WO2024038737A1 - Polyimide, solution de polyimide, matériau de revêtement et matériau de formation - Google Patents

Polyimide, solution de polyimide, matériau de revêtement et matériau de formation Download PDF

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WO2024038737A1
WO2024038737A1 PCT/JP2023/027166 JP2023027166W WO2024038737A1 WO 2024038737 A1 WO2024038737 A1 WO 2024038737A1 JP 2023027166 W JP2023027166 W JP 2023027166W WO 2024038737 A1 WO2024038737 A1 WO 2024038737A1
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mol
polyimide
diamine component
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acid component
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PCT/JP2023/027166
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Japanese (ja)
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丈人 小倉
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Ｊｆｅケミカル株式会社
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Priority to KR1020237041748A priority Critical patent/KR20240024797A/ko
Priority to CN202380012401.6A priority patent/CN117897431A/zh
Publication of WO2024038737A1 publication Critical patent/WO2024038737A1/fr

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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
    • C08G73/1046—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
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to polyimides, polyimide solutions, coating materials, and molding materials.
  • Polyimide (polyimide resin) has properties such as not only excellent heat resistance but also chemical resistance, radiation resistance, electrical insulation, and excellent mechanical properties. Therefore, polyimide is known as a material used for flexible printed wiring circuit boards, insulating coating paints, heat-resistant molding materials, and the like.
  • polyimides are synthesized, for example, as described in Patent Document 1. That is, first, in an aprotic polar organic solvent such as N-methyl-2-pyrrolidone, an aromatic tetracarboxylic dianhydride such as 3,3',4,4'-biphenyltetracarboxylic dianhydride and , and an aromatic diamine such as 1,4-phenylenediamine to obtain polyamic acid (polyamic acid), which is a precursor of polyimide. Thereafter, this polyamic acid is heated at 250° C. to 400° C. to proceed with dehydration and cyclization (imidization), thereby obtaining polyimide.
  • an aprotic polar organic solvent such as N-methyl-2-pyrrolidone
  • aromatic tetracarboxylic dianhydride such as 3,3',4,4'-biphenyltetracarboxylic dianhydride and , and an aromatic diamine such as 1,4-phenylenediamine
  • polyimide material Most industrially used polyimides dissolve in organic solvents in the polyamic acid state, but in the polyimide state, they gel or precipitate immediately after synthesis or after being left for about a day, and do not dissolve. becomes insoluble. Therefore, in order to obtain a material containing polyimide (polyimide material), it is common to apply a solution of polyamic acid, volatilize and remove the solvent, and then heat to imidize the material. However, since condensed water is generated during the process of imidizing polyamic acid, voids may occur in the polyimide material. Furthermore, the polyimide material may shrink and its thickness may change.
  • the present invention has been made in view of the above points, and an object of the present invention is to provide a polyimide that has excellent solubility in solvents (does not cause gelation or precipitation). Furthermore, another object of the present invention is to provide a polyimide solution, a coating material, and a molding material containing the above polyimide.
  • the present invention provides the following [1] to [9].
  • [2] Contains more than 70.0 mol% but less than 100.0 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and more than 0.0 mol% and less than 30.0 mol% of pyromellitic dianhydride and a diamine component containing 20.0 to 80.0 mol% of Compound A and 20.0 to 80.0 mol% of 2,2-bis-[4-(4-aminophenoxy)phenyl]propane.
  • Polyimide made by polymerizing and.
  • [4] Contains more than 70.0 mol% but less than 100.0 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and more than 0.0 mol% and less than 30.0 mol% of pyromellitic dianhydride
  • the acid component 15.0 to 80.0 mol% of Compound A described below, 15.0 to 80.0 mol% of 2,2-bis-[4-(4-aminophenoxy)phenyl]propane, and 2,4 - A polyimide obtained by polymerizing a diamine component containing more than 0.0 mol% and less than 30.0 mol% of diaminotoluene.
  • [6] Contains more than 70.0 mol% but less than 100.0 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and more than 0.0 mol% and less than 30.0 mol% of pyromellitic dianhydride and 15.0 to 80.0 mol% of Compound A, which will be described later, 15.0 to 80.0 mol% of 2,2-bis-[4-(4-aminophenoxy)phenyl]propane, and 4,4 A polyimide obtained by polymerizing a diamine component containing more than 0.0 mol% and less than 30.0 mol% of '-oxydianiline and/or 3,4'-oxydianiline.
