Classifications

• • 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
  • 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
• • 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
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
  • C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
• • 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
• • 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
  • C08G73/14—Polyamide-imides
• • 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
  • C08G73/16—Polyester-imides
• • 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
• • 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
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • 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
  • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a polyimide resin precursor, a polyimide resin, and a polyimide film.
• Polyimide resins have excellent heat resistance and mechanical properties, and therefore various applications in the fields of electric and electronic parts have been considered.
• polyimide resins which have heat resistance and transparency among electric and electronic components, are used in the field of displays, where glass is generally used as a supporting substrate.
• Patent Document 1 discloses a polyimide precursor having a repeating unit derived from 4-aminophenyl-4-aminobenzoate, for the purpose of obtaining a polyimide film having improved heat resistance, linear thermal expansion coefficient, and light transmittance, and further improved adhesion to a laminate of a polyimide film and a glass substrate.
• Polyimide resins are used not only in the display field but also as insulating film materials in the semiconductor field.
• Polyimide resins used in the semiconductor field are required to have not only heat resistance but also adhesion to the supporting substrate such as silicon, silicon nitride, silicon oxide, etc.
• silicon has fewer functional groups on the surface and has low adhesion to resins, so the polyimide resins are required to have higher adhesion.
• semiconductors require a curing reaction at a lower temperature because high-temperature processing affects the supporting substrate depending on the device configuration, and therefore it is necessary to develop adhesion even at a lower temperature.
• the resin varnish is mainly applied by spin coating, so it is necessary to remove the varnish that has spread to the outer periphery or back surface of the silicon wafer.
• polyimide resins and polyimide resin precursors are generally difficult to dissolve in the rinse liquid (propylene glycol monomethyl ether, cyclohexanone, etc.) used to remove the varnish. Therefore, there is a demand for polyimide resin precursor varnishes that are excellent in solubility in the rinse liquid, i.e., excellent in applicability.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyimide resin precursor which can provide a polyimide resin having excellent heat resistance and adhesion and has excellent coatability, and further to provide a polyimide resin and a polyimide film having excellent heat resistance and adhesion.
• the inventors discovered that a polyimide resin precursor having specific structural units, a polyimide film obtained using the precursor, and a polyimide resin can solve the above problems, and thus completed the invention.
• the organic solvent contains at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone.
• the present invention it is possible to obtain a polyimide resin having excellent heat resistance and adhesion, and to provide a polyimide resin precursor having excellent coatability. It is also possible to provide a polyimide resin and a polyimide film having excellent heat resistance and adhesion. Since the polyimide resin precursor of the present invention has the above-mentioned properties, it is useful as a raw material in the semiconductor field.
• the polyimide resin precursor of the present invention is a polyimide resin precursor having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, in which the structural unit A includes a structural unit (A1) derived from a compound represented by the following formula (a1), and the structural unit B includes at least one selected from the group consisting of a structural unit (B1) derived from a compound represented by the following formula (b1), a structural unit (B2) derived from a compound represented by the following formula (b2), and a structural unit (B3) derived from a compound represented by the following formula (b3).
• the reason why the polyimide resin precursor of the present invention has excellent coatability and why a polyimide resin having excellent heat resistance and adhesion can be obtained by using the polyimide resin precursor of the present invention is not clear, but is thought to be as follows.
• the polyimide resin precursor of the present invention contains a structure derived from a specific tetracarboxylic dianhydride component having a substituent with large steric hindrance and a flexible portion, and contains a structure derived from a specific diamine having an ester skeleton with high linearity and relatively low water absorption, and is considered to increase the solubility of the polyimide precursor while providing a resin obtained after thermal imidization with excellent heat resistance.
• the polyimide resin precursor of the present invention contains the above structure, and is considered to provide a resin that is less likely to absorb moisture that inhibits adhesion.
• the polyimide resin precursor of the present invention can provide a polyimide resin with excellent heat resistance and adhesion, and is considered to provide excellent coatability.
• the structural unit A is a structural unit derived from a tetracarboxylic dianhydride contained in a polyimide resin precursor.
• the structural unit A contains a structural unit (A1) derived from a compound represented by the following formula (a1).
• the structural unit A contains the structural unit (A1), the coatability of the varnish and the adhesion of the polyimide resin can be improved.
• the compound represented by formula (a1) is 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA).
• DSDA 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride
• the ratio of the structural unit (A1) in the structural unit A is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, and still more preferably 95 to 100 mol. It may even be 100 mol, and the structural unit A may be composed only of the structural unit (A1).
• the structural unit A may be composed only of the structural unit (A1), or may include a structural unit other than the structural unit (A1).
• the structural unit other than the structural unit (A1) it is preferable that the structural unit A further includes at least one selected from the group consisting of a structural unit (A3) derived from a compound represented by the following formula (a3) and a structural unit (A4) derived from a compound represented by the following formula (a4), and more preferably includes a structural unit (A3) derived from a compound represented by the following formula (a3).
• the structural unit A includes at least one selected from the group consisting of the structural unit (A3) derived from a compound represented by formula (a3) and the structural unit (A4) derived from a compound represented by formula (a4), and a structural unit (A1) derived from a compound represented by formula (a1), or is composed only of the structural unit (A1).
• the compound represented by formula (a3) is pyromellitic anhydride (PMDA).
• PMDA pyromellitic anhydride
• the compound represented by formula (a4) is 4,4-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl (BP-TME).
• BP-TME 4,4-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl
• the structural unit A contains the structural unit (A4), it is possible to improve the heat resistance of the polyimide resin while maintaining good coatability of the varnish and adhesion of the polyimide resin.
