decomposition starting temperature Tm of 500 to 560 ° C. This is presumably because the molecule contains an oxazole group rich in thermal stability.
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Abstract
Description
(1)ピロメリット酸ジ無水物(PMDA)、
(2)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)、
(3)ジアミノジフェニルエーテル(DADE)、ならびに
(4)ビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)を重合して得られる、有機溶媒に可溶なポリイミドを提供する。
―[PMDA]-[HOABSO2]-[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-[HOABSO2]-[PMDA]―U1― (I)
{式中、[PMDA]は、前記ピロメリット酸ジ無水物残基であり、
[HOABSO2]は、前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基であり、
[DADE]は、前記ジアミノジフェニルエーテル残基であり、
[DA]は、前記カルボン酸ジ無水物残基であり、
U1は、X1、またはX1-[DA]-X1で表される基であり、
(ここで、X1は、フェニレンジアミン残基、アルキル置換フェニレンジアミン残基、ジアミノジフェニルスルホン残基、ビス(アミノフェノキシ)ベンゼン残基、または前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基である)
[DADE]と[DA]、および[DADE]と[PMDA]の結合はイミド結合であり、
[PMDA]と[HOABSO2]との結合は、一般式(i)または(ii)で表される結合であり、
[PMDA]とU1の結合は、U1中のX1がビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基である場合は、前記一般式(i)または(ii)で表される結合であり、それ以外の場合は、イミド結合である。)}
また、前記ポリイミドは、一般式(II)で表される繰り返し単位を有するポリイミドであってもよい。
{式中、[PMDA]は、前記ピロメリット酸ジ無水物残基であり、
[HOABSO2]は、前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基であり、
[DADE]は、前記ジアミノジフェニルエーテル残基であり、
[DA]は、前記カルボン酸ジ無水物残基であり、
U2は、[DA]、または[DA]-X2-[DA]で表される基であり、
(ここで、X2は、フェニレンジアミン残基、アルキル置換フェニレンジアミン残基、ジアミノジフェニルスルホン残基、1,3-ビス(4-アミノフェノキシ)ベンゼン、または前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基である)
[DADE]と[DA]、[DADE]と[PMDA]、および[DADE]とU2の結合はイミド結合であり、
[HOABSO2]と[PMDA]の結合は、前記一般式(i)または(ii)で表される結合である。}
さらに、前記ポリイミドは、一般式(III)で表される繰り返し単位を有するポリイミドであってもよい。
{式中、[PMDA]は、前記ピロメリット酸ジ無水物残基であり、
[DADE]は、前記ジアミノジフェニルエーテル残基であり、
[DA]は、前記カルボン酸ジ無水物残基であり、
X3は、フェニレンジアミン残基、アルキル置換フェニレンジアミン残基、ジアミノジフェニルスルホン残基、またはビス(アミノフェノキシ)ベンゼン残基であり、
U3は、[HOABSO2]、[HOABSO2]-[DA]-[HOABSO2]、[HOABSO2]-[DA]-X3、またはX3-[DA]-[HOABSO2]で表される基であり(ここで、[HOABSO2]は、前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基であり、[DA]、X3は前記のとおり定義される)、
[DADE]と[DA]、[DADE]と[PMDA]、[PMDA]とX3の結合はイミド結合であり、
[HOABSO2]と[PMDA]、および[HOABSO2]と[DA]の結合は、前記一般式(i)または(ii)で表される結合である。}
本発明の好ましい実施態様は、一般式(1)で表される繰り返し単位を含むポリイミドである。
Rは独立に、水素原子またはカルボキシル基であり、
a~hは、炭素原子の位置を示し、a、c、e、gの炭素がRと結合する場合は、b、d、f、hの炭素がオキサゾール基と結合することを表し、
Y1は、一般式(11)~(13)で表される基であり、
*は、フェニレン基とイミド基が結合していることを表す。]
本発明の好ましい別の実施態様は、一般式(2)で表される繰り返し単位を含むポリイミドである。
Rは独立に、水素原子またはカルボキシル基であり、
a~dは、炭素原子の位置を示し、a、cの炭素がRと結合する場合は、b、dの炭素がオキサゾール基と結合することを表し、
Y2は、一般式(21)、(22)または(23)で表される基であり、
*は、フェニレン基とイミド基が結合していることを表す。]
本発明の好ましい別の実施態様は、一般式(3-1)で表される繰り返し単位を含む、ポリイミドである。