  • a polyimide having excellent solubility in solvents can be provided. If a solution containing such a polyimide (polyimide solution) is used, since imidization has already progressed, the generation of voids etc. can be suppressed in the resulting polyimide material. That is, a polyimide material having an arbitrary shape can be obtained by simply applying a polyimide solution and volatilizing off the solvent. Furthermore, the mechanical strength and thermal properties are comparable.
  • polyimide First to sixth embodiments of the polyimide (polyimide resin) of the present invention will be described in detail below.
  • the polyimide of the first embodiment contains an acid component containing 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 20.0 to 80.0 mol% of compound A, which will be described later, and 2,2-biphenyltetracarboxylic dianhydride.
  • a diamine component containing 20.0 to 80.0 mol% of bis-[4-(4-aminophenoxy)phenyl]propane is polymerized.
  • the acid component contains 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the content of BPDA is preferably 90.0 mol% or more, more preferably 95.0 mol% or more, and even more preferably 100.0 mol%, for the reason that both strength and solubility are achieved.
  • the diamine component contains compound A represented by the following formula (A).
  • R 1 , R 2 , R 3 and R 4 in the above formula (A) are each independently a methyl group or an ethyl group.
  • Examples of compound A include 4,4'-methylenebis(2-ethyl-6-methylaniline) (MED) represented by formula (3) described later, and 4,4'-methylenebis(2-ethyl-6-methylaniline) (MED) represented by formula (4) described later.
  • Preferred examples include '-methylenebis(2,6-dimethylaniline) (MMD) and 4,4'-methylenebis(2,6-diethylaniline) (EED) represented by formula (5) described below.
  • the content of compound A is 20.0 to 80.0 mol%, preferably 23.0 to 77.0 mol%, and 25.0 to 75 mol%, for the reason of achieving both strength and solubility. .0 mol% is more preferable.
  • the diamine component further contains 2,2-bis-[4-(4-aminophenoxy)phenyl]propane (BAPP).
  • BAPP 2,2-bis-[4-(4-aminophenoxy)phenyl]propane
  • the content of BAPP is 20.0 to 80.0 mol%, preferably 23.0 to 77.0 mol%, and 25.0 to 75.0 mol%, in order to achieve both strength and solubility. 0 mol% is more preferable.
  • the polyimide of the second embodiment contains more than 70.0 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and less than 100.0 mol% and more than 0.0 mol% of pyromellitic dianhydride.
  • An acid component containing less than .0 mol%, and 20.0 to 80.0 mol% of compound A and 20.0 to 80.0 mol% of 2,2-bis-[4-(4-aminophenoxy)phenyl]propane. It is obtained by polymerizing a diamine component.
  • the acid component contains 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the content of BPDA is more than 70.0 mol% and less than 100.0 mol%, preferably 73.0 to 97.0 mol%, and 75.0 to 75.0 mol%, in order to achieve both strength and solubility. 90.0 mol% is more preferable.
  • the acid component further contains pyromellitic dianhydride (PMDA).
  • PMDA pyromellitic dianhydride
  • the content of PMDA is more than 0.0 mol% and less than 30.0 mol%, preferably 3.0 to 27.0 mol%, and 10.0 to 27.0 mol%, in order to achieve both strength and solubility. 27.0 mol% is more preferable.
  • the diamine component contains compound A.
  • the content of compound A is 20.0 to 80.0 mol%, preferably 23.0 to 77.0 mol%, and 25.0 to 75 mol%, in order to achieve both strength and solubility. .0 mol% is more preferable.
  • the diamine component further contains 2,2-bis-[4-(4-aminophenoxy)phenyl]propane (BAPP).
  • BAPP 2,2-bis-[4-(4-aminophenoxy)phenyl]propane
  • the content of BAPP is 20.0 to 80.0 mol%, preferably 23.0 to 77.0 mol%, and 25.0 to 75.0 mol%, in order to achieve both strength and solubility. 0 mol% is more preferable.