• the molar ratio of the structural unit (A1) to the total of the structural units (A3) and (A4) in the structural unit A [(A1)/((A3)+(A4))] is preferably 30/70 to 100/0, more preferably 40/60 to 100/0, even more preferably 50/50 to 100/0, still more preferably 60/40 to 100/0, even more preferably 60/40 to 90/10, and even more preferably 60/40 to 80/20.
• the structural unit A does not include the structural units (A3) and (A4).
• the molar ratio of the structural unit (A1) to the structural unit (A3) in the structural unit A [(A1)/(A3)] is preferably 30/70 to 100/0, more preferably 40/60 to 100/0, even more preferably 40/60 to 90/10, still more preferably 40/60 to 80/20, even more preferably 40/60 to 70/30, and even more preferably 40/60 to 60/40.
• the structural unit A does not include the structural unit (A3).
• the structural unit A may contain structural units other than the structural unit (A1), the structural unit (A3) and the structural unit (A4).
• the tetracarboxylic dianhydride that gives such a structural unit is not particularly limited, but includes aromatic tetracarboxylic dianhydrides other than the compound represented by formula (a1), other than the compound represented by formula (a3), other than the compound represented by formula (a4), alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.
• the structural unit A contains structural units other than the structural unit (A1), the structural unit (A3) and the structural unit (A4), it is preferable to contain an aromatic tetracarboxylic dianhydride among tetracarboxylic dianhydrides other than the compound represented by formula (a1), other than the compound represented by formula (a3), and other than the compound represented by formula (a4).
• aromatic tetracarboxylic dianhydrides include 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride (BPF-PA), 2,3,6,7-naphthalene tetracarboxylic 2,3:6,7-dianhydride (NTCDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and 4,4'-oxydiphthalic anhydride (ODPA).
• BPF-PA 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride
• NTCDA 2,3,6,7-naphthalene t
• dianhydride examples include 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis(trimellitate) dianhydride (TMEG), and p-phenylene bis(trimellitate) dianhydride (TAHQ).
• s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
• a-BPDA 2,3,3',4'-biphenyltetracarboxylic dianhydride
• BPAF 9,9'-bis(3,4-dicarboxy
• 3,3',4,4'-benzophenone tetracarboxylic dianhydride is preferred.
• alicyclic tetracarboxylic dianhydrides include cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclohexane-1,2,3,4-tetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5',6,6'-tetracarboxylic dianhydride (CpODA), 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, Examples of the dianhydride include pentan
• aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride.
• aromatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more aromatic rings
• alicyclic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing one or more alicyclic rings but no aromatic rings
• aliphatic tetracarboxylic acid dianhydride refers to a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
• the structural unit optionally contained in the structural unit A may be of one type, or of two or more types.
• the structural unit B is a structural unit derived from a diamine contained in the polyimide resin precursor.
• the structural unit B includes at least one selected from the group consisting of a structural unit (B1) derived from a compound represented by the following formula (b1), a structural unit (B2) derived from a compound represented by the following formula (b2), and a structural unit (B3) derived from a compound represented by the following formula (b3):
• the compound represented by formula (b1) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
• the compound represented by formula (b2) is bis(4-aminophenyl)terephthalate (APTP).
• APTP bis(4-aminophenyl)terephthalate
• the compound represented by formula (b3) is 1,4-bis(4-aminobenzoyloxy)benzene.
• the structural unit B contains at least one selected from the group consisting of the structural unit (B1), the structural unit (B2), and the structural unit (B3), preferably includes at least one selected from the group consisting of the structural unit (B1) and the structural unit (B2), and more preferably includes the structural unit (B1).
• the total of the ratio of the structural unit (B1), the ratio of the structural unit (B2), and the ratio of the structural unit (B3) in the structural unit B is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the structural unit B may be composed of only at least one unit selected from the group consisting of the structural unit (B1), the structural unit (B2), and the structural unit (B3).
• the ratio of the structural unit (B1) in the structural unit B is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, and still more preferably 95 to 100 mol.
• the structural unit B may be composed only of the structural unit (B1).
• the ratio of the structural unit (B2) in the structural unit B is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, and still more preferably 95 to 100 mol. It may even be 100 mol, and the structural unit B may be composed only of the structural unit (B2).
• the ratio of the structural unit (B3) in the structural unit B is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, and still more preferably 95 to 100 mol. It may even be 100 mol, and the structural unit B may be composed only of the structural unit (B3).
• the heat resistance of the resulting polyimide resin is excellent, and furthermore, the coatability of the varnish and the adhesion of the polyimide resin can be improved.
• the structural unit B may contain structural units other than the structural unit (B1), the structural unit (B2), and the structural unit (B3).
• Diamines that provide such structural units are not particularly limited, and examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines excluding any of the compounds represented by formula (b1), the compounds represented by formula (b2), and the compounds represented by formula (b3).
• aromatic diamines examples include 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-TFMB), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane (HFDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diamino diphenyl ether, 4,4'-dia
• alicyclic diamine examples include 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, isophoronediamine, bis(aminomethyl)norbornane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, and 2,2-bis(4-aminocyclohexyl)propane.
• Aliphatic diamines include ethylenediamine and hexamethylenediamine.
• an aromatic diamine means a diamine containing one or more aromatic rings
• an alicyclic diamine means a diamine containing one or more alicyclic rings but no aromatic rings
• an aliphatic diamine means a diamine containing neither an aromatic ring nor an alicyclic ring.
• the structural units other than the structural units (B1), (B2), and (B3) optionally contained in the structural unit B may be of one type, or of two or more types.