Rは独立に、水素原子またはカルボキシル基であり、
a~dは炭素原子の位置を表し、a、cの炭素がRと結合する場合は、b、dの炭素がオキサゾール基と結合することを表し、
Ar1は、独立に一般式(11)~(13)で表される基であり、
*は、フェニレン基とイミド基が結合していることを表す。]
本発明の好ましい別の実施態様は、一般式(3-2)で表される繰り返し単位を含むポリイミドである。
Rは独立に、水素原子またはカルボキシル基であり、
a~dは、炭素原子の位置を表し、a、cの炭素がRと結合する場合は、b、dの炭素がオキサゾール基と結合することを表し、
Ar1は、独立に一般式(11)~(13)で表される基であり、
*は、フェニレン基とイミド基が結合していることを表す。]
本発明によれば、(A1)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、2モル当量のジアミノジフェニルエーテル(DADE)とを反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、
(A2)A1工程で得たオリゴマーと、4モル当量のピロメリット酸ジ無水物(PMDA)と2モル当量のビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)とを反応させて両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、および
(A3)A2工程で得たオリゴマーと、1モル当量の芳香族ジアミン、あるいは、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と芳香族ジアミン2モル当量とを反応させて重合体を得る工程を含む、ポリイミドの製造方法が提供される。
(B2)B1工程で得たオリゴマーと、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)2モル当量と、4モル当量のジアミノジフェニルエーテル(DADE)を反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、および
(B3)B2工程で得たオリゴマーと、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量、あるいは、2モル当量の前記カルボン酸ジ無水物(DA)と1モル当量の芳香族ジアミンを反応させて重合体を得る工程を含む、ポリイミドの製造方法が提供される。
(C2)C1工程で得たオリゴマーと、4モル当量のピロメリット酸ジ無水物(PMDA)と2モル当量の芳香族ジアミンを反応させて、両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、ならびに
(C3)C2工程で得たオリゴマーと、1モル当量のビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)、あるいは、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、1モル当量のビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)と、1モル当量の芳香族ジアミンを反応させて重合体を得る工程を含む、ポリイミドの製造方法が提供される。
前記溶液を、基材の上に流延または塗布して膜を形成する工程、および
前記膜を乾燥させる工程を含む、複合材料の製造方法が提供される。
本発明のポリイミドは、
(1)ピロメリット酸ジ無水物(PMDA)、
(2)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)、
(3)ジアミノジフェニルエーテル(DADE)、ならびに
(4)ビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)を重合して得られる。
(1)PMDA
ピロメリット酸ジ無水物(PMDA)は化学式(m1)で表される化合物である。
(3)DADE
ジアミノジフェニルエーテル(DADE)は、ジフェニルエーテルのベンゼン環に一つずつアミノ基が結合した化合物である。その例には、4,4’-ジアミノジフェニルエーテル、および3,4’-ジアミノジフェニルエーテルが含まれる。本発明においては、4,4’-ジアミノジフェニルエーテルが好ましい。これを原料とするポリイミドは耐熱性により優れるからである。4,4’-ジアミノジフェニルエーテルは、化学式(m3)で表される。
ビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)は、化学式(m4)で表される化合物である。この化合物は、分子内にスルホニル基、2つのアミノ基、および2つの水酸基を有する、ジヒドロキシジアミンである。
(5)本発明のポリイミドの特性
本発明のポリイミドは、有機溶媒、好ましくは極性有機溶媒に可溶である。このような極性有機溶媒の例には、N-メチルピロリドン、N,N’-ジメチルアセトアミド、およびN,N’-ジメチルホルムアミドが含まれる。ポリイミドが有機溶媒へ溶解する量は、前述の有機溶媒100質量部に対し、10~15質量部が好ましい。本発明において記号「~」はその両端の値を含む。このような溶解性を持つポリイミドは、ポリイミド溶液としたときの取り扱い性に優れるからである。ポリイミドの溶解性の程度に応じて、有機溶媒は適宜選択してよい。
(6)本発明のポリイミドの構造
本発明のポリイミドは、以下の一般式(I)、(II)または(III)の繰り返し単位を有することが好ましい。