  • the polyimide of the third embodiment contains an acid component containing 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 15.0 to 80.0 mol% of compound A, 2,2-bis- A diamine component containing 15.0 to 80.0 mol% of [4-(4-aminophenoxy)phenyl]propane and more than 0.0 mol% but less than 30.0 mol% of 2,4-diaminotoluene. .
  • the acid component contains 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the content of BPDA is preferably 90.0 mol% or more, more preferably 95.0 mol% or more, and even more preferably 100.0 mol%, for the reason that both strength and solubility are achieved.
  • the diamine component contains compound A.
  • the content of compound A is 15.0 to 80.0 mol%, preferably 20.0 to 70.0 mol%, and 20.0 to 60 mol%, in order to achieve both strength and solubility. .0 mol% is more preferable.
  • the diamine component further contains 2,2-bis-[4-(4-aminophenoxy)phenyl]propane (BAPP).
  • BAPP 2,2-bis-[4-(4-aminophenoxy)phenyl]propane
  • the content of BAPP is 15.0 to 80.0 mol%, preferably 20.0 to 70.0 mol%, and 25.0 to 60.0 mol%, in order to achieve both strength and solubility. 0 mol% is more preferable.
  • the diamine component further contains 2,4-diaminotoluene (DAT).
  • DAT 2,4-diaminotoluene
  • the content of DAT is more than 0.0 mol% and less than 30.0 mol%, preferably 5.0 to 28.0 mol%, and 10.0 to 28.0 mol%, in order to achieve both strength and solubility. 27.0 mol% is more preferable.
  • the polyimide of the fourth embodiment contains more than 70.0 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and less than 100.0 mol% and more than 0.0 mol% of pyromellitic dianhydride.
  • An acid component containing less than .0 mol%, 15.0 to 80.0 mol% of compound A, 15.0 to 80.0 mol% of 2,2-bis-[4-(4-aminophenoxy)phenyl]propane, and A diamine component containing more than 0.0 mol% and less than 30.0 mol% of 2,4-diaminotoluene.
  • the acid component contains 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the content of BPDA is more than 70.0 mol% and less than 100.0 mol%, preferably 73.0 to 97.0 mol%, and 75.0 to 75.0 mol%, in order to achieve both strength and solubility. 90.0 mol% is more preferable.
  • the acid component further contains pyromellitic dianhydride (PMDA).
  • PMDA pyromellitic dianhydride
  • the content of PMDA is more than 0.0 mol% and less than 30.0 mol%, preferably 3.0 to 27.0 mol%, and 10.0 to 27.0 mol%, in order to achieve both strength and solubility. 25.0 mol% is more preferable.
  • the diamine component contains compound A.
  • the content of compound A is 15.0 to 80.0 mol%, preferably 20.0 to 60.0 mol%, and 22.0 to 45 mol%, for the reason of achieving both strength and solubility. .0 mol% is more preferable.
  • the diamine component further contains 2,2-bis-[4-(4-aminophenoxy)phenyl]propane (BAPP).
  • BAPP 2,2-bis-[4-(4-aminophenoxy)phenyl]propane
  • the content of BAPP is 15.0 to 80.0 mol%, preferably 25.0 to 60.0 mol%, and 30.0 to 55.0 mol%, for the purpose of achieving both strength and solubility. 0 mol% is more preferable.
  • the diamine component further contains 2,4-diaminotoluene (DAT).
  • DAT 2,4-diaminotoluene
  • the content of DAT is more than 0.0 mol% and less than 30.0 mol%, preferably 5.0 to 28.0 mol%, and 10.0 to 28.0 mol%, in order to achieve both strength and solubility. 27.0 mol% is more preferable.
  • the polyimide of the fifth embodiment contains an acid component containing 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 15.0 to 80.0 mol% of compound A, 2,2-bis- 15.0 to 80.0 mol% of [4-(4-aminophenoxy)phenyl]propane and more than 0.0 mol% of 4,4'-oxydianiline and/or 3,4'-oxydianiline to 30.0 mol%
  • a diamine component containing less than % of the diamine component is polymerized.
  • the acid component contains 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the content of BPDA is preferably 90.0 mol% or more, more preferably 95.0 mol% or more, and even more preferably 100.0 mol%, for the reason that both strength and solubility are achieved.
  • the diamine component contains compound A.