• the number average molecular weight of the polyimide resin precursor is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the resulting polyimide film. Also, from the same viewpoint, the weight average molecular weight (Mw) is preferably 10,000 to 800,000, more preferably 30,000 to 300,000. The number average molecular weight and weight average molecular weight of the polyimide resin precursor can be determined from standard polymethyl methacrylate (PMMA) equivalent values measured by gel filtration chromatography.
• PMMA polymethyl methacrylate
• the polyimide resin precursor of the present invention is preferably a polyimide resin precursor having a polyamic acid structure, and more preferably a polyamic acid.
• the polyimide resin precursor may be produced by any method, but is preferably produced by the following method. As described above, the polyimide resin precursor is preferably produced by a production method in which a compound (tetracarboxylic acid component) that provides the above-mentioned structural unit A is reacted with a compound (diamine component) that provides the above-mentioned structural unit B to obtain a polyimide resin precursor having a polyamic acid structure.
• a preferred method for producing a polyimide resin precursor is a method for producing a polyimide resin precursor having a polyamic acid structure by reacting a tetracarboxylic acid component containing a compound represented by formula (a1) with a diamine component containing at least one selected from the group consisting of a compound represented by formula (b1), a compound represented by formula (b2), and a compound represented by formula (b3).
• the tetracarboxylic acid component used in the present production method includes a compound that provides the structural unit (A1), and may also include a tetracarboxylic acid component other than the compound that provides the structural unit (A1), provided that the effects of the present invention are not impaired.
• the diamine component used in the present production method preferably contains at least one selected from the group consisting of a compound that provides the structural unit (B1), a compound that provides the structural unit (B2), and a compound that provides the structural unit (B3), and may contain diamine components other than the compound that provides the structural unit (B1), the compound that provides the structural unit (B2), and the compound that provides the structural unit (B3), provided that the effects of the present invention are not impaired.
• the amount of the diamine component relative to the tetracarboxylic acid component is preferably 0.9 to 1.1 moles.
• the method for reacting the tetracarboxylic acid component with the diamine component is not particularly limited, and any known method can be used.
• Specific examples of the reaction method include a method in which a tetracarboxylic acid component, a diamine component, a solvent, and, if necessary, an end-capping agent are charged into a reactor, and the mixture is stirred at a temperature in the range of preferably 0 to 120° C., more preferably 5 to 80° C., for 1 to 72 hours. When the reaction is carried out at 80° C.
• the molecular weight of the polyimide resin precursor does not vary depending on the temperature history during polymerization, and the progress of thermal imidization can be suppressed, so that a polyimide resin precursor having a polyamic acid structure can be stably produced.
• a polyimide resin precursor solution having a polyamic acid structure dissolved in a solvent can be obtained.
• the concentration of the polyimide resin precursor in the resulting solution is preferably from 1 to 50% by mass, more preferably from 3 to 35% by mass, and further preferably from 5 to 30% by mass.
• the tetracarboxylic acid component used as a raw material in the present production method is preferably the tetracarboxylic acid dianhydride described above in the section on ⁇ Structural Unit (A)>.
• the tetracarboxylic acid dianhydride used as the tetracarboxylic acid component in the present production method may be in any form of dianhydride, tetracarboxylic acid (free acid), or alkyl ester of tetracarboxylic acid, but is preferably a dianhydride.
• the tetracarboxylic acid component used as a starting material in the present production method includes a compound represented by the above formula (a1) (a compound that provides the structural unit (A1)).
• the ratio of the compound represented by formula (a1) in the tetracarboxylic acid component is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, and still more preferably 95 to 100 mol. It may be 100 mol, and the tetracarboxylic acid component may consist only of the compound represented by formula (a1).
• the ratio of the compound represented by formula (a1) is within the above range, the heat resistance of the resulting polyimide resin is excellent, and further, the coatability of the precursor varnish and the adhesion of the polyimide resin can be improved.
• the tetracarboxylic acid component may consist only of the compound represented by formula (a1), or may contain a tetracarboxylic acid component other than the compound represented by formula (a1).
• a tetracarboxylic acid component other than the compound represented by formula (a1) preferably, it further contains at least one selected from the group consisting of a compound represented by the following formula (a3) and a compound represented by the following formula (a4), and more preferably contains a compound represented by the following formula (a3).
• the compound represented by formula (a3) is pyromellitic anhydride (PMDA).
• PMDA pyromellitic anhydride
• the compound represented by formula (a4) is 4,4-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl (BP-TME).
• BP-TME 4,4-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl
• the molar ratio of the compound represented by formula (a1) to the compound represented by formula (a3) and the compound represented by formula (a4) in the structural unit A [(a1)/((a3)+(a4))] is preferably 30/70 to 100/0, more preferably 40/60 to 100/0, even more preferably 50/50 to 100/0, even more preferably 60/40 to 100/0, even more preferably 60/40 to 90/10, and even more preferably 60/40 to 80/20.
• the tetracarboxylic acid component does not include the compound represented by formula (a3) and the compound represented by formula (a4).
• the molar ratio [(a1)/(a3)] of the compound represented by formula (a1) to the compound represented by formula (a3) in the tetracarboxylic acid component is preferably 30/70 to 100/0, more preferably 40/60 to 100/0, even more preferably 40/60 to 90/10, still more preferably 40/60 to 80/20, still more preferably 40/60 to 70/30, and still more preferably 40/60 to 60/40.
• the tetracarboxylic acid component does not contain the compound represented by formula (a3).
• the heat resistance of the polyimide resin can be increased while maintaining good coatability of the varnish and adhesion of the polyimide resin.
• the tetracarboxylic acid component may contain a tetracarboxylic acid component other than the compound represented by formula (a1), the compound represented by formula (a3), and the compound represented by formula (a4).
