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WO2025084154A1 - Procédé de fabrication de résine polyimide - Google Patents

Procédé de fabrication de résine polyimide Download PDF

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Publication number
WO2025084154A1
WO2025084154A1 PCT/JP2024/035483 JP2024035483W WO2025084154A1 WO 2025084154 A1 WO2025084154 A1 WO 2025084154A1 JP 2024035483 W JP2024035483 W JP 2024035483W WO 2025084154 A1 WO2025084154 A1 WO 2025084154A1
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Prior art keywords
compound represented
formula
polyimide resin
mol
diamine
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Japanese (ja)
Inventor
舜 星野
孝博 村谷
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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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

Definitions

  • the present invention relates to a method for producing polyimide resin.
  • polyimide resins are being considered in the fields of electrical and electronic components. For example, it is desirable to replace the glass substrates used in image display devices such as liquid crystal displays and OLED displays with plastic substrates in order to make the devices lighter and more flexible, and research is being conducted into polyimide films suitable for such plastic substrates. Polyimide films for such applications require transparency and low yellowness.
  • Patent Document 1 discloses a polyimide precursor that contains two specific types of specific amide acid structural units in a specific ratio, with the aim of obtaining a polyimide film that has low residual stress, little warping, low yellowness, and high elongation.
  • polyimide films for specific applications are required to have transparency and low yellowness.
  • the device type LTPS low temperature polysilicon TFT
  • the polyimide substrate is required to have heat resistance capable of withstanding multiple treatments at high temperatures of 400° C. or higher, and is required to maintain transparency and low yellowness even during such a thermal history.
  • Patent Document 1 discloses a technique for reducing residual stress and reducing yellowness, but this is still insufficient, and in particular it has not been possible to obtain a polyimide film that is excellent in heat resistance and the like while maintaining transparency and low yellowness.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a polyimide resin, which can give a polyimide resin that is excellent in heat resistance and has excellent colorlessness and transparency after heat treatment.
  • the inventors discovered that the above problems could be solved by a manufacturing method in which a specific tetracarboxylic dianhydride and a diamine are polymerized and imidized to obtain a polyimide resin, and thus completed the invention.
  • a method for producing a polyimide resin comprising polymerizing a tetracarboxylic dianhydride (a) and a diamine (b) to form an imidized product, the method comprising the steps of: (a) polymerizing a tetracarboxylic dianhydride (a) and a diamine (b) to form an imidized product; wherein the tetracarboxylic dianhydride (a) comprises at least one selected from the group consisting of a compound represented by the following formula (a1), a compound represented by the following formula (a2), a compound represented by the following formula (a3), a compound represented by the following formula (a4), a compound represented by the following formula (a5), and a compound represented by the following formula (a6); the diamine (b) comprises a compound represented by the following formula (b1); and the total amount of the compound represented by the following formula (b2) and the
  • [2] The method for producing a polyimide resin according to the above [1], comprising a step of preparing a raw material containing the compound represented by formula (b1), the raw material having a total content of the compound represented by formula (b2) and the compound represented by formula (b3) of 0.05 mol % or less.
  • step 1 comprises the following steps 1a and 1b, and is a step for obtaining an imide-amic acid copolymer, which is a polyimide resin precursor: Step 1a: reacting a tetracarboxylic dianhydride with a diamine in the presence of a solvent to obtain an imide oligomer; and Step 1b: mixing and polymerizing the imide oligomer obtained in Step 1a, and at least one of a tetracarboxylic dianhydride and a diamine.
  • the present invention provides a method for producing polyimide resin that can produce polyimide resin that has excellent heat resistance and is colorless and transparent after heat treatment.
  • the method for producing a polyimide resin of the present invention is a method for producing a polyimide resin, comprising polymerizing a tetracarboxylic dianhydride (a) and a diamine (b) to form an imidized product, the method comprising the steps of:
  • the tetracarboxylic dianhydride (a) contains at least one selected from the group consisting of a compound represented by the following formula (a1), a compound represented by the following formula (a2), a compound represented by the following formula (a3), a compound represented by the following formula (a4), a compound represented by the following formula (a5), and a compound represented by the following formula (a6)
  • the diamine (b) contains a compound represented by the following formula (b1), and the total amount of a compound represented by the following formula (b2) and a compound represented by the following formula (b3) relative to the compound represented by the following formula (b1) is 0.05 mol % or less.
  • the reason why the above-mentioned production method can provide a polyimide resin that is excellent in heat resistance and colorless and transparent after heat treatment is not clear, but is thought to be as follows.
  • the diamine compound represented by formula (b2) is derived from an azo structure, and is therefore considered to have visible light absorption.
  • the diamine compound represented by formula (b3) is considered to be transformed into the compound represented by formula (b2) by storage under exposure or by heat treatment for obtaining polyimide. Therefore, when the compound represented by formula (b2) and the compound represented by formula (b3) are incorporated into the polyimide chain, they become a factor that reduces the colorless transparency of the polyimide.
  • the diamine compound represented by formula (b1) is an important structure in polyimide resins having excellent heat resistance and colorless transparency.
  • the tetracarboxylic dianhydride (a) used in the method for producing a polyimide resin of the present invention contains at least one selected from the group consisting of a compound represented by the following formula (a1), a compound represented by the following formula (a2), a compound represented by the following formula (a3), a compound represented by the following formula (a4), a compound represented by the following formula (a5), and a compound represented by the following formula (a6).
  • the tetracarboxylic dianhydride (a) includes at least one selected from the group consisting of a compound represented by formula (a1), a compound represented by formula (a2), a compound represented by formula (a3), a compound represented by formula (a4), a compound represented by formula (a5), and a compound represented by formula (a6), but preferably includes at least one selected from the group consisting of a compound represented by formula (a1) and a compound represented by formula (a2), more preferably includes a compound represented by formula (a2), and even more preferably includes a compound represented by formula (a1) and a compound represented by formula (a2).
  • the compound represented by formula (a1) is 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF).
  • BPAF 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride
  • the compound represented by formula (a2) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a2s), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a2a), and 2,2',3,3'-biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a2i).