  • the content of compound A is 15.0 to 80.0 mol%, preferably 20.0 to 60.0 mol%, and 23.0 to 52 mol%, for the reason of achieving both strength and solubility. % is more preferable.
  • the diamine component further contains 2,2-bis-[4-(4-aminophenoxy)phenyl]propane (BAPP).
  • BAPP 2,2-bis-[4-(4-aminophenoxy)phenyl]propane
  • the content of BAPP is 15.0 to 80.0 mol%, preferably 20.0 to 60.0 mol%, and 23.0 to 52.0 mol%, for the purpose of achieving both strength and solubility. 0 mol% is more preferable.
  • the diamine component further contains 4,4'-oxydianiline (ODA) and/or 3,4'-oxydianiline (DAPE).
  • ODA 4,4'-oxydianiline
  • DAPE 3,4'-oxydianiline
  • the total content of ODA and DAPE is more than 0.0 mol% and less than 30.0 mol%, preferably 5.0 to 28.0 mol%, and 10 .0 to 27.0 mol% is more preferable.
  • the polyimide of the sixth embodiment contains more than 70.0 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and less than 100.0 mol% and more than 0.0 mol% of pyromellitic dianhydride.
  • An acid component containing less than .0 mol%, 15.0 to 80.0 mol% of compound A, 15.0 to 80.0 mol% of 2,2-bis-[4-(4-aminophenoxy)phenyl]propane, and and a diamine component containing more than 0.0 mol% and less than 30.0 mol% of 4,4'-oxydianiline and/or 3,4'-oxydianiline.
  • the acid component contains 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the content of BPDA is more than 70.0 mol% and less than 100.0 mol%, preferably 73.0 to 97.0 mol%, and 75.0 to 75.0 mol%, in order to achieve both strength and solubility. 90.0 mol% is more preferable.
  • the acid component further contains pyromellitic dianhydride (PMDA).
  • PMDA pyromellitic dianhydride
  • the content of PMDA is more than 0.0 mol% and less than 30.0 mol%, preferably 3.0 to 27.0 mol%, and 10.0 to 27.0 mol%, in order to achieve both strength and solubility. 25.0 mol% is more preferable.
  • the diamine component contains compound A.
  • the content of compound A is 15.0 to 80.0 mol%, preferably 20.0 to 60.0 mol%, and 22.0 to 55 mol%, in order to achieve both strength and solubility. .0 mol% is more preferable.
  • the diamine component further contains 2,2-bis-[4-(4-aminophenoxy)phenyl]propane (BAPP).
  • BAPP 2,2-bis-[4-(4-aminophenoxy)phenyl]propane
  • the content of BAPP is 15.0 to 80.0 mol%, preferably 20.0 to 60.0 mol%, and 23.0 to 55.0 mol%, in order to achieve both strength and solubility. 0 mol% is more preferable.
  • the diamine component further contains 4,4'-oxydianiline (ODA) and/or 3,4'-oxydianiline (DAPE).
  • ODA 4,4'-oxydianiline
  • DAPE 3,4'-oxydianiline
  • the total content of ODA and DAPE is more than 0.0 mol% and less than 30.0 mol%, preferably 5.0 to 28.0 mol%, and 10 .0 to 27.0 mol% is more preferable.
  • This production method is generally a method in which the above-mentioned diamine component and acid component are polymerized (dehydration condensation) in a solvent to obtain the above-mentioned polyimide (first to sixth embodiments).
  • the diamine component is as described above.
  • the diamine component further includes aromatic diamines such as 1,4-phenylenediamine; aliphatic diamines such as 1,2-diaminoethane, 1,3-diaminopropane, 1,5-diaminopentane, and 1,6-hexanediamine.
  • Diamines; generally known polyvalent amines; etc. may also be used. These may be used alone or in combination of two or more.
  • the acid component is as described above.
  • the acid component further includes aromatic tetracarboxylic dianhydrides such as 4,4'-oxydiphthalic dianhydride (ODPA) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA).
  • aromatic tetracarboxylic dianhydrides such as 4,4'-oxydiphthalic dianhydride (ODPA) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA).
  • aliphatic tetracarboxylic dianhydrides such as cyclohexane tetracarboxylic dianhydride; etc. may be used. These may be used alone or in combination of two or more.