• a tetracarboxylic acid component is not particularly limited, and examples thereof include aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aliphatic tetracarboxylic acid dianhydrides other than the compound represented by formula (a1), the compound represented by formula (a3), and the compound represented by formula (a4).
• the tetracarboxylic acid component contains a tetracarboxylic acid component other than the compound represented by formula (a1), the compound represented by formula (a3), and the compound represented by formula (a4)
• aromatic tetracarboxylic dianhydrides include 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride (BPF-PA), 2,3,6,7-naphthalene tetracarboxylic 2,3:6,7-dianhydride (NTCDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and 4,4'-oxydiphthalic anhydride (ODPA).
• BPF-PA 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride
• NTCDA 2,3,6,7-naphthalene t
• dianhydride examples include 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis(trimellitate) dianhydride (TMEG), and p-phenylene bis(trimellitate) dianhydride (TAHQ).
• s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
• a-BPDA 2,3,3',4'-biphenyltetracarboxylic dianhydride
• BPAF 9,9'-bis(3,4-dicarboxy
• 3,3',4,4'-benzophenone tetracarboxylic dianhydride is preferred.
• alicyclic tetracarboxylic dianhydrides include cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclohexane-1,2,3,4-tetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5',6,6'-tetracarboxylic dianhydride (CpODA), 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, Examples of the dianhydride include pentan
• aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
• the diamine component used as a raw material in the present production method is preferably the diamine described above in the section on ⁇ Structural unit (B)>.
• the diamine used as the diamine component in the present production method may be in the form of either a diamine or a diisocyanate corresponding to the diamine, but is preferably a diamine.
• the diamine component used as a raw material in this production method includes at least one selected from the group consisting of the compound represented by formula (b1) (compound that provides structural unit (B1)), the compound represented by formula (b2) (compound that provides structural unit (B2)), and the compound represented by formula (b3) (compound that provides structural unit (B3)), preferably includes at least one selected from the group consisting of the compound represented by formula (b1) and the compound represented by formula (b2), more preferably includes the compound represented by formula (b1). It may include two or three of the compounds represented by formula (b1), (b2), and (b3).
• the total ratio of the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3) in the diamine component is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the diamine component may consist of only at least one selected from the group consisting of the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3).
• the ratio of the compound represented by formula (b1) in the diamine component is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the diamine component may consist of only the compound represented by formula (b1).
• the ratio of the compound represented by formula (b2) in the diamine component is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the diamine component may consist of only the compound represented by formula (b2).
• the ratio of the compound represented by formula (b3) in the diamine component is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the diamine component may consist of only the compound represented by formula (b3).
• the ratio of the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3) is within the above range, the heat resistance of the obtained polyimide resin is excellent, and further, the coatability of the precursor varnish and the adhesion of the polyimide resin can be improved.
• the diamine component may contain a diamine component other than the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3).
• diamine components are not particularly limited, and examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines excluding any of the compounds represented by formula (b1), the compounds represented by formula (b2), and the compounds represented by formula (b3).
• aromatic diamines examples include 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-TFMB), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane (HFDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diamino diphenyl ether, 4,4'-dia
• alicyclic diamine examples include 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, isophoronediamine, bis(aminomethyl)norbornane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, and 2,2-bis(4-aminocyclohexyl)propane.
• Aliphatic diamines include ethylenediamine and hexamethylenediamine. The diamine may be used alone or in combination of two or more.
• a terminal blocking agent may be used in the production of the polyimide resin precursor.
• the terminal blocking agent is preferably a monoamine or a dicarboxylic acid, and more preferably a monoamine.
• the amount of the terminal blocking agent to be introduced is preferably 0.0001 to 0.2 mol, more preferably 0.0001 to 0.1 mol, even more preferably 0.001 to 0.06 mol, and even more preferably 0.01 to 0.06 mol, relative to 1 mol of the tetracarboxylic acid component.
• the amount of the terminal blocking agent to be introduced is preferably 0.001 to 0.2 mol, more preferably 0.01 to 0.2 mol, even more preferably 0.06 to 0.2 mol, and even more preferably 0.1 to 0.2 mol, relative to 1 mol of the tetracarboxylic acid component.
• Examples of the monoamine end-capping agent include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, o-aminophenol (2-aminophenol), m-aminophenol (3-aminophenol), p-aminophenol (4-aminophenol), o-aminobenzoic acid, m-aminobenzoic acid, and p-aminobenzoic acid.
• dicarboxylic acid end-capping agent examples include dicarboxylic acids, which may be partially ring-closed. Examples include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc. Of these, phthalic acid and phthalic anhydride are more preferred.
• the solvent (organic solvent) used in the production of the polyimide resin precursor may be any solvent capable of dissolving the polyimide resin precursor produced.
• the solvent include aprotic solvents, phenolic solvents, ether solvents, and carbonate solvents, and aprotic solvents are preferred.
• aprotic solvents include amide solvents, lactone solvents, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents, among which amide solvents or lactone solvents are preferred, and amide solvents are more preferred.
• the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and the like.
• At least one selected from the group consisting of 1,3-dimethyl-2-imidazolidone and N-methyl-2-pyrrolidone is preferred, N-methyl-2-pyrrolidone is more preferred in terms of resin solubility, and 1,3-dimethyl-2-imidazolidinone is more preferred in terms of obtaining a resin with high heat resistance.
• lactone solvents include ⁇ -butyrolactone and ⁇ -valerolactone, with ⁇ -butyrolactone being preferred.
• Examples of phosphorus-containing amide solvents include hexamethylphosphoric amide and hexamethylphosphine triamide.