―[PMDA]-[HOABSO2]-[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-[HOABSO2]-[PMDA]―U1―(I)
―[DADE]-[DA]-[DADE]―[PMDA]-[HOABSO2]-[PMDA]―[DADE]-[DA]-[DADE]―U2― (II)
―[PMDA]-X3-[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-X3-[PMDA]―U3― (III)
(I)の繰り返し単位
―[PMDA]-[HOABSO2]-[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-[HOABSO2]-[PMDA]―U1―(I)
式中、[PMDA]は、前記ピロメリット酸ジ無水物残基である。[HOABSO2]は、前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基である。[DADE]は、前記ジアミノジフェニルエーテル残基である。[DA]は、前記カルボン酸ジ無水物残基である。残基とは、ポリマーにおける部分構造であって、化学結合以外の構造をいう。例えば、一般式(I)において、[DADE]、すなわちジアミノジフェニルエーテル残基は、二価のジフェニルエーテル基である。
(II)の繰り返し単位
―[DADE]-[DA]-[DADE]―[PMDA]-[HOABSO2]-[PMDA]―[DADE]-[DA]-[DADE]―U2― (II)
この繰り返し構造は、HOABSO2が酸ジ無水物とオキサゾール結合しうることを特徴とする。
(2)の繰り返し単位
(III)の繰り返し単位
―[PMDA]-X3-[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-X3-[PMDA]―U3― (III)
式中、[PMDA]等は、式(I)および(II)において説明したとおりである。
(3-1)の繰り返し単位
(3-2)の繰り返し単位
―[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-X3-[PMDA]―U3― (III’)
これらの構造において、[PMDA]等は、式(I)~(III)において説明したとおりである。
2.本発明のポリイミドの製造方法
本発明のカルボン酸ジ無水物(DA)は、1つのベンゼン環に1つの酸無水物基を有する。一方、ピロメリット酸ジ無水物(PMDA)は、1つのベンゼン環に2つの酸無水物基を有する。すなわち、酸ジ無水物の構造の違いによって、1分子中に存在する酸無水物基同士の近さが異なるため、イミド化反応の反応性も大きく異なる。
1)三つの段階で逐次重合を行う、三段階逐次重合法を採用する。
2)第1および第2工程で、両末端にアミノ基を有するオリゴマー、または両末端に酸無水物基を有するオリゴマーを得る。
3)第3工程で、前工程で得たオリゴマーを重合し、高分子量のポリイミドを得る。
4)同一の工程に、ジアミノジフェニルエーテル(DADE)とピロメリット酸ジ無水物(PMDA)同時に存在させないようにし、有機溶媒に難溶な成分である[PMDA]-[DADE]-[PMDA]または[DADE]-[PMDA]-[DADE]で表されるオリゴマーが製造中に生成されないか、あるいはこれらの構造がポリマーに形成されないようにする。
製造方法Aは、
(A1)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、ジアミノジフェニルエーテル(DADE)2モル当量を反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、
(A2)A1工程で得たオリゴマーと、ピロメリット酸ジ無水物(PMDA)4モル当量とビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)2モル当量とを反応させて両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、および
(A3)A2工程で得たオリゴマーと芳香族ジアミン1モル当量、あるいは、
A2工程で得たオリゴマーと、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、芳香族ジアミン2モル当量を反応させ、重合体を得る工程、を含む方法である。
この工程では、BPDAの一つの酸無水物基と、DADEの一つのアミノ基が反応し、さらにBPDAの他方の酸無水物基と、別分子のDADEの一つのアミノ基が反応する。この結果、末端がアミノ基であるオリゴマー(a1)が生成する。このオリゴマーは安定であって、かつ有機溶媒に可溶であるため、反応液中にオリゴマーが析出しない。
この工程は、4モル当量のピロメリット酸ジ無水物(PMDA)と2モル当量のビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)を添加して、前工程で得たオリゴマーと反応させる。反応機構は限定されないが以下のように推察される。
この工程は、1モル当量のビフェニルテトラカルボン酸ジ無水物(BPDA)と2モル当量の2,4’-ジアミノトルエン(DAT)を添加して、前工程で得たオリゴマーと、1モル当量のBPDAと2モル当量のDATを反応させ、重合体を得る。
製造方法Bは、
(B1)ピロメリット酸ジ無水物(PMDA)2モル当量とビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)1モル当量とを反応させて、両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、