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3',4'-biphenyltetracarboxylic dianhydride
  • i-BPDA 2,2',3,3'-biphenyltetracarboxylic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the resulting polyimide resin preferably has high heat resistance.
  • the compound represented by formula (a3) is p-phenylenebis(trimellitate)dianhydride (TAHQ). By including the compound represented by formula (a3), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a4) is pyromellitic anhydride (PMDA). By including the compound represented by formula (a4), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a5) is p-biphenylene bis(trimellitate) dianhydride (BP-TME). By including the compound represented by formula (a5), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a6) is bis(benzene-3,4-dicarboxylic anhydride) ester (BBDE). By including the compound represented by formula (a6), the obtained polyimide resin is preferably high in heat resistance.
  • the tetracarboxylic dianhydride (a) may include a tetracarboxylic dianhydride other than the compounds represented by formula (a1), (a2), (a3), (a4), (a5), and (a6).
  • tetracarboxylic dianhydrides are not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides other than the above-mentioned compounds.
  • the tetracarboxylic dianhydride (a) does not contain a fluorine atom, and it is preferable that the tetracarboxylic dianhydrides other than the compounds represented by the formulas (a1), (a2), (a3), (a4), (a5) and (a6) also do not contain fluorine.
  • Aromatic tetracarboxylic dianhydrides other than the above compounds include 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride.
  • ODPA 4,4'-oxydiphthalic anhydride
  • DSDA 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride
  • BTDA 3,3',4,4'-benzophenonetetracarboxylic dianhydride
  • 6FCDA 9,9-
  • HQDEA diphthalic anhydride
  • TMEG ethylene glycol bis(trimellitate) dianhydride
  • 6FDA 4,4'-(hexafluoroisopropylidene) diphthalic anhydride
  • 2,2',3,3',5,5'-hexamethyl[1,1'-biphenyl]-4,4'-diyl bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) (TMPBP-TME), and 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride.
  • alicyclic tetracarboxylic dianhydrides include cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclohexane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, decahydro-1,4:5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA), 5,5'-(1,4-phenylene)-bis
  • Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride.
  • the tetracarboxylic dianhydride optionally contained in the tetracarboxylic dianhydride (a) may be one type or two or more types.
  • 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 tetracarboxylic dianhydride (a) may be an acid dianhydride, but is not limited thereto and may be a derivative thereof. Such derivatives include tetracarboxylic acid (free acid) and alkyl esters of the tetracarboxylic acid. Among these, acid dianhydrides are preferred.
  • the total ratio of the compounds represented by formula (a1), (a2), (a3), (a4), (a5) and (a6) in the tetracarboxylic dianhydride (a) is preferably 70 mol% or more and 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, even more preferably 90 mol% or more and 100 mol% or less, still more preferably 95 mol% or more and 100 mol% or less, and even more preferably 99 mol% or more and 100 mol% or less, based on the total amount of the tetracarboxylic dianhydride (a).
  • the molar ratio of the compound represented by formula (a1) to the compound represented by formula (a2) in the tetracarboxylic dianhydride (a) [(a1)/(a2)] is preferably 5/95 to 60/40, more preferably 10/90 to 60/40, and even more preferably 15/85 to 60/40, from the viewpoints of transparency, low yellowness, and high heat resistance.
  • the diamine (b) used in the method for producing a polyimide resin of the present invention contains a compound represented by the following formula (b1), and the total amount of a compound represented by the following formula (b2) and a compound represented by the following formula (b3) relative to the compound represented by the following formula (b1) is 0.05 mol % or less.
  • the compound represented by formula (b1) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
  • the resulting polyimide resin is preferably highly heat resistant.
  • the total amount of the compound represented by formula (b2) and the compound represented by formula (b3) in the diamine (b) is 0.05 mol% or less, preferably 0.04 mol% or less, more preferably 0.03 mol% or less, and even more preferably 0.02 mol% or less, relative to the compound represented by formula (b1).
  • the diamine (b) may not contain either the compound represented by formula (b2) or the compound represented by formula (b3).
  • the diamine (b) may include a diamine other than the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3).
  • Such diamines include, but are not limited to, aromatic diamines, alicyclic diamines, and aliphatic diamines other than the above compounds.
  • the diamine (b) does not contain fluorine atoms
  • the diamine other than the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3) does not contain fluorine atoms.
  • neither the tetracarboxylic dianhydride (a) nor the diamine (b) contains fluorine atoms.
  • "not containing fluorine atoms in the diamine (b)” means that the raw material for the diamine (b) does not contain fluorine atoms, or that fluorine atoms are not inevitably mixed in during the production process.
  • Aromatic diamines other than the above compounds include bis(4-aminophenyl)terephthalate (APTP), 1,4-bis(4-aminobenzoyloxy)benzene, 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, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.
  • APTP
  • 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 optionally contained in the diamine (b) may be one kind or two or more kinds.
  • 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.
  • Diamine (b) may be, but is not limited to, a diamine, and may be a derivative thereof. Such derivatives include diisocyanates corresponding to the diamines. Among these, diamines are preferred.
  • the ratio of the compound represented by formula (b1) in the diamine (b) is preferably 70 mol% or more and 100 mol% or less. More preferably, it is 80 mol% or more and 100 mol% or less, even more preferably, it is 90 mol% or more and 100 mol% or less, even more preferably, it is 95 mol% or more and 100 mol% or less, even more preferably, it is 99 mol% or more and 100 mol% or less, even more preferably, it is 99.5 mol% or more and 100 mol% or less, and even more preferably, it is 99.9 mol% or more and 100 mol% or less.
  • the diamine (b) used in the method for producing a polyimide resin of the present invention contains a compound represented by formula (b1), and the total amount of the compound represented by formula (b2) and the compound represented by formula (b3) is 0.05 mol% or less relative to the compound represented by formula (b1). Therefore, the amount of the compound represented by formula (b2) and the compound represented by formula (b3) contained in the compound represented by formula (b1) is important. Therefore, it is preferable to have, as an optional step, a step of preparing or selecting a raw material containing the compound represented by formula (b1), the compound represented by formula (b2) and the compound represented by formula (b3) in specific amounts.