• Examples of the sulfur-containing solvent include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, and cyclopentanone.
• Examples of the ester solvent include 2-methoxy-1-methylethyl acetate.
• phenol-based solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol.
• ether solvent examples include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, and propylene glycol monomethyl ether.
• the carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
• At least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone and ⁇ -butyrolactone is more preferable, 1,3-dimethyl-2-imidazolidinone or ⁇ -butyrolactone is even more preferable, and ⁇ -butyrolactone is even more preferable.
• the above solvents may be used alone or in combination of two or more kinds.
• the organic solvent preferably contains at least one selected from the group consisting of amide solvents and lactone solvents, more preferably contains at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone, even more preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone and ⁇ -butyrolactone, and still more preferably contains ⁇ -butyrolactone.
• the varnish of the present invention contains the above-mentioned polyimide resin precursor and an organic solvent, that is, the polyimide resin precursor is dissolved in the organic solvent.
• the organic solvent is not particularly limited as long as it dissolves the polyimide resin precursor, but the compounds described above as solvents used in the production of the polyimide resin precursor (solvents described in the [Solvent (organic solvent)] section) are preferred, and the same is true for more preferred solvents. Specific examples include aprotic solvents, phenol-based solvents, ether-based solvents, carbonate-based solvents, etc., and aprotic solvents are preferred.
• aprotic solvents include amide solvents, lactone solvents, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents, among which amide solvents or lactone solvents are preferred, and amide solvents are more preferred.
• amide solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc., and at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidone is preferred, and from the viewpoint of resin solubility, N-methyl-2-pyrrolidone is more preferred.
• 1,3-dimethyl-2-imidazolidinone used in the production of the precursor is more preferred.
• lactone solvents include ⁇ -butyrolactone and ⁇ -valerolactone, with ⁇ -butyrolactone being preferred.
• phosphorus-containing amide solvents include hexamethylphosphoric amide and hexamethylphosphine triamide.
• sulfur-containing solvent include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.
• the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, and cyclopentanone.
• ester solvent include 2-methoxy-1-methylethyl acetate.
• phenol-based solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol.
• ether solvent examples include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, and propylene glycol monomethyl ether.
• the carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
• organic solvents at least one selected from the group consisting of amide-based solvents and lactone-based solvents is preferred, an amide-based solvent or a lactone-based solvent is preferred, at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone is preferred, at least one selected from the group consisting of N-methyl-2-pyrrolidone and ⁇ -butyrolactone is more preferred, N-methyl-2-pyrrolidone or ⁇ -butyrolactone is even more preferred, and ⁇ -butyrolactone is even more preferred.
• At least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone and ⁇ -butyrolactone used in the production of the precursor is more preferred, 1,3-dimethyl-2-imidazolidinone or ⁇ -butyrolactone is even more preferred, and ⁇ -butyrolactone is even more preferred.
• the above organic solvents may be used alone or in combination of two or more kinds.
• the organic solvent preferably contains at least one selected from the group consisting of amide solvents and lactone solvents, more preferably contains at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone, even more preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone and ⁇ -butyrolactone, and even more preferably contains ⁇ -butyrolactone.
• the organic solvent more preferably contains at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone and ⁇ -butyrolactone used in the production of the precursor, even more preferably contains 1,3-dimethyl-2-imidazolidinone or ⁇ -butyrolactone, and even more preferably contains ⁇ -butyrolactone.
• the varnish of the present invention may be the polyimide resin precursor solution itself after the production of the polyimide resin precursor, or may be a solution obtained by further diluting the polyimide resin precursor solution by mixing it with an organic solvent.
• the varnish of the present invention may further contain an imidization catalyst and a dehydration catalyst from the viewpoint of efficiently proceeding with the imidization of the polyamic acid portion of the polyimide resin precursor of the present invention.
• an imidization catalyst having a boiling point of 40° C. or more is preferable. If the imidization catalyst has a boiling point of 40° C. or more, the imidization can be sufficiently proceeded before volatilization.
• the imidization catalyst include amine compounds such as pyridine and picoline, imidazole compounds such as imidazole, 1,2-dimethylimidazole, 1-benzylimidazole, 1-benzyl-2-methylimidazole, and benzimidazole, etc.
• the above imidization catalysts may be used alone or in combination of two or more kinds.
• the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. These may be used alone or in combination of two or more kinds.
• the polyimide resin precursor contained in the varnish of the present invention has solvent solubility, and therefore can be made into a high-concentration varnish that is stable at room temperature.
• the varnish of the present invention preferably contains 3 to 40 mass % of the polyimide resin precursor, and more preferably contains 5 to 30 mass %.
• the viscosity of the varnish is preferably 0.1 to 100 Pa ⁇ s, and more preferably 0.1 to 20 Pa ⁇ s.
• the viscosity of the varnish is a value measured at 25°C using an E-type viscometer.
• the varnish of the present invention may also contain various additives such as inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, surfactants, leveling agents, defoamers, fluorescent brightening agents, crosslinking agents, polymerization initiators, and photosensitizers, as long as the additives do not impair the required properties of the resulting polyimide resin and polyimide film.
• the method for producing the varnish of the present invention is not particularly limited, and a known method can be applied.
• the varnish can be obtained by mixing a further solvent, if necessary, with the solution of the polyimide resin precursor obtained by the above-mentioned production method to adjust the concentration.
• the polyimide film of the present invention is preferably produced using the above-mentioned varnish.
• the polyimide film of the present invention is obtained by imidizing the above-mentioned polyimide resin precursor.
• the method for producing a polyimide film using the varnish of the present invention is not particularly limited, and a known method can be used.