  • a diamine component and an acid component blended in an appropriate molar ratio are reacted in a solvent to obtain a polyamic acid. That is, a solution containing polyamic acid (polyamic acid solution) is obtained.
  • the reaction temperature is preferably 30 to 70°C, more preferably 40 to 60°C.
  • the reaction time is preferably 1 to 36 hours, more preferably 6 to 30 hours.
  • the reaction is carried out, for example, under atmospheric pressure.
  • polyamic acid solution a solution containing polyimide (polyimide solution) is obtained.
  • the temperature (heating temperature) at which the polyamic acid (polyamic acid solution) is heated is not particularly limited as long as the temperature is selected so that the azeotropic solvent can be distilled off, but 140 to 220°C is preferable, and 160 to 200°C is preferable. More preferred.
  • the holding time (heating time) at this heating temperature is preferably 0.5 to 10 hours, more preferably 2 to 7 hours. Further, temperature control may be performed in an inert gas blowing environment or a reduced pressure environment as necessary.
  • a container equipped with various cooling devices such as a Dean-Stark trap or a condenser. After that, a desired polyimide solution may be obtained while removing moisture generated as imidization progresses.
  • the molar ratio between the acid component and the diamine component may be arbitrarily set depending on the viscosity of the polyimide solution used for coating, and is preferably 0.90 to 1.10. Preferably, 0.95 to 1.05 is more preferable.
  • the molecular structure of polyimide is not particularly limited.
  • random copolymers, alternating copolymers, block copolymers, etc. can be exemplified depending on the polymerization conditions.
  • the weight average molecular weight of the obtained polyimide is preferably 1,500 or more.
  • this molecular weight is preferably 200,000 or less.
  • problems with stirring equipment can be suppressed.
  • the solvent used in this production method it is preferable to use a polar organic solvent because the obtained polyimide exhibits sufficient solubility.
  • a polar organic solvent for example, benzene, toluene, xylene, etc.
  • the polyimide solution has fluidity suitable for coating and is a uniform and transparent solution free of precipitates.
  • amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.
  • the solid content concentration of the polyimide solution is not particularly limited, and is appropriately set depending on the desired viscosity, etc., and is, for example, 5 to 50% by mass.
  • the viscosity of the polyimide solution may be set as appropriate within a range that allows the polyimide solution to be stirred and mixed or transported using a pump, and that does not cause any inconvenience in coating.
  • the viscosity at 25° C. is preferably 0.3 to 200 Pa ⁇ s.
  • a dehydrating agent and an imidization catalyst may be added to the solvent in order to promote imidization.
  • the dehydrating agent any commonly known dehydrating agent may be used, and examples thereof include acid anhydrides such as acetic anhydride and oxalic anhydride; ⁇ -valerolactone; and the like.
  • the imidization catalyst any commonly known catalyst may be used, and examples thereof include tertiary amines such as isoquinoline, ⁇ -picoline, and pyridine.
  • a plurality of dehydrating agents and imidization catalysts may be used in combination.
  • a crosslinking agent for the purpose of modifying the main chain of the polyimide and imparting various properties to the extent that the mechanical properties and electrical properties of the obtained polyimide are not impaired.
  • the crosslinking agent any commonly known ones may be used, such as oxazolines, melamines, isocyanates, aziridines, benzoxazines, bismaleimides, etc., and multiple types may be used in combination. You may.
  • a viscosity stabilizer may be added within a range that does not impair the mechanical properties, electrical properties, etc. of the resulting polyimide.
  • a polyimide film is also a molding material containing polyimide, and depending on the thickness, it can be handled as a film, sheet, panel, etc. It may also be applied to seamless cylindrical tubes, belts, and molded parts using molds.
  • a polyimide film can be used, for example, as a heat-resistant molding material in fields such as flexible printed circuits (FPC), chip-on-film (COF), and electronic circuit boards for tape automated bonding (TAB).
  • FPC flexible printed circuits
  • COF chip-on-film
  • TAB tape automated bonding
  • the conditions for obtaining a polyimide film from a polyimide solution may vary depending on the composition of the polyimide, the type of solvent, the substrate to be coated, etc., but any known method can be used, and there are no particular restrictions. Not done.
  • a cured polyimide film can be obtained by coating a polyimide solution onto a base material and then drying it.