  • the method for producing a polyimide resin of the present invention preferably includes a step of preparing a raw material containing the compound represented by formula (b1), the raw material having a total content of the compound represented by formula (b2) and the compound represented by formula (b3) of 0.05 mol % or less. Further, it is more preferable to have a step of preparing a raw material containing the compound represented by the formula (b2) and the compound represented by the formula (b3) as the raw material containing the compound represented by the formula (b1).
  • the compound represented by formula (b2) and the compound represented by formula (b3) are considered to be produced during the production process of a raw material containing the compound represented by formula (b1). Therefore, examples of the method for obtaining the raw material in which the total amount of the compound represented by formula (b2) and the compound represented by formula (b3) is 0.05 mol % or less relative to the compound represented by formula (b1) include removal of inorganic substances such as hydrochloric acid by washing with water in the steps represented by the reaction formula (1) and the reaction formula (2), and purification with activated carbon or the like in the step of the reaction formula (2).
  • the total content of the compound represented by the formula (b2) and the compound represented by the formula (b3) in a raw material containing the compound represented by the formula (b1) can be measured by a nuclear magnetic resonance (NMR) method. Specifically, it is preferable to measure by the method described in the Examples.
  • NMR nuclear magnetic resonance
  • a step of preparing or selecting a raw material containing the compound represented by formula (b1) in a specific amount it is preferable to have a step of preparing a raw material containing the compound represented by formula (b1), the raw material having a content of the compound represented by formula (b1) of 99.9% or more. Further, it is more preferable to have a step of measuring the content of the compound represented by the formula (b1) in a raw material containing the compound represented by the formula (b1), and selecting a raw material having a content of the compound represented by the formula (b1) of 99.9% or more.
  • the content of the compound represented by formula (b1) in the raw material containing the compound represented by formula (b1) can be measured by liquid chromatography (LC). Specifically, it is preferable to measure by the method described in the Examples. As described above, by including the step of preparing or selecting a raw material containing a specific amount of the compound represented by formula (b1) as the raw material containing the compound represented by formula (b1), the obtained polyimide resin has excellent heat resistance and excellent colorless transparency after heat treatment.
  • LC liquid chromatography
  • the method for producing a polyimide resin of the present invention may directly produce a polyimide resin by polymerizing a tetracarboxylic dianhydride (a) and a diamine (b), or may include a process having a step 1 of polymerizing a tetracarboxylic dianhydride (a) and a diamine (b) to produce a polyimide resin precursor, that is, a polyamic acid or an imide-amic acid copolymer, and a step 2 of imidizing the polyimide resin precursor to produce a polyimide resin.
  • the step 1 is preferably a step of obtaining an imide-amic acid copolymer, which comprises the following steps 1a and 1b:
  • Step 1a A step of reacting a tetracarboxylic dianhydride with a diamine in the presence of a solvent to obtain an imide oligomer.
  • Step 1b A step of mixing the imide oligomer obtained in step 1a with at least one of a tetracarboxylic dianhydride and a diamine, and polymerizing the mixture.
  • the tetracarboxylic dianhydride (a) and diamine (b) include a tetracarboxylic dianhydride and diamine used to obtain an imide oligomer in step 1a (the tetracarboxylic dianhydride and diamine constituting the imide portion in the imide-amic acid copolymer; hereinafter, also referred to as tetracarboxylic dianhydride (ai) and diamine (bi)), and a tetracarboxylic dianhydride and diamine used to obtain an amic acid portion in step 1b (the tetracarboxylic dianhydride and diamine constituting the amic acid portion in the imide-amic acid copolymer; hereinafter, also referred to as tetracarboxylic dianhydride (aa) and diamine (ba)).
  • the tetracarboxylic dianhydride (a) and diamine (b) include a tetrac
  • the tetracarboxylic dianhydride (ai) constituting the imide moiety includes at least one selected from the group consisting of a compound represented by the following formula (a1), a compound represented by the following formula (a2), a compound represented by the following formula (a3), a compound represented by the following formula (a4), a compound represented by the following formula (a5), and a compound represented by the following formula (a6).
  • the tetracarboxylic dianhydride (ai) includes at least one selected from the group consisting of the compound represented by formula (a1), the compound represented by formula (a2), the compound represented by formula (a3), the compound represented by formula (a4), the compound represented by formula (a5), and the compound represented by formula (a6), but preferably includes at least one selected from the group consisting of the compound represented by formula (a1) and the compound represented by formula (a2), and more preferably includes the compound represented by formula (a1).
  • the compound represented by formula (a1) is 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF).
  • BPAF 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride
  • the compound represented by formula (a2) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a2s), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a2a), and 2,2',3,3'-biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a2i).
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3',4'-biphenyltetracarboxylic dianhydride
  • i-BPDA 2,2',3,3'-biphenyltetracarboxylic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the resulting polyimide resin preferably has high heat resistance.
  • the compound represented by formula (a3) is p-phenylenebis(trimellitate)dianhydride (TAHQ). By including the compound represented by formula (a3), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a4) is pyromellitic anhydride (PMDA). By including the compound represented by formula (a4), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a5) is p-biphenylene bis(trimellitate) dianhydride (BP-TME). By including the compound represented by formula (a5), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a6) is bis(benzene-3,4-dicarboxylic anhydride) ester (BBDE). By including the compound represented by formula (a6), the obtained polyimide resin is preferably high in heat resistance.
  • the tetracarboxylic dianhydride (ai) may include a tetracarboxylic dianhydride other than the compounds represented by formula (a1), (a2), (a3), (a4), (a5), and (a6).
  • Such tetracarboxylic dianhydrides are not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides other than the above-mentioned compounds.
  • the tetracarboxylic dianhydride (ai) does not contain a fluorine atom, and it is preferable that the tetracarboxylic dianhydrides other than the compounds represented by the formulas (a1), (a2), (a3), (a4), (a5) and (a6) do not contain fluorine.