• the varnish of the present invention is applied to a smooth support such as a glass plate, a metal plate, or a plastic plate, or formed into a film, and then the organic solvent contained in the varnish, such as a reaction solvent or a dilution solvent, is removed by heating to obtain a polyamic acid film, and the polyamic acid in the polyamic acid film is imidized (dehydration ring closure) by heating, and then peeled off from the support, thereby producing a polyimide film.
• the support is preferably made of silicon, silicon nitride, silicon oxide, etc., and more preferably silicon. That is, the polyimide film of the present invention is preferably a film obtained by applying the above-mentioned varnish onto a support and heating it, and the method for producing the polyimide film of the present invention is preferably a method of applying the above-mentioned varnish onto a support and heating it.
• the heating temperature when the varnish containing the polyimide resin precursor is dried to obtain a polyimide resin precursor (polyamic acid) film is preferably 50 to 150° C.
• the heating temperature when the polyimide resin precursor is imidized by heating is preferably 300 to 420° C., more preferably 350 to 400° C.
• the heating time is preferably 1 minute to 6 hours, more preferably 5 minutes to 2 hours, and even more preferably 15 minutes to 1 hour. By using such a temperature and time, the physical properties of the obtained polyimide film are improved.
• Examples of the heating atmosphere include air gas, nitrogen gas, oxygen gas, hydrogen gas, and nitrogen/hydrogen mixed gas.
• nitrogen gas having an oxygen concentration of 100 ppm or less and nitrogen/hydrogen mixed gas containing hydrogen at a concentration of 0.5% or less are preferred.
• the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.
• the thickness of the polyimide film of the present invention can be appropriately selected depending on the application, etc., but is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, even more preferably 1 ⁇ m or more, even more preferably 5 ⁇ m or more, even more preferably 7 ⁇ m or more. Also, it is preferably 250 ⁇ m or less, more preferably 100 ⁇ m or less, even more preferably 50 ⁇ m or less, and even more preferably 20 ⁇ m or less. When the thickness is in the above range, it can be practically used as an insulating film. The thickness of the polyimide film can be easily controlled by adjusting the solids concentration and viscosity of the varnish.
• the polyimide film of the present invention preferably has the following physical properties. By satisfying the following physical properties, the polyimide film of the present invention has excellent heat resistance.
• the glass transition temperature (Tg) is preferably 320° C. or higher, more preferably 330° C. or higher, even more preferably 350° C. or higher, and still more preferably 400° C. or higher.
• the 5% weight loss temperature (Td5%) is preferably 500°C or higher, and more preferably greater than 500°C.
• the polyimide film of the present invention has the excellent properties described above and can be used for a variety of applications, but is particularly suitable for use as a film for various members of semiconductor components. In particular, it is suitable for use as an insulating film for semiconductors.
• the polyimide resin of the present invention is a polyimide resin having a structural unit AI derived from a tetracarboxylic dianhydride and a structural unit BI derived from a diamine, in which the structural unit AI includes a structural unit (AI1) derived from a compound represented by formula (a1) below, and the structural unit BI includes at least one selected from the group consisting of a structural unit (BI1) derived from a compound represented by formula (b1) below, a structural unit (BI2) derived from a compound represented by formula (b2) below, and a structural unit (BI3) derived from a compound represented by formula (b3) below.
• the structural unit AI includes a structural unit (AI1) derived from a compound represented by formula (a1) below
• the structural unit BI includes at least one selected from the group consisting of a structural unit (BI1) derived from a compound represented by formula (b1) below, a structural unit (BI2) derived from a compound represented by formula (b2) below, and a structural
• the polyimide resin of the present invention constitutes the above-mentioned polyimide film, and the above-mentioned polyimide film is made of the polyimide resin of the present invention.
• the polyimide resin of the present invention may be obtained by any production method, but is preferably obtained by a production method in which the above-mentioned polyimide resin precursor is imidized.
• the reason why the polyimide resin of the present invention and the polyimide film containing the polyimide resin have excellent heat resistance and adhesion is not clear, but is thought to be as follows.
• the polyimide resin and polyimide film of the present invention are believed to have excellent heat resistance by including a structure derived from a specific tetracarboxylic dianhydride component having a substituent with large steric hindrance and a flexible portion, and a structure derived from a specific diamine having an ester skeleton with high linearity and relatively low water absorption.
• the polyimide resin and polyimide film of the present invention are believed to be less likely to absorb moisture that inhibits adhesion by including the above structure.
• the polyimide resin and polyimide film of the present invention are believed to have excellent heat resistance and adhesion.
• the structural unit AI contains a structural unit (AI1) derived from a compound represented by the following formula (a1).
• AI1 structural unit derived from a compound represented by the following formula (a1).
• the ratio of the structural unit (AI1) in the structural unit AI is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the structural unit AI may be composed only of the structural unit (AI1).
• the proportion of the structural unit (AI1) is within the above range, the polyimide resin will have excellent heat resistance and improved adhesion.
• the structural unit AI contains at least one selected from the group consisting of the structural unit (AI3) derived from a compound represented by formula (a3) and the structural unit (AI4) derived from a compound represented by formula (a4), and the structural unit (AI1) derived from a compound represented by formula (a1), or is composed only of the structural unit (AI1).
• the molar ratio of the structural unit (AI1) to the total of the structural units (AI3) and (AI4) in the structural unit AI [(AI1)/((AI3)+(AI4))] is preferably 30/70 to 100/0, more preferably 40/60 to 100/0, even more preferably 50/50 to 100/0, even more preferably 60/40 to 100/0, even more preferably 60/40 to 90/10, and even more preferably 60/40 to 80/20.