(B2)B1工程で得たオリゴマーと、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)2モル当量と、ジアミノジフェニルエーテル(DADE)4モル当量とを反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、および
(B3)B3工程で得たオリゴマーと、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量、あるいは、
B3工程で得たオリゴマーと、前記カルボン酸ジ無水物(DA)2モル当量と、芳香族ジアミン1モル当量とを反応させ、重合体を得る工程、を含む方法である。
製造方法Cは、
(C1)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、ジアミノジフェニルエーテル(DADE)2モル当量とを反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、
(C2)前工程で得たオリゴマーと、ピロメリット酸ジ無水物(PMDA)4モル当量と芳香族ジアミン2モル当量とを反応させて、両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、ならびに
(C3)前工程で得たオリゴマーとビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)1モル当量、あるいは、
前工程で得たオリゴマーと、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、ビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)1モル当量と、芳香族ジアミン1モル当量とを反応させ、重合体を得る工程を含む、方法である。
3.本発明のポリイミドの用途
(1)複合材料
本発明のポリイミドは、他の材料と複合化された複合材料として用いることができる。特に、基材の上に本発明のポリイミドから得られたフィルムを積層して得た複合材料が好ましい。前述のとおり、本発明のポリイミドは、優れた耐熱性と接着性を有するので、高耐熱かつ高強度の複合材料が得られる。このような複合材料は、航空宇宙材料、輸送用車両材料、半導体用材料として用いることができる。
1)本発明のポリイミドと有機溶媒を含む溶液を準備する工程、
2)前記溶液を、基材の上に流延または塗布して膜を形成する工程、および
3)前記膜を乾燥させる工程を含む方法で製造されることが好ましい。
本発明のポリイミドは、前述のとおり、分子内にオキサゾール基を有するため感光性を有する。よって、ポジ型レジスト材料として有用である。一般にポジ型レジストは、極めて微細なパターンを描画できるため、次世代の半導体材料として用いることができる。
本発明のポリイミドは、有機溶媒に可溶であり、その溶液は安定であって、かつ接着性に優れることから、コーティング剤、塗料、または接着剤として用いることができる。特に、医療用材料、建築材料、家庭用高耐熱材料(アイロンの底、なべの内張り用材料)、難燃性カーテン、ポリテトラフルオロエチレン代替としてコーティング剤等に用いることができる。さらに、本発明のポリイミドが、分子内にカルボキシル基を有する場合、電着塗装が可能な電着塗料としても用いることができる。
実施例においては、特に4,4’-ジアミノジフェニルエーテルをDADEと表記し、3,4’-ジアミノジフェニルエーテルをmDADEと表記した。
(BPDA+2DADE)(4PMDA+2HOABSO2)(BPDA+2DAT)
ガラス製のセパラブルフラスコに、碇型の撹拌羽(ステンレス製)を備えた撹拌装置と水分離トラップ(ディーンスタークトラップ)と還流冷却器を取り付けた。フラスコ内に窒素ガスを流しながら、上記フラスコをシリコン浴に浸漬した。
(BPDA+2DADE)(4PMDA+2HOABSO2)(BPDA+DAT+mTPE)
以下の変更点以外は、実施例1と同様にして10質量%のポリイミド溶液を得た。
1)の工程においてγ-バレロラクトンを1.0g用いた。
2)の工程において添加するNMPの量を140gとした。
3)の工程において添加する原料を、BPDA 2.94g(10mmol)、DAT 1.22g(10mmol)、1,3-ビス(4-アミノフェノキシ)ベンゼン(mTPE) 2.92gとし、添加するNMPの量を80gとした。また、反応時間を6時間とした。
得られたポリイミドの分子量、および耐熱性を表1に示す。
(BPDA+2DADE)(4PMDA+2HOABSO2)(BTDA+DAT+HOABSO2)
以下の変更点以外は、実施例1と同様にしてポリイミド溶液を得た。
1)の工程においてγ-バレロラクトンを1.0g用いた。
2)の工程において添加するNMPの量を140gとした。
3)の工程において添加する原料を、ベンゾフェノンテトラカルボン酸ジ無水物(BTDA)3.22g(10mmol)、DAT 1.22g(10mmol)、4,4’-ジアミノジフェニルスルホン 2.48g(10mmol)とし、かつ反応時間を6.5時間とした。
得られたポリイミドの分子量、および耐熱性を表1に示す。
(BPDA+2DADE)(3PMDA+HOABSO2)(BTDA+2DAT)
以下の変更点以外は、実施例1と同様にしてポリイミド溶液を得た。
1)の工程においてピリジンを1.2g用いた。