  • the total ratio of the compounds represented by formula (a1), (a2), (a3), (a4), (a5) and (a6) in the tetracarboxylic dianhydride (ai) is preferably 70 mol% or more and 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, even more preferably 90 mol% or more and 100 mol% or less, still more preferably 95 mol% or more and 100 mol% or less, and even more preferably 99 mol% or more and 100 mol% or less, based on the total amount of the tetracarboxylic dianhydride (ai).
  • the ratio of the compound represented by formula (a1) in the tetracarboxylic dianhydride (ai) is preferably 70 mol% or more and 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, even more preferably 90 mol% or more and 100 mol% or less, still more preferably 95 mol% or more and 100 mol% or less, and even more preferably 99 mol% or more and 100 mol% or less, based on the total amount of the tetracarboxylic dianhydride (ai).
  • the diamine (bi) constituting the imide moiety contains a compound represented by the following formula (b1), and the total amount of a compound represented by the following formula (b2) and a compound represented by the following formula (b3) relative to the compound represented by the following formula (b1) is 0.05 mol % or less.
  • the compound represented by formula (b1) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
  • the resulting polyimide resin is preferably highly heat resistant.
  • the total amount of the compound represented by formula (b2) and the compound represented by formula (b3) in the diamine (bi) is 0.05 mol% or less, preferably 0.04 mol% or less, more preferably 0.03 mol% or less, and even more preferably 0.02 mol% or less, relative to the compound represented by formula (b1).
  • the diamine (bi) may not contain either the compound represented by formula (b2) or the compound represented by formula (b3).
  • the diamine (bi) may include a diamine other than the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3).
  • Such diamines include, but are not limited to, aromatic diamines, alicyclic diamines, and aliphatic diamines other than the above compounds.
  • the diamine (bi) does not contain a fluorine atom
  • the diamine other than the compound represented by formula (b1), the compound represented by formula (b2) and the compound represented by formula (b3) also does not contain a fluorine atom. It is more preferable that neither the tetracarboxylic dianhydride (ai) nor the diamine (bi) contains a fluorine atom.
  • the ratio of the compound represented by formula (b1) in the diamine (bi) is preferably 70 mol% or more and 100 mol% or less. More preferably, it is 80 mol% or more and 100 mol% or less, even more preferably, it is 90 mol% or more and 100 mol% or less, even more preferably, it is 95 mol% or more and 100 mol% or less, even more preferably, it is 99 mol% or more and 100 mol% or less, even more preferably, it is 99.5 mol% or more and 100 mol% or less, and even more preferably, it is 99.9 mol% or more and 100 mol% or less.
  • the diamine (bi) contains a compound represented by formula (b1), and the total amount of the compound represented by formula (b2) and the compound represented by formula (b3) is 0.05 mol% or less relative to the compound represented by formula (b1). Therefore, the amount of the compound represented by formula (b2) and the compound represented by formula (b3) contained in the compound represented by formula (b1) is important. Therefore, it is preferable to have, as an optional step, a step of preparing or selecting a raw material containing the compound represented by formula (b1), the compound represented by formula (b2) and the compound represented by formula (b3) in specific amounts.
  • a step of preparing or selecting a raw material containing the compound represented by formula (b1) in a specific amount it is preferable to have a step of preparing a raw material containing the compound represented by formula (b1), the raw material having a content of the compound represented by formula (b1) of 99.9% or more. Further, it is more preferable to have a step of measuring the content of the compound represented by the formula (b1) in a raw material containing the compound represented by the formula (b1), and selecting a raw material having a content of the compound represented by the formula (b1) of 99.9% or more.
  • the tetracarboxylic dianhydride (aa) constituting the amic acid portion includes at least one selected from the group consisting of a compound represented by the following formula (a1), a compound represented by the following formula (a2), a compound represented by the following formula (a3), a compound represented by the following formula (a4), a compound represented by the following formula (a5), and a compound represented by the following formula (a6).
  • the tetracarboxylic dianhydride (aa) includes at least one selected from the group consisting of the compound represented by formula (a1), the compound represented by formula (a2), the compound represented by formula (a3), the compound represented by formula (a4), the compound represented by formula (a5), and the compound represented by formula (a6), but preferably includes at least one selected from the group consisting of the compound represented by formula (a1) and the compound represented by formula (a2), and more preferably includes the compound represented by formula (a2).
  • the compound represented by formula (a1) is 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF).
  • BPAF 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride
  • the compound represented by formula (a2) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a2s), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a2a), and 2,2',3,3'-biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a2i).
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3',4'-biphenyltetracarboxylic dianhydride
  • i-BPDA 2,2',3,3'-biphenyltetracarboxylic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the resulting polyimide resin preferably has high heat resistance.
  • the compound represented by formula (a3) is p-phenylenebis(trimellitate)dianhydride (TAHQ). By including the compound represented by formula (a3), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a4) is pyromellitic anhydride (PMDA). By including the compound represented by formula (a4), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a5) is p-biphenylene bis(trimellitate) dianhydride (BP-TME). By including the compound represented by formula (a5), the obtained polyimide resin is preferably high in heat resistance.
  • the compound represented by formula (a6) is bis(benzene-3,4-dicarboxylic anhydride) ester (BBDE). By including the compound represented by formula (a6), the obtained polyimide resin is preferably high in heat resistance.
  • the tetracarboxylic dianhydride (aa) may include a tetracarboxylic dianhydride other than the compounds represented by formula (a1), (a2), (a3), (a4), (a5), and (a6).
  • Such tetracarboxylic dianhydrides are not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides other than the above-mentioned compounds.
  • the tetracarboxylic dianhydride (aa) does not contain a fluorine atom, and it is preferable that the tetracarboxylic dianhydrides other than the compounds represented by the formulas (a1), (a2), (a3), (a4), (a5) and (a6) do not contain fluorine.
  • the total ratio of the compounds represented by formula (a1), (a2), (a3), (a4), (a5) and (a6) in the tetracarboxylic dianhydride (aa) is preferably 70 mol% or more and 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, even more preferably 90 mol% or more and 100 mol% or less, still more preferably 95 mol% or more and 100 mol% or less, and even more preferably 99 mol% or more and 100 mol% or less, based on the total amount of the tetracarboxylic dianhydride (aa).