• the structural unit AI does not include the structural units (AI3) and (AI4).
• the molar ratio of the structural unit (AI1) to the structural unit (AI3) in the structural unit AI [(AI1)/(AI3)] is preferably 30/70 to 100/0, more preferably 40/60 to 100/0, even more preferably 40/60 to 90/10, even more preferably 40/60 to 80/20, even more preferably 40/60 to 70/30, and even more preferably 40/60 to 60/40.
• the structural unit AI does not include the structural unit (AI3).
• the structural units constituting the structural unit AI are in the above molar ratio, it is possible to enhance the heat resistance of the polyimide resin while maintaining good coatability of the varnish and adhesion of the polyimide resin.
• the structural unit AI may contain structural units other than the structural unit (AI1), the structural unit (AI3) and the structural unit (AI4).
• the tetracarboxylic dianhydride that gives such a structural unit is not particularly limited, but includes aromatic tetracarboxylic dianhydrides other than the compound represented by formula (a1), other than the compound represented by formula (a3), other than the compound represented by formula (a4), alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.
• aromatic tetracarboxylic dianhydrides include 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride (BPF-PA), 2,3,6,7-naphthalene tetracarboxylic 2,3:6,7-dianhydride (NTCDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and 4,4'-oxydiphthalic anhydride (ODPA).
• BPF-PA 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride
• NTCDA 2,3,6,7-naphthalene t
• dianhydride examples include 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis(trimellitate) dianhydride (TMEG), and p-phenylene bis(trimellitate) dianhydride (TAHQ).
• s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
• a-BPDA 2,3,3',4'-biphenyltetracarboxylic dianhydride
• BPAF 9,9'-bis(3,4-dicarboxy
• 3,3',4,4'-benzophenone tetracarboxylic dianhydride is preferred.
• alicyclic tetracarboxylic dianhydrides include cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclohexane-1,2,3,4-tetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5',6,6'-tetracarboxylic dianhydride (CpODA), 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, Examples of the dianhydride include pentan
• the structural unit BI is a structural unit derived from a diamine.
• the structural unit BI includes at least one selected from the group consisting of a structural unit (BI1) derived from a compound represented by the following formula (b1), a structural unit (BI2) derived from a compound represented by the following formula (b2), and a structural unit (BI3) derived from a compound represented by the following formula (b3):
• the compound represented by formula (b1) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
• the compound represented by formula (b2) is bis(4-aminophenyl)terephthalate (APTP).
• APTP bis(4-aminophenyl)terephthalate
• the structural unit BI contains the structural unit (BI2)
• the polyimide resin has excellent heat resistance and improved adhesion.
• the compound represented by formula (b3) is 1,4-bis(4-aminobenzoyloxy)benzene.
• the structural unit BI contains the structural unit (BI3), the polyimide resin has excellent heat resistance and improved adhesion.
• the ratio of the structural unit (BI1) in the structural unit BI is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the structural unit BI may be composed only of the structural unit (BI1).
• the ratio of the structural unit (BI2) in the structural unit BI is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol, and the structural unit BI may be composed only of the structural unit (BI2).
• the ratio of the structural unit (BI3) in the structural unit BI is preferably 30 to 100 mol, more preferably 70 to 100 mol, even more preferably 90 to 100 mol, still more preferably 95 to 100 mol, or may be 100 mol.
• the structural unit BI may be composed only of the structural unit (BI3). When the ratio of the structural unit (BI1), the structural unit (BI2), and the structural unit (BI3) is within the above-mentioned range, the heat resistance of the obtained polyimide resin is excellent, and the adhesion of the polyimide resin can also be improved.
• the structural unit BI may contain structural units other than the structural units (BI1), (BI2) and (BI3).
• Diamines that provide such structural units are not particularly limited, and include aromatic diamines, alicyclic diamines and aliphatic diamines excluding any of the compounds represented by formula (b1), (b2) and (b3).
• aromatic diamines examples include 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-TFMB), 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane (HFDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diamino diphenyl ether, 4,4'-dia
• alicyclic diamine examples include 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, isophoronediamine, bis(aminomethyl)norbornane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, and 2,2-bis(4-aminocyclohexyl)propane.
• Aliphatic diamines include ethylenediamine and hexamethylenediamine.
• the structural units other than the structural units (BI1), (BI2), and (BI3) optionally contained in the structural unit BI may be of one type or of two or more types.
• the polyimide resin of the present invention may contain a structure other than a polyimide chain (a structure formed by imide bonds between structural units AI and BI) within the scope of the present invention.
• structures other than polyimide chains that can be contained in the polyimide resin include structures containing amide bonds.
• the polyimide resin of the present invention preferably contains a polyimide chain (a structure formed by imide bonding between the structural unit AI and the structural unit BI) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin of the present invention is preferably 80 mass % or more, more preferably 90 mass % or more, even more preferably 99 mass % or more, and still more preferably 100 mass %.
• the polyimide resin of the present invention preferably has the following physical properties. By satisfying the following physical properties, the polyimide resin of the present invention has excellent heat resistance.
• the glass transition temperature (Tg) is preferably 400°C or higher, more preferably 410°C or higher, even more preferably 420°C or higher, still more preferably 430°C or higher, still more preferably 440°C or higher, and still more preferably 450°C or higher.
• the 5% weight loss temperature (Td5%) is preferably 500°C or higher, and more preferably greater than 500°C.
• the above-mentioned physical properties in the present invention can be specifically measured by the methods described in the Examples.
• the polyimide resin of the present invention has the excellent properties described above and can be used for a variety of applications, but is particularly suitable for use as a resin for various members of semiconductor components. In particular, it is suitable for use as an insulating film for semiconductors.