  • the substrate is not eroded by the solvent of the polyimide solution.
  • the base material includes, for example, glass; wood; stone; triacetate cellulose (TAC), polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, acrylic resin, polyurethane. Examples include resins such as polyester, polycarbonate, polysulfone, polyether, trimethylpentene, polyetherketone, and (meth)acrylonitrile; rubber; metals such as SUS and copper; and the like.
  • TAC triacetate cellulose
  • PET polyethylene terephthalate
  • diacetyl cellulose acetate butyrate cellulose
  • polyether sulfone acrylic resin
  • polyurethane examples include resins such as polyester, polycarbonate, polysulfone, polyether, trimethylpentene, polyetherketone, and (meth)acrylonitrile; rubber; metals such as SUS and copper; and the like.
  • any commonly known method may be used, for example, a roll coating method, a gravure coating method, a slide coating method, a spray method, a dipping method, a screen printing method, a spray method, etc. may be adopted as appropriate.
  • a roll coating method a gravure coating method, a slide coating method, a spray method, a dipping method, a screen printing method, a spray method, etc.
  • a spray method a dipping method
  • a screen printing method a spray method, etc.
  • any commonly known method may be used, and examples thereof include methods using hot air drying, a far-infrared heating furnace, a ceramic heater, a muffle furnace, etc., and a plurality of methods may be combined.
  • the drying temperature is set, for example, according to the boiling point of the solvent. It may be set in consideration of the glass transition point of the polyimide and the base material.
  • imide ring closure has already progressed due to heating of the solvent carried out in the present production method. Therefore, in order to form a cured film, it is sufficient to simply volatilize and remove the solvent after coating the polyimide solution. By setting the time and pressure appropriately, a cured film can be obtained even under conditions below the boiling point of the solvent.
  • the resulting cured polyimide film does not require the dehydration condensation process required for general polyimides, and therefore does not suffer from curing shrinkage that is characteristic of polyimides. Therefore, steps required for conventional polyimide, such as fixing and stretching the ends of the intermediate film, can be omitted.
  • a filler may be added to the polyimide solution for the purpose of improving various properties of the cured film.
  • any commonly known filler may be used. Examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and carbon black. May be used in combination. Further, a conductive component, a coloring component, an adhesion imparting component, etc. may coexist in these.
  • additives such as a mold release agent, an antifoaming agent, a leveling agent, an ion trapper, a polymerization inhibitor, an antioxidant, a viscosity modifier, and an antistatic agent may be added as necessary.
  • the polyimide film can be used for conventionally known polyimide applications. For example, it is used in electronic devices such as displays, touch panels, projectors, printers, earphones, speakers, and antennas.
  • the base material may be selected on the premise that it will be installed in these electronic devices.
  • the resulting polyimide has good mechanical properties as well as excellent physical properties such as heat resistance and hardness, so it can be used as a binder for carbon fibers, glass fibers, metal nanowires, etc. can. Since the heating load can be reduced, it can be applied to electrodes of secondary batteries whose base material is metal foil. It does not cause curing shrinkage and is dimensionally stable, so it can be applied to porous materials with internal voids.
  • Polyimide membranes can be made into cylindrical shapes and used as tubes and belts. A polyimide film obtained by ensuring film thickness accuracy, applying it smoothly, and drying it can also be peeled off and handled as a film, sheet, panel, etc.
  • Polyimide membranes can be expected to have sufficient durability against solvents with low polarity and moisture, so they can also be used in applications that require water resistance and chemical resistance. Furthermore, by applying this property, a solid substance (powder) of polyimide can be obtained by precipitating polyimide while mixing with a poor solvent such as alcohol, and washing and drying as necessary.
  • ⁇ Preparation of polyimide membrane 15 g of the obtained polyimide solution (within 1 day after synthesis) was applied to a glass plate using a bar coater, and heated at 100°C for 30 minutes, 150°C for 30 minutes, 200°C for 90 minutes, and 220°C for 30 minutes. The mixture was heated for a minute to obtain a polyimide film with a thickness of about 50 ⁇ m.
  • the obtained polyimide film was tested under the following conditions to determine the glass transition temperature (unit: °C), linear thermal expansion coefficient (unit: ppm/K), and thermal decomposition temperature (unit: °C). The results are shown in Table 1 below.