  • the ratio of the compound represented by formula (a2) in the tetracarboxylic dianhydride (aa) is preferably 70 mol% or more and 100 mol% or less, based on the total amount of the tetracarboxylic dianhydride (aa). More preferably, it is 80 mol% or more and 100 mol% or less, even more preferably, it is 90 mol% or more and 100 mol% or less, even more preferably, it is 95 mol% or more and 100 mol% or less, and even more preferably, it is 99 mol% or more and 100 mol% or less.
  • the molar ratio of the compound represented by formula (a1) to the compound represented by formula (a2) in the tetracarboxylic dianhydride (a) [(a1)/(a2)] is preferably 5/95 to 60/40, more preferably 10/90 to 60/40, and even more preferably 15/85 to 60/40, from the viewpoints of transparency, low yellowness, and high heat resistance.
  • the diamine (ba) constituting the amide acid portion contains a compound represented by the following formula (b1), and the total amount of the compound represented by the following formula (b2) and the compound represented by the following formula (b3) relative to the compound represented by the following formula (b1) is 0.05 mol % or less.
  • the compound represented by formula (b1) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
  • the resulting polyimide resin is preferably highly heat resistant.
  • the total amount of the compound represented by formula (b2) and the compound represented by formula (b3) in the diamine (ba) is 0.05 mol% or less, preferably 0.04 mol% or less, more preferably 0.03 mol% or less, and even more preferably 0.02 mol% or less, relative to the compound represented by formula (b1).
  • the diamine (ba) may not contain either the compound represented by formula (b2) or the compound represented by formula (b3).
  • the diamine (ba) may include a diamine other than the compound represented by formula (b1), the compound represented by formula (b2), and the compound represented by formula (b3).
  • Such diamines include, but are not limited to, aromatic diamines, alicyclic diamines, and aliphatic diamines other than the above compounds.
  • the diamine (ba) does not contain a fluorine atom
  • the diamine other than the compound represented by formula (b1), the compound represented by formula (b2) and the compound represented by formula (b3) does not contain a fluorine atom either. It is more preferable that neither the tetracarboxylic dianhydride (aa) nor the diamine (ba) contains a fluorine atom.
  • the ratio of the compound represented by formula (b1) in the diamine (ba) is preferably 70 mol% or more and 100 mol% or less. More preferably, it is 80 mol% or more and 100 mol% or less, even more preferably, it is 90 mol% or more and 100 mol% or less, even more preferably, it is 95 mol% or more and 100 mol% or less, even more preferably, it is 99 mol% or more and 100 mol% or less, even more preferably, it is 99.5 mol% or more and 100 mol% or less, and even more preferably, it is 99.9 mol% or more and 100 mol% or less.
  • the diamine (bi) contains a compound represented by formula (b1), and the total amount of the compound represented by formula (b2) and the compound represented by formula (b3) is 0.05 mol% or less relative to the compound represented by formula (b1). Therefore, the amount of the compound represented by formula (b2) and the compound represented by formula (b3) contained in the compound represented by formula (b1) is important. Therefore, it is preferable to have, as an optional step, a step of preparing or selecting a raw material containing the compound represented by formula (b1), the compound represented by formula (b2) and the compound represented by formula (b3) in specific amounts.
  • a step of preparing or selecting a raw material containing the compound represented by formula (b1) in a specific amount it is preferable to have a step of preparing a raw material containing the compound represented by formula (b1), the raw material having a content of the compound represented by formula (b1) of 99.9% or more. Further, it is more preferable to have a step of measuring the content of the compound represented by the formula (b1) in a raw material containing the compound represented by the formula (b1), and selecting a raw material having a content of the compound represented by the formula (b1) of 99.9% or more.
  • the polyimide resin of the present invention may be produced by any method as long as it is capable of polymerizing a tetracarboxylic dianhydride (a) and a diamine (b) and imidizing the polymer. However, the following method is preferred.
  • a polyimide resin may be obtained directly by polymerizing tetracarboxylic dianhydride (a) (hereinafter also referred to as tetracarboxylic acid component (a)) and diamine (b) (hereinafter also referred to as diamine component (b)).
  • a polyimide resin may be obtained by a method including step 1 of polymerizing tetracarboxylic dianhydride (a) and diamine (b) to obtain a polyamic acid or an imide-amic acid copolymer, which is a polyimide resin precursor, and step 2 of imidizing the polyimide resin precursor to obtain a polyimide resin.
  • step 1 of polymerizing tetracarboxylic dianhydride (a) and diamine (b) to obtain a polyamic acid or an imide-amic acid copolymer, which is a polyimide resin precursor
  • step 2 of imidizing the polyimide resin precursor to obtain a polyimide resin.
  • the method including steps 1 and 2 is preferred, and the method in which step 1 is a step of obtaining an imide-amic acid copolymer is more preferred.
  • polyimide resin precursors imide-amic acid copolymer and polyamic acid
  • polyimide resin precursors imide-amic acid copolymer and polyamic acid
  • polyimide resin precursors and polyimide resins are sometimes collectively called polymers.
  • Step 1 Method for producing imide-amic acid copolymer, which is a polyimide resin precursor (Step 1))
  • the step 1 comprises the following steps 1a and 1b, and is a step for obtaining an imide-amic acid copolymer, which is a polyimide resin precursor:
  • Step 1a A step of reacting a tetracarboxylic dianhydride with a diamine in the presence of a solvent to obtain an imide oligomer.
  • Step 1b A step of mixing the imide oligomer obtained in step 1a with at least one of a tetracarboxylic dianhydride and a diamine, and polymerizing the mixture.
  • Step 1a is a step of reacting a tetracarboxylic dianhydride constituting an imide portion with a diamine in the presence of a solvent to obtain an imide oligomer.
  • the amount of diamine relative to the tetracarboxylic dianhydride is preferably from 1.01 to 2 mol, more preferably from 1.05 to 1.9 mol, and even more preferably from 1.1 to 1.7 mol.
  • the method for reacting a tetracarboxylic dianhydride with a diamine to obtain an imide oligomer in step 1a is not particularly limited, and any known method can be used.