2)の工程において添加する原料を、PMDA 6.64g(30mmol)、HOABSO2 2.80g(10mmol)とし、添加するNMPの量を60gとした。
3)の工程において添加するNMPの量を80gとし、かつ反応時間を4.75時間とした。
得られたポリイミドの分子量、および耐熱性を表1に示す。
(2PMDA+HOABSO2)(2BPDA+4DADE)(2BPDA+mPD)
実施例1と同様のフラスコを準備し、シリコン浴に浸漬した。
窒素ガス気流下、180rpm、シリコン浴温度180℃の条件で、40分間加熱撹拌して反応を行った。その後、反応混合物を撹拌しながら20分間空冷した。
(2PMDA+HOABSO2)(2BPDA+4DADE)(2BPDA+HOABSO2)
以下の変更点以外は、実施例5と同様にしてポリイミド溶液を得た。
1)の工程においてピリジンを2.4g、NMPを80g用い、かつ反応時間を50分とした。
3)の工程において添加する原料を、BPDA 5.88g(20mmol)、続いてHOABSO2 2.80g(10mmol)とし、かつ添加するNMPの量を60gとし、反応時間を2.75時間とした。
3)の工程の後に、反応混合物にNMP 100gをさらに加え、10質量%のポリイミド溶液を得た。
得られたポリイミドの分子量、および耐熱性を表1に示す。
(2PMDA+HOABSO2)(2BPDA+4DADE)(2BTDA+HOABSO2)
以下の変更点以外は、実施例5と同様にしてポリイミド溶液を得た。
3)の工程において添加する原料を、BTDA 6.46g(20mmol)、HOABSO2 2.80g(10mmol)にし、反応時間を4時間とした。なお、反応が2時間経過したところでNMP 60gを加えた。
3)の工程の後に、反応混合物にNMP 40gをさらに加え、10質量%のポリイミド溶液を得た。
得られたポリイミド溶液をガラス板表面に塗布し、空気通気下、150℃で30分間乾燥した。乾燥された塗布膜をガラス板から遊離して金属製の枠に貼り付けた。この状態で、250℃で1時間さらに加熱して、ポリイミドフィルムを得た。
得られたポリイミドの分子量、および耐熱性を表1に示す。
(2PMDA+HOABSO2)(2BPDA+4mDADE)(2BTDA+mTPE)
以下の変更点以外は、実施例5と同様にしてポリイミド溶液を得た。
2)の工程において添加する原料を、3,4’-ジアミノジフェニルエーテル(mDADE) 8.00g(40mmol)、BPDA 5.88g(20mmol)とした。
3)の工程において添加する原料を、BTDA 6.46g(20mmol)、1,3-ビス(4-アミノフェノキシ)ベンゼン(mTPE) 2.92g(10mmol)とし、添加するNMPの量を50gとした。反応時間は4時間20分としたが、反応が3時間経過したところでNMP 50gを追加した。
3)の工程の後に、反応混合物にNMP 100gをさらに加え、10質量%のポリイミド溶液を得た。
得られたポリイミドの分子量、および耐熱性を表1に示す。
(BPDA+2DADE)(4PMDA+2DAT)(BPDA+DAT+HOABSO2)
実施例1と同様のフラスコを準備し、シリコン浴に浸漬した。
(BPDA+2DADE)(4PMDA+2DAT)(BTDA+DAT+HOABSO2)
以下の変更点以外は、実施例9と同様にしてポリイミド溶液を得た。
1)工程における反応時間を40分とし、かつその後の空冷時間を40分とした。
2)工程で加えるNMPの量を70gとした。
3)工程で加える原料を、BTDA 4.51g(14mmol)、DAT 1.71g(14mmol)、HOABSO2 3.93g(14mmol)とし、かつ加えるNMPの量を58gとした。また、この工程の反応時間を5時間とした。このようにして14質量%のポリイミド溶液を得た。
得られたポリイミドを実施例1と同様に評価した。結果を表1に示す。
(BPDA+2DADE)(4PMDA+2DAT)(HOABSO2)
以下の変更点以外は、実施例9と同様にしてポリイミド溶液を得た。
1)の工程で加える原料を、BPDA 2.94g(10mmol)、DADE 4.00g(20mmol)、γ-バレロラクトン 0.9g、ピリジン 1.8g、NMP 100g、トルエン 35gとした。また反応時間を1時間とし、かつその後の空冷時間を15分とした。
2)の工程で加える原料を、PMDA 8.72g(40mmol)、DAT 2.44g(20mmol)とし、加えるNMPの量を44gとした。反応後の空冷時間を30分とした。
3)の工程で加える原料を、HOABSO2 2.80g(10mmol)とし、加えるNMPの量を44gとした。また、この工程の反応時間を3.5時間とした。このようにして10質量%のポリイミド溶液を得た。
得られたポリイミドを実施例1と同様に評価した。結果を表1に示す。
(BPDA+2DADE)(3PMDA)(2DAT+HOABSO2+BPDA)
以下の変更点以外は、実施例9と同様にしてポリイミド溶液を得た。
1)の工程における反応後の冷却時間を50分とした。
2)の工程で加える原料を、PMDA 9.15g(42mmol)とし、加えるNMPの量を50gとした。反応後の空冷時間を25分とした。
3)の工程において、先にDAT 3.42g(28mmol)、HOABSO2 3.93g(14mmol)を添加し、撹拌後BPDA 4.12g(14mmol)およびNMP 80gを加えた。得られたポリイミドを実施例1と同様に評価した。結果を表1に示す。
(BPDA+2DADE)(3PMDA+DAT)(BTDA+HOABSO2+SO2AB)
以下の変更点以外は、実施例9と同様にしてポリイミド溶液を得た。