  • Examples 2 to 25 and Comparative Examples 1 to 7> A polyimide solution was prepared and evaluated in the same manner as in Example 1 using the diamine component and acid component shown in Table 1 below in the amounts shown in Table 1 below. The results are shown in Table 1 below.
  • polyimide films were created under the same conditions as ⁇ Creation of polyimide film>> using samples stored at room temperature for two months after production, and mechanical strength and thermal properties were measured. The results are shown in Table 2 below. Even after storage for February, almost the same results as those immediately after synthesis were obtained.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (1)
  • PMDA Pyromellitic dianhydride represented by the following formula (2)
  • MED The following formula ( 3) 4,4'-methylenebis(2-ethyl-6-methylaniline)
  • MMD 4,4'-methylenebis(2,6-dimethylaniline) represented by the following formula (4)
  • EED 4,4'-methylenebis(2,6-diethylaniline) represented by the following formula (5)
  • MDA 4,4'-methylene dianiline represented by the following formula (6)
  • BAPP 2,2-bis-[4-(4-aminophenoxy)phenyl]propane represented by the following formula (7)
  • DAT 2,4-diaminotoluene represented by the following formula (8)
  • ODA 4,4'-oxydianiline represented by the following formula (9)
  • DAPE 3,4'- represented by the following formula (10)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne un polyimide qui présente une excellente solubilité dans un solvant. Ce polyimide est obtenu par polymérisation d'un composant acide qui contient du dianhydride 3,3',4,4'-biphényltétracarboxylique et un composant diamine qui contient 20,0 à 80,0 % en moles d'un composé spécifique A et 20,0 à 80,0 % en moles de 2,2-bis-[4-(4-aminophénoxy)phényl]propane.
PCT/JP2023/027166 2022-08-15 2023-07-25 Polyimide, solution de polyimide, matériau de revêtement et matériau de formation WO2024038737A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10120785A (ja) * 1996-10-21 1998-05-12 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物およびフィルム接着剤とその製造方法
JPH10231426A (ja) * 1997-02-18 1998-09-02 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物
JPH10265760A (ja) * 1997-03-24 1998-10-06 Sumitomo Bakelite Co Ltd フィルム接着剤とその製造方法
JPH10301281A (ja) * 1997-02-25 1998-11-13 Toray Ind Inc 感光性ポリイミド前駆体組成物
JPH11335652A (ja) * 1998-05-22 1999-12-07 Sumitomo Bakelite Co Ltd フィルム接着剤
JP2002265918A (ja) * 2001-03-08 2002-09-18 Sumitomo Bakelite Co Ltd 絶縁接着剤
JP2003253125A (ja) * 2001-01-31 2003-09-10 Sumitomo Bakelite Co Ltd 絶縁樹脂組成物及び絶縁樹脂シート並びにプリント配線板
JP2003298242A (ja) * 2002-03-29 2003-10-17 Sumitomo Bakelite Co Ltd 多層配線板およびその製造方法ならびに半導体装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6042817A (ja) 1983-08-19 1985-03-07 Mitsui Toatsu Chem Inc 水素化アモルフアスシリコン膜の価電子制御方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10120785A (ja) * 1996-10-21 1998-05-12 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物およびフィルム接着剤とその製造方法
JPH10231426A (ja) * 1997-02-18 1998-09-02 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物
JPH10301281A (ja) * 1997-02-25 1998-11-13 Toray Ind Inc 感光性ポリイミド前駆体組成物
JPH10265760A (ja) * 1997-03-24 1998-10-06 Sumitomo Bakelite Co Ltd フィルム接着剤とその製造方法
JPH11335652A (ja) * 1998-05-22 1999-12-07 Sumitomo Bakelite Co Ltd フィルム接着剤
JP2003253125A (ja) * 2001-01-31 2003-09-10 Sumitomo Bakelite Co Ltd 絶縁樹脂組成物及び絶縁樹脂シート並びにプリント配線板
JP2002265918A (ja) * 2001-03-08 2002-09-18 Sumitomo Bakelite Co Ltd 絶縁接着剤
JP2003298242A (ja) * 2002-03-29 2003-10-17 Sumitomo Bakelite Co Ltd 多層配線板およびその製造方法ならびに半導体装置

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