  • Specific reaction methods include (1) a method in which a tetracarboxylic dianhydride, a diamine, and a solvent are charged into a reactor, and the mixture is stirred at 10 to 110° C. for 0.5 to 30 hours, and then the temperature is raised to carry out an imidization reaction; (2) a method in which a diamine and a solvent are charged into a reactor and dissolved, and then a tetracarboxylic dianhydride is charged, and the mixture is stirred at 10 to 110° C.
  • a known imidization catalyst can be used, such as a base catalyst or an acid catalyst.
  • the base catalyst include organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline; and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate.
  • the acid catalyst examples include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid, etc.
  • the above imidization catalysts may be used alone or in combination of two or more kinds.
  • a base catalyst is preferred, an organic base catalyst is more preferred, one or more selected from triethylamine and triethylenediamine is even more preferred, and triethylamine is even more preferred.
  • the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C, from the viewpoint of reaction rate and suppression of gelation, etc.
  • the reaction time is preferably 0.5 to 10 hours after the start of distillation of the generated water.
  • the above method provides a solution containing an imide oligomer dissolved in a solvent.
  • the imide oligomer-containing solution obtained in step 1 may contain at least a portion of the components used as the tetracarboxylic dianhydride or diamine in step 1 as unreacted monomers, as long as the effect of the present invention is not impaired.
  • Step 1b is a step of mixing the imide oligomer obtained in step 1a with at least one of a tetracarboxylic dianhydride and a diamine, and polymerizing the mixture.
  • the ratio of the diamine component to the tetracarboxylic acid component in step 1a and step 1b as a whole is preferably 0.9 to 1.1 moles.
  • step 1b the method for polymerizing the imide oligomer obtained in step 1a, the tetracarboxylic dianhydride, and the diamine is not particularly limited, and any known method can be used.
  • the reaction method include: (1) a method in which an imide oligomer and at least one of a tetracarboxylic dianhydride and a diamine are charged into a reactor and stirred at 0 to 120° C., preferably 5 to 80° C., for 1 to 72 hours; and (2) a method in which an imide oligomer and a solvent are charged into a reactor and dissolved, and then at least one of a tetracarboxylic dianhydride and a diamine is charged and stirred at 0 to 120° C., preferably 5 to 80° C., for 1 to 72 hours.
  • the molecular weight of the copolymer obtained in step 2 does not vary depending on the temperature history during polymerization, and the progress of thermal imidization can be suppressed, so that the copolymer can be stably produced.
  • the concentration of the copolymer in the resulting solution is preferably 1 to 50% by mass, more preferably 3 to 35% by mass, and even more preferably 5 to 30% by mass.
  • Method for producing polyamic acid which is a polyimide resin precursor (Step 1)
  • a preferred method for producing the polyimide resin precursor is a method in which a tetracarboxylic dianhydride and a diamine are reacted in the presence of a solvent to obtain a polyamic acid.
  • the method for polymerizing the tetracarboxylic dianhydride and the diamine is not particularly limited, and any known method can be used.
  • a specific reaction method includes a method in which a solution containing a diamine and a solvent and a tetracarboxylic dianhydride are charged into a reactor and stirred at a temperature in the range of preferably 0 to 120° C., more preferably 5 to 80° C., for 1 to 72 hours.
  • the ratio of the diamine component to the tetracarboxylic acid component is preferably 0.9 to 1.1 moles.
  • the concentration of polyamic acid in the resulting solution is preferably 1 to 50% by mass, more preferably 3 to 35% by mass, and even more preferably 5 to 30% by mass.
  • This step is a step of imidizing the polyimide resin precursor to obtain a polyimide resin.
  • the polyimide resin precursor is preferably used in the form of a solution, the solution containing the polyimide resin precursor and a solvent.
  • the solvent is not particularly limited as long as the polyimide resin precursor dissolves therein, but it is preferable to use a solvent used in the production of the polyimide resin precursor, either alone or in a mixture of two or more kinds. Specific solvents will be described later.
  • the solvent may be added to dilute the mixture.
  • the solution further contains an imidization catalyst and a dehydration catalyst.
  • the imidization catalyst may be one having a boiling point of 40° C. or higher, and an imidization catalyst having a boiling point of 40° C. or higher can avoid the possibility of volatilization before the imidization has sufficiently proceeded.
  • the imidization catalyst include amine compounds such as pyridine or 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.
  • dehydration catalyst examples 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 concentration in the solution is preferably 3 to 40% by mass, more preferably 5 to 40% by mass, and even more preferably 6 to 30% by mass.
  • the solution viscosity is preferably 0.1 to 100 Pa ⁇ s, and more preferably 0.1 to 20 Pa ⁇ s.
  • the solution viscosity is a value measured at 25°C using an E-type viscometer.
  • the solution may also contain various additives such as inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, surfactants, leveling agents, defoamers, fluorescent brighteners, crosslinking agents, polymerization initiators, and photosensitizers.
  • the solution is applied to a smooth support such as a glass plate, a metal plate, or plastic, and then the solvent is removed by heating to obtain a film, and the amide acid moiety is imidized (dehydration ring closure) by heating, and then peeled off from the support to produce a film-like polyimide resin.
  • the temperature for removing the solvent is preferably 50 to 150° C.
  • the heating temperature for imidization is preferably 200 to 500° C., more preferably 300 to 470° C., and even more preferably 400 to 450° 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.
  • 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 hydrogen concentration of 0.5% or less are preferred.
  • the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.
  • a preferred method for directly obtaining a polyimide resin is to react a tetracarboxylic dianhydride with a diamine in the presence of a solvent to obtain a polyimide resin.
  • the method for polymerizing the tetracarboxylic dianhydride and the diamine is not particularly limited, and any known method can be used.
  • Specific examples of the reaction method include (1) a method in which a solution containing a diamine and a solvent, and a tetracarboxylic dianhydride are charged into a reactor, and the mixture is stirred at 10 to 110° C. for 0.5 to 30 hours as necessary, and then heated to carry out an imidization reaction; and (2) a method in which a solution containing a diamine and a solvent, and a tetracarboxylic dianhydride are charged into a reactor, and the mixture is immediately heated to carry out an imidization reaction.