2)の工程で加える原料を、PMDA 9.15g(42mmol)、DAT 1.71g(14mmol)とし、加えるNMPの量を60gとした。
3)の工程で加える原料を、HOABSO2 3.93g(14mmol)、SO2AB 3.48g(14mmol)とし、加えるNMPの量を80gとした。また、この工程の反応は、室温で20分行った後、さらに180℃で11時間45分間を要した。このようにして10質量%のポリイミド溶液を得た。得られたポリイミドを実施例1と同様に評価した。結果を表1に示す。
(BPDA+2DADE)(3PMDA+BPDA+mPD)(HOABSO2)
以下の変更点以外は、実施例9と同様にしてポリイミド溶液を得た。
1)の工程で加える原料を、BPDA 2.94g(10mmol)、DADE 4.00g(20mmol)、γ-バレロラクトン 1.2g、ピリジン 2.0g、NMP 80g、トルエン 25gとした。
2)の工程で加える原料を、PMDA 4.36g(20mmol)、BPDA 2.94g(10mmol)、mPD 1.00g(10mmol)とし、加えるNMPの量を60gとした。これらを添加した後、30分間室温で撹拌し、その後180℃で20分間反応した。
3)の工程で加える原料を、HOABSO2 2.80g(10mmol)、加えるNMPの量を40gとした。また、この工程の反応時間は4時間40分とした。このようにして10質量%のポリイミド溶液を得た。得られたポリイミドを実施例1と同様に評価した。結果を表1に示す。
(BPDA+2DADE)(4PMDA+2DAT)(BPDA+2DAT)
実施例1と同様の装置を準備した。
BPDA 5.88g(20ミリモル)、DADE 8.01g(40ミリモル)、γ-バレロラクトン 1.5g(15ミリモル)、ピリジン 3.5g(44ミリモル)、NMP 150g、トルエン 45gを前記装置に装入した。窒素を通じながら、シリコン浴温度180℃、180rpm回転数で1時間加熱、撹拌した。水-トルエン留分20mlを除いた。
1時間180rpmで空冷、撹拌した。ついでPMDA 17.45g(80ミリモル)、ついでDAT 4.88g(40ミリモル)を加え、さらにNMP 250gを加えて、室温で20分間窒素を通じながら180rpmで撹拌した。
次に、BPDA 5.88g(20ミリモル)、DAT 4.88g(40ミリモル)、NMP 120g、トルエン 30gを加え、230rpmで30分間撹拌して、180℃のシリコン浴で加熱して180rpmで撹拌した。トルエン20mlを除去した。5時間10分間、180℃、180rpmで反応して10質量%のポリイミド溶液を得た。
反応液の一部をジメチルホルムアミドで稀釈して、実施例1と同様にして分子量を測定した。
乾燥ポリイミドフィルムの一部をとり、理学電機製熱分析装置Thermo Plus Tg 8120で熱分解開始温度(Tm)を測定した。条件は、昇温速度 10℃/1分、昇温600℃までとした。Tmは、512.5℃であった。
Perkin Elmer Pyrid Diameter DSCを用いてガラス転位温度(Tg)を測定した。条件は、昇温速度10℃/1分で400℃まで昇温し、その後、空冷して再び10℃/1分で430℃まで昇温した。Tgは観察されなかった。
Claims (16)
- (1)ピロメリット酸ジ無水物(PMDA)、
(2)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)、
(3)ジアミノジフェニルエーテル(DADE)、ならびに
(4)ビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)を重合して得られる、有機溶媒に可溶なポリイミド。 - 一般式(I)で表される繰り返し単位を有する、請求項1記載のポリイミド。
―[PMDA]-[HOABSO2]-[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-[HOABSO2]-[PMDA]―U1― (I)
{式中、[PMDA]は、前記ピロメリット酸ジ無水物残基であり、
[HOABSO2]は、前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基であり、
[DADE]は、前記ジアミノジフェニルエーテル残基であり、
[DA]は、前記カルボン酸ジ無水物残基であり、
U1は、X1、またはX1-[DA]-X1で表される基であり、
(ここで、X1は、フェニレンジアミン残基、アルキル置換フェニレンジアミン残基、ジアミノジフェニルスルホン残基、ビス(アミノフェノキシ)ベンゼン残基、または前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基である)
[DADE]と[DA]、および[DADE]と[PMDA]の結合はイミド結合であり、
[PMDA]と[HOABSO2]との結合は、一般式(i)または(ii)で表される結合であり、
[PMDA]とU1の結合は、U1中のX1がビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基である場合は、前記一般式(i)または(ii)で表される結合であり、それ以外の場合は、イミド結合である。)} - 一般式(II)で表される繰り返し単位を有する、請求項1記載のポリイミド。
―[DADE]-[DA]-[DADE]―[PMDA]-[HOABSO2]-[PMDA]―[DADE]-[DA]-[DADE]―U2― (II)
{式中、[PMDA]は、前記ピロメリット酸ジ無水物残基であり、
[HOABSO2]は、前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基であり、