• the present invention also includes a polyimide film made of the polyimide resin of the present invention.
• the polyimide film made of the polyimide resin of the present invention is preferably obtained by a production method in which the polyimide resin precursor is imidized.
• the thickness of the polyimide film made of the polyimide resin of the present invention can be appropriately selected depending on the application, etc., but is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, even more preferably 1 ⁇ m or more, even more preferably 5 ⁇ m or more, even more preferably 7 ⁇ m or more.
• the polyimide film made of the polyimide resin of the present invention preferably has the following physical properties. By satisfying the following physical properties, the polyimide film has excellent heat resistance.
• the glass transition temperature (Tg) is preferably 400°C or higher, more preferably 410°C or higher, even more preferably 420°C or higher, still more preferably 430°C or higher, still more preferably 440°C or higher, and still more preferably 450°C or higher.
• the 5% weight loss temperature (Td5%) is preferably 500°C or higher, and more preferably greater than 500°C.
• the polyimide film made of the polyimide resin of the present invention has the above-mentioned excellent properties, it can be used for various applications, and is particularly suitable for use as a film for various members of semiconductor parts, and particularly suitable for use as an insulating film for semiconductors.
• a solution in which the polyimide resin precursor was dissolved and became a homogeneous solution was rated as having "suitability for rinsing," and a solution in which the polyimide resin precursor was precipitated and became a non-uniform dispersion was rated as having "no suitability for rinsing.”
• a solution with rinsing suitability has excellent coatability. Also, a solution with rinsing suitability in a larger number of solvents has better coatability.
• (2) Film Thickness The film thickness was measured using a digital gauge SA-S110/03N manufactured by Citizen Finedevices Co., Ltd.
• a polyimide layer (polyimide film) was obtained on a 4-inch silicon wafer by the method described in the examples. Using a cutter knife, the polyimide layer was cut into a grid of 100 squares (each square was 1 mm x 1 mm), which was used as the grid portion (cross-cut portion). Tape (Cellotape (registered trademark), CT-24, manufactured by Nichiban Co., Ltd.) was applied to the entire surface of the grid portion (cross-cut portion). The applied tape was peeled off in 0.5 to 1 second. Thereafter, the number of squares of the polyimide layer remaining in the grid portion was counted. The more squares of the polyimide layer remaining after the tape peeling, the better the adhesion.
• tetracarboxylic acid component> DSDA 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by ChinaTech Chemical (Tianjin) Co., Ltd.; compound represented by formula (a1))
• PMDA pyromellitic anhydride (compound represented by formula (a3))
• 6FDA 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Daikin Industries, Ltd.)
• s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation)
• ODPA 4,4'-oxydiphthalic anhydride (manufactured by Manac Corporation)
• NMP N-methyl-2-pyrrolidone (Tokyo Pure Chemical Industries, Ltd.)
• GBL ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Corporation)
• DMI 1,3-dimethyl-2-imidazolidinone (manufactured by Mitsui Chemicals, Inc.)
• Example 1 22.825 g (0.100 mol) of 4-BAAB and 187.690 g of NMP were placed in a 500 mL five-neck round-bottom flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet tube, a Dean-Stark equipped with a cooling tube, a thermometer, and a glass end cap, and the mixture was stirred at a system temperature of 50° C. under a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution. To this solution, 35.828 g (0.100 mol) of DSDA and 46.922 g of NMP were added all at once, and the mixture was stirred for 3 hours while being kept at 50° C.
• Examples 2 to 8 and Comparative Example 3 A polyamic acid (polyimide resin precursor) varnish having a solid content concentration of 20 mass % was obtained in the same manner as in Example 1, except that the types of tetracarboxylic acid component, diamine component, and solvent were changed as shown in Table 1. Further, a polyimide film was obtained in the same manner as in Example 1. In Examples 6 and 7, 4-aminophenol was added as an end-capping agent in the amount shown in Table 1 simultaneously with the tetracarboxylic acid component. The evaluation results of the varnish and film are shown in Table 1.
• Comparative Example 1 22.825 g (0.100 mol) of 4-BAAB and 167.190 g of NMP were placed in a 500 mL five-neck round-bottom flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet tube, a Dean-Stark equipped with a cooling tube, a thermometer, and a glass end cap, and the mixture was stirred at a system temperature of 50° C. under a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution. To this solution, 29.422 g (0.100 mol) of s-BPDA and 41.798 g of NMP were added all at once, and the mixture was stirred for 3 hours while maintaining the temperature at 50° C.
• Comparative Example 2 22.825 g (0.100 mol) of 4-BAAB and 172.307 g of NMP were placed in a 500 mL five-neck round-bottom flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet tube, a Dean-Stark equipped with a cooling tube, a thermometer, and a glass end cap, and the mixture was stirred at a system temperature of 50° C. under a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution. To this solution, 31.021 g (0.100 mol) of ODPA and 43.077 g of NMP were added all at once, and the mixture was stirred for 3 hours while maintaining the temperature at 50° C. with a mantle heater.
• the polyimide resin precursor varnish of the examples has good rinsing suitability and therefore excellent coatability.
• the polyimide film (polyimide resin) obtained from the polyimide resin precursor of the examples has a large glass transition temperature and a large 5% weight loss temperature and therefore excellent heat resistance. It is also found to have excellent adhesion to silicon wafers. From this, it is clear that the polyimide resin precursor of the present invention can obtain polyimide resin and polyimide film with excellent coatability, heat resistance and adhesion, and is useful as a raw material in the semiconductor field.

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