  • a known imidization catalyst can be used, such as a base catalyst or an acid catalyst.
  • the base catalyst include organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline; and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate.
  • the acid catalyst examples include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid, etc.
  • the above imidization catalysts may be used alone or in combination of two or more kinds.
  • a base catalyst is preferred, an organic base catalyst is more preferred, one or more selected from triethylamine and triethylenediamine is even more preferred, and triethylamine is even more preferred.
  • the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C, from the viewpoint of reaction rate and suppression of gelation, etc.
  • the reaction time is preferably 0.5 to 10 hours after the start of distillation of the generated water.
  • the concentration of polyimide in the resulting solution is preferably 1 to 50% by mass, more preferably 3 to 35% by mass, and even more preferably 5 to 30% by mass.
  • a terminal blocking agent may be used in the production of the polymer.
  • the terminal blocking agent is preferably used in step 2.
  • the terminal blocking agent is preferably a monoamine, a dicarboxylic acid, or an acid anhydride.
  • the amount of the terminal blocking agent introduced is preferably 0.0001 to 20 moles, more preferably 0.1 to 10 moles, and even more preferably 0.5 to 5 moles, per mole of the tetracarboxylic acid component.
  • the monoamine terminal blocking agent for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and the like are recommended.
  • benzylamine, aniline, o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, and p-aminobenzoic acid can be preferably used.
  • dicarboxylic acid end-capping agent dicarboxylic acids are preferred, and a part of them may be ring-closed.
  • phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trimellitic anhydride, and the like are recommended.
  • phthalic acid, phthalic anhydride, and trimellitic anhydride can be preferably used.
  • the solvent used in the method for producing the polymer may be any solvent capable of dissolving the polymer to be produced, and examples of such solvents include aprotic solvents, phenol-based solvents, ether-based solvents, and carbonate-based solvents.
  • aprotic solvents include amide solvents such as cyclic amides and chain amides, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents including cyclic esters.
  • the solvent preferably contains at least one selected from the group consisting of cyclic amides, chain amides, and cyclic esters, and more preferably contains a cyclic amide.
  • the cyclic amide include N-methylpyrrolidone, N-methylcaprolactam, and 1,3-dimethylimidazolidinone, with N-methylpyrrolidone being preferred.
  • Examples of the chain amide include N,N-dimethylformamide, N,N-dimethylacetamide, and tetramethylurea.
  • Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -valerolactone.
  • Other ester solvents include 2-methoxy-1-methylethyl acetate.
  • 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, and methylcyclohexanone.
  • phenol-based solvents 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 solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, and 1,4-dioxane.
  • carbonate solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
  • the solvent contains at least one selected from the group consisting of cyclic amides, linear amides, and cyclic esters, more preferably, the solvent contains at least one selected from the group consisting of cyclic amides and cyclic esters, and even more preferably, the solvent contains a cyclic ester. More specifically, the solvent contains at least one selected from the group consisting of N-methylpyrrolidone and ⁇ -butyrolactone, and even more preferably, the solvent contains ⁇ -butyrolactone.
  • the above solvents may be used alone or in combination of two or more kinds.
  • the polyimide resin of the present invention is a polyimide resin obtained by the above-mentioned production method. Therefore, the polyimide resin of the present invention is a polyimide resin obtained by polymerizing a tetracarboxylic dianhydride (a) and a diamine (b) and imidizing the polymer, the tetracarboxylic dianhydride (a) containing at least one selected from the group consisting of a compound represented by the following formula (a1), a compound represented by the following formula (a2), a compound represented by the following formula (a3), a compound represented by the following formula (a4), a compound represented by the following formula (a5), and a compound represented by the following formula (a6), the diamine (b) containing a compound represented by the following formula (b1), and the total amount of the compound represented by the following formula (b2) and the compound represented by the following formula (b3) relative to the compound represented by the following formula (b1) is 0.05 mol
  • the polyimide resin has a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine.
  • the structural unit A and the structural unit B form an imide structure.
  • the polyimide resin of the present invention preferably has a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A preferably comprises at least one selected from the group consisting of a structural unit (A1) derived from a compound represented by formula (a1), a structural unit (A2) derived from a compound represented by formula (a2), a structural unit (A3) derived from a compound represented by formula (a3), a structural unit (A4) derived from a compound represented by formula (a4), a structural unit (A5) derived from a compound represented by formula (a5), and a structural unit (A6) derived from a compound represented by formula (a6), and the structural unit B comprises a structural unit (B1) derived from a compound represented by formula (b1), and the total amount of the structural unit (B2) derived from a
  • the structural unit A preferably includes at least one selected from the group consisting of the structural unit (A1) derived from a compound represented by formula (a1), the structural unit (A2) derived from a compound represented by formula (a2), the structural unit (A3) derived from a compound represented by formula (a3), the structural unit (A4) derived from a compound represented by formula (a4), the structural unit (A5) derived from a compound represented by formula (a5), and the structural unit (A6) derived from a compound represented by formula (a6), and more preferably includes the structural unit (A2) derived from a compound represented by formula (a2), and even more preferably includes the structural unit (A1) derived from a compound represented by formula (a1) and the structural unit (A2) derived from a compound represented by formula (a2).
  • the total ratio of the structural units (A1), (A2), (A3), (A4), (A5) and (A6) in the structural unit A is preferably 70 mol% or more and 100 mol% or less, based on the total amount of the structural unit A. More preferably, it is 80 mol% or more and 100 mol% or less, even more preferably, it is 90 mol% or more and 100 mol% or less, still more preferably, it is 95 mol% or more and 100 mol% or less, and still more preferably, it is 99 mol% or more and 100 mol% or less.
  • the molar ratio of the structural unit (A1) to the structural unit (A2) in the structural unit A [(A1)/(A2)] is preferably 5/95 to 60/40, more preferably 10/90 to 60/40, and even more preferably 15/85 to 60/40, from the viewpoints of transparency, low yellowness, and high heat resistance.