[DADE]は、前記ジアミノジフェニルエーテル残基であり、
[DA]は、前記カルボン酸ジ無水物残基であり、
U2は、[DA]、または[DA]-X2-[DA]で表される基であり、
(ここで、X2は、フェニレンジアミン残基、アルキル置換フェニレンジアミン残基、ジアミノジフェニルスルホン残基、ビス(アミノフェノキシ)ベンゼン残基、または前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基である)
[DADE]と[DA]、[DADE]と[PMDA]、および[DADE]とU2の結合はイミド結合であり、
[HOABSO2]と[PMDA]の結合は、一般式(i)または(ii)
- 一般式(III)で表される繰り返し単位を有する、請求項1記載のポリイミド。
―[PMDA]-X3-[PMDA]―[DADE]-[DA]-[DADE]―[PMDA]-X3-[PMDA]―U3― (III)
{式中、[PMDA]は、前記ピロメリット酸ジ無水物残基であり、
[DADE]は、前記ジアミノジフェニルエーテル残基であり、
[DA]は、前記カルボン酸ジ無水物残基であり、
X3は、フェニレンジアミン残基、アルキル置換フェニレンジアミン残基、ジアミノジフェニルスルホン残基、またはビス(アミノフェノキシ)ベンゼン残基であり、
U3は、[HOABSO2]、
[HOABSO2]-[DA]-[HOABSO2]、
[HOABSO2]-[DA]-X3、または
X3-[DA]-[HOABSO2]で表される基であり
(ここで、[HOABSO2]は、前記ビス(3-アミノ-4-ヒドロキシフェニル)スルホン残基であり、[DA]、X3は前記のとおり定義される)、
[DADE]と[DA]、[DADE]と[PMDA]、[PMDA]とX3の結合はイミド結合であり、
[HOABSO2]と[PMDA]、および[HOABSO2]と[DA]の結合は、一般式(i)または(ii)
- 一般式(2)で表される繰り返し単位を含む、請求項3記載のポリイミド。
Rは独立に、水素原子またはカルボキシル基であり、
a~dは、炭素原子の位置を示し、a、cの炭素がRと結合する場合は、b、dの炭素がオキサゾール基と結合することを表し、
Y2は、一般式(21)、(22)または(23)で表される基であり、
e~hは、前記a~dと同様に定義され、
Ar1は、一般式(11)~(13)で表される基であり、
*は、フェニレン基とイミド基が結合していることを表す。] - 一般式(3-1)で表される繰り返し単位を含む、請求項4記載のポリイミド。
Rは独立に、水素原子またはカルボキシル基であり、
a~dは炭素原子の位置を表し、a、cの炭素がRと結合する場合は、b、dの炭素がオキサゾール基と結合することを表し、
Ar1は、独立に一般式(11)~(13)で表される基であり、
Y3は、単結合であるか、または式(31)で表される基であり、
*は、フェニレン基とイミド基が結合していることを表す。] - (A1)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、ジアミノジフェニルエーテル(DADE)2モル当量とを反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、
(A2)A1工程で得たオリゴマーと、ピロメリット酸ジ無水物(PMDA)4モル当量とビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)2モル当量とを反応させて両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、および
(A3)A2工程で得たオリゴマーと、
芳香族ジアミン1モル当量、あるいは、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と芳香族ジアミン2モル当量とを反応させて重合体を得る工程を含む、請求項1に記載のポリイミドの製造方法。 - (B1)ピロメリット酸ジ無水物(PMDA)2モル当量とビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)1モル当量とを反応させて、両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、
(B2)B1工程で得たオリゴマーと、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)2モル当量と、ジアミノジフェニルエーテル(DADE)4モル当量とを反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、および
(B3)B2工程で得たオリゴマーと、
ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量、あるいは、前記カルボン酸ジ無水物(DA)2モル当量と芳香族ジアミン1モル当量とを反応させて重合体を得る工程を含む、請求項1に記載のポリイミドの製造方法。 - (C1)ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量と、ジアミノジフェニルエーテル(DADE)2モル当量とを反応させて、両末端がDADE由来のアミノ基であるオリゴマーを得る工程、
(C2)C1工程で得たオリゴマーと、ピロメリット酸ジ無水物(PMDA)4モル当量と芳香族ジアミン2モル当量とを反応させて、両末端がPMDA由来の酸無水物基であるオリゴマーを得る工程、ならびに
(C3)前工程で得たオリゴマーと、
ビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)1モル当量、あるいは、ビフェニルテトラカルボン酸ジ無水物(BPDA)またはベンゾフェノンテトラカルボン酸ジ無水物(BTDA)を含むカルボン酸ジ無水物(DA)1モル当量とビス(3-アミノ-4-ヒドロキシフェニル)スルホン(HOABSO2)1モル当量と、芳香族ジアミン1モル当量とを反応させて重合体を得る工程を含む、請求項1に記載のポリイミドの製造方法。 - 前記製造方法における反応は、γ-バレロラクトンおよびピリジン、または、γ-バレロラクトンおよびN-メチルモルフォリンの存在下で行われる、請求項9~11いずれかに記載の製造方法。
- 請求項1記載のポリイミドから得たフィルムを含む複合材料。
- 請求項1記載のポリイミドを含む電着塗料。
- 請求項1記載のポリイミドと有機溶媒を含む溶液を準備する工程、
前記溶液を、基材の上に流延または塗布して膜を形成する工程、および
前記膜を乾燥させる工程を含む、請求項13記載の複合材料の製造方法。 - 前記乾燥工程は、300℃以下である、請求項15記載の複合材料の製造方法。
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KR1020127001998A KR101472328B1 (ko) | 2009-06-29 | 2009-06-29 | 유기 용매에 가용인, PMDA (pyromellitic dianhydride), DADE (diaminodiphenyl ether), DA (carboxylic dianhydride), 비스(아미노-4-하이드록시페닐)술폰 성분을 함유하는 폴리이미드 및 그 제조 방법 |
JP2011520686A JP5523456B2 (ja) | 2009-06-29 | 2009-06-29 | 有機溶媒に可溶な、pmda、dade、da、ビス(アミノ−4−ヒドロキシフェニル)スルホン成分を含むポリイミドおよびその製造方法 |
PCT/JP2009/061865 WO2011001493A1 (ja) | 2009-06-29 | 2009-06-29 | 有機溶媒に可溶な、pmda、dade、da、ビス(アミノ-4-ヒドロキシフェニル)スルホン成分を含むポリイミドおよびその製造方法 |
TW099121237A TW201114808A (en) | 2009-06-29 | 2010-06-29 | Polyimide soluble in organic solvent and comprising PMDA, DADE, DA AND bis(amino-4-hydroxyphenyl)sulfone component, and process for production thereof |
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JP2016091709A (ja) * | 2014-10-31 | 2016-05-23 | 岡谷電機産業株式会社 | 放電管の製造方法及び放電管 |
CN115850776A (zh) * | 2022-11-29 | 2023-03-28 | 桂林电器科学研究院有限公司 | 高结合力聚酰亚胺薄膜及其制备方法 |
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---|---|---|---|---|
WO2004035689A1 (ja) * | 2002-10-16 | 2004-04-29 | Pi R & D Co., Ltd. | ピロメリット酸ジ無水物を含むブロック共重合ポリイミド溶液組成物及びその製造方法 |
WO2008120398A1 (ja) * | 2007-04-03 | 2008-10-09 | Solpit Industries, Ltd. | 溶剤に可溶な6,6-ポリイミド共重合体及びその製造方法 |
WO2008155811A1 (ja) * | 2007-06-18 | 2008-12-24 | Solpit Industries, Ltd. | 6,6-ポリイミド共重合体及びその製造方法 |
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WO2008120398A1 (ja) * | 2007-04-03 | 2008-10-09 | Solpit Industries, Ltd. | 溶剤に可溶な6,6-ポリイミド共重合体及びその製造方法 |
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JP2015000938A (ja) * | 2013-06-14 | 2015-01-05 | ソマール株式会社 | ポリイミド共重合体オリゴマー、ポリイミド共重合体、およびそれらの製造方法 |
JP2016091709A (ja) * | 2014-10-31 | 2016-05-23 | 岡谷電機産業株式会社 | 放電管の製造方法及び放電管 |
CN115850776A (zh) * | 2022-11-29 | 2023-03-28 | 桂林电器科学研究院有限公司 | 高结合力聚酰亚胺薄膜及其制备方法 |
CN115850776B (zh) * | 2022-11-29 | 2024-01-30 | 桂林电器科学研究院有限公司 | 高结合力聚酰亚胺薄膜及其制备方法 |
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