  • the total amount of the structural unit (B2) and the structural unit (B3) in the structural unit B is preferably 0.05 mol% or less, more preferably 0.04 mol% or less, even more preferably 0.03 mol% or less, and even more preferably 0.02 mol% or less, relative to the structural unit (B1).
  • the structural unit B may not contain either the structural unit (B2) or the structural unit (B3).
  • the ratio of the structural unit (B1) in the structural unit B is preferably 70 mol% or more and 100 mol% or less. More preferably, it is 80 mol% or more and 100 mol% or less, even more preferably, it is 90 mol% or more and 100 mol% or less, even more preferably, it is 95 mol% or more and 100 mol% or less, even more preferably, it is 99 mol% or more and 100 mol% or less, even more preferably, it is 99.5 mol% or more and 100 mol% or less, and even more preferably, it is 99.9 mol% or more and 100 mol% or less.
  • the method for producing an image display device substrate of the present invention is a method for producing an image display device substrate, which comprises molding the polyimide resin obtained by the method for producing a polyimide resin or the polyimide resin.
  • the polyimide resin obtained by the method for producing a polyimide resin and the polyimide resin described above have excellent heat resistance and excellent colorless transparency after heat treatment, and therefore are useful as materials for image display device substrates.
  • the method for molding the polyimide resin may be appropriately selected depending on the application, size, etc. of the image display device. Specifically, the method for producing a film-shaped polyimide resin (polyimide resin film) described above in the section (Imidization (Step 2)) is preferred.
  • the polyimide resin precursor solution is applied onto a smooth support such as a glass plate, a metal plate, or a plastic plate, the solvent is then removed by heating to obtain a film, the amide acid moiety is imidized (dehydration ring closure) by heating, and then the film is peeled off from the support, whereby an image display device substrate, which is a film-like polyimide resin, can be produced.
  • a smooth support such as a glass plate, a metal plate, or a plastic plate
  • the solvent is then removed by heating to obtain a film
  • the amide acid moiety is imidized (dehydration ring closure) by heating
  • the film is peeled off from the support, whereby an image display device substrate, which is a film-like polyimide resin, can be produced.
  • the temperature for removing the solvent is preferably 50 to 150° C.
  • the heating temperature for imidization is preferably 200 to 500° C., more preferably 300 to 470° C., and even more preferably 400 to 450° 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.
  • 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 hydrogen 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 polyimide resin film thus obtained has excellent heat resistance and excellent colorless transparency after heat treatment, and is therefore suitably used as a substrate for an image display device.
  • NMP N-methyl-2-pyrrolidone (Tokyo Pure Chemical Industries, Ltd.)
  • TEA Triethylamine (Kanto Chemical Co., Ltd.)
  • Example 1 As a diamine raw material, 4-BAAB was prepared, in which the content of (b1) in the raw material (b1) was 99.9% and the total amount of (b2) and (b3) in the raw material (b1) was 0.02 mol %. 9.370 g (0.041 mol) of 4-BAAB and 207.059 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 under a nitrogen atmosphere at an internal temperature of 70° C. to obtain a solution.
  • the plate was held in a hot air dryer at 150° C. for 30 minutes, 200° C. for 15 minutes, 350° C. for 15 minutes, and 450° C. for 10 minutes to obtain a polyimide film.
  • the evaluation results of the film are shown in Table 1.
  • Comparative Examples 1 and 2 A polyimide resin film was obtained in the same manner as in Example 1, except that 4-BAAB was changed to 4-BAAB having the (b1) content and the total amount of (b2) and (b3) shown in Table 1. The evaluation results of the film are shown in Table 1.
  • the polyimide resins of the examples have a small yellowness even after heat treatment. This shows that the polyimide resins obtained by the manufacturing method of the present invention have excellent heat resistance and excellent colorless transparency after heat treatment. Therefore, the manufacturing method of the present invention can obtain polyimide resins that have excellent heat resistance and excellent colorless transparency after heat treatment, and are therefore useful as substrate materials used in image display devices such as liquid crystal displays and OLED displays.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention fournit un procédé de fabrication de résine polyimide qui permet d'obtenir une résine polyimide excellente en termes de résistance à la chaleur et de transparence incolore après traitement thermique. Plus précisément, l'invention concerne un procédé de fabrication de résine polyimide selon lequel un dianhydride d'acide tétracarboxylique (a) et une diamine (b) sont polymérisés et soumis à une imidisation. Le dianhydride d'acide tétracarboxylique (a) contient au moins un composé choisi dans un groupe constitué d'un composé représenté par la formule (a1), d'un composé représenté par la formule (a2), d'un composé représenté par la formule (a3), d'un composé représenté par la formule (a4), d'un composé représenté par la formule (a5) et d'un composé représenté par la formule (a6). La diamine (b) contient un composé représenté par la formule (b1), la quantité totale de composé représenté par la formule (b2) et de composé représenté par la formule (b3), étant inférieure ou égale à ０,０５% en moles pour le composé représenté par la formule (b1).
PCT/JP2024/035483 2023-10-19 2024-10-03 Procédé de fabrication de résine polyimide Pending WO2025084154A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1085869B (de) * 1959-07-11 1960-07-28 Bayer Ag Verfahren zur Herstellung von monomeren aromatischen Estergruppen aufweisenden Polyisocyanaten
CN101481320A (zh) * 2009-01-20 2009-07-15 常州市阳光医药原料有限公司 一种4-氨基苯甲酸(4-氨基苯基)酯的制备方法
WO2017051827A1 (fr) * 2015-09-24 2017-03-30 旭化成株式会社 Précurseur de polyimide, composition de résine, et procédé de production d'un film de résine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1085869B (de) * 1959-07-11 1960-07-28 Bayer Ag Verfahren zur Herstellung von monomeren aromatischen Estergruppen aufweisenden Polyisocyanaten
CN101481320A (zh) * 2009-01-20 2009-07-15 常州市阳光医药原料有限公司 一种4-氨基苯甲酸(4-氨基苯基)酯的制备方法
WO2017051827A1 (fr) * 2015-09-24 2017-03-30 旭化成株式会社 Précurseur de polyimide, composition de résine, et procédé de production d'un film de résine

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