WO2020246466A1 - Résine de polyimide et son procédé de production, et film de polyimide et son procédé de production - Google Patents

Résine de polyimide et son procédé de production, et film de polyimide et son procédé de production Download PDF

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Publication number
WO2020246466A1
WO2020246466A1 PCT/JP2020/021778 JP2020021778W WO2020246466A1 WO 2020246466 A1 WO2020246466 A1 WO 2020246466A1 JP 2020021778 W JP2020021778 W JP 2020021778W WO 2020246466 A1 WO2020246466 A1 WO 2020246466A1
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polyimide
acid dianhydride
polyimide resin
diamine
dianhydride
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PCT/JP2020/021778
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English (en)
Japanese (ja)
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裕之 後
紘平 小川
正広 宮本
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株式会社カネカ
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Priority to CN202080041238.2A priority Critical patent/CN113906083B/zh
Priority to KR1020217043294A priority patent/KR20220016917A/ko
Priority to JP2021524858A priority patent/JPWO2020246466A1/ja
Publication of WO2020246466A1 publication Critical patent/WO2020246466A1/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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide resin and a method for producing the same, a polyimide solution, and a polyimide film and a method for producing the same.
  • polyimide film as an alternative material to glass conventionally used as a substrate or surface protection material is being considered.
  • a general polyimide is colored yellow or brown and does not show solubility in an organic solvent, but a low-colored polyimide can be obtained by introducing an alicyclic structure or a fluoroalkyl group (for example, Patent Document 1). ).
  • the polyimide film obtained from the polyimide resin of Patent Document 1 does not have sufficient mechanical strength to be used for a cover window or the like arranged on the outer surface of the device.
  • An object of the present invention is to provide a polyimide resin and a polyimide film which are soluble in a low boiling point solvent such as dichloromethane and have excellent transparency and mechanical strength.
  • the polyimide resin according to one embodiment of the present invention has an acid dianhydride-derived structure and a diamine-derived structure, and the acid dianhydride and the cyclobutane structure represented by the general formula (1) are used as the acid dianhydride. It contains an acid dianhydride having and contains a fluoroalkyl-substituted benzidine as a diamine.
  • R 1 to R 8 are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or perfluoroalkyl groups having 1 to 20 carbon atoms, and R 1 to R 4 respectively.
  • one or more of the one or more and R 5 ⁇ R 8 of is an alkyl group or a fluoroalkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms.
  • the amount of acid dianhydride represented by the general formula (1) is preferably 40 to 85 mol% with respect to 100 mol% of the total amount of acid dianhydride.
  • the amount of the acid dianhydride having a cyclobutane structure is preferably 15 to 60 mol% with respect to 100 mol% of the total amount of the acid dianhydride.
  • the amount of the fluoroalkyl-substituted benzidine is preferably 40 to 100 mol% with respect to 100 mol% of the total diamine.
  • Specific examples of the acid dianhydride represented by the general formula (1) include a compound represented by the formula (2).
  • cyclobutane structure-containing acid dianhydride examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
  • fluoroalkyl-substituted benzidine examples include 2,2'-bis (trifluoromethyl) benzidine.
  • Polyimide may contain an acid dianhydride component or a diamine component other than the above.
  • acid dianhydrides other than the above include 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1, Examples thereof include 3,3,3-hexafluoropropane dianhydride.
  • diamines other than the above include diaminodiphenyl sulfone.
  • a polyimide film can be obtained by dissolving a polyimide resin in a solvent to prepare a polyimide solution, applying the polyimide solution on a substrate, and removing the solvent.
  • a solvent for dissolving the polyimide a low boiling point solvent such as dichloromethane is preferable.
  • the thickness of the polyimide film may be 40 ⁇ m or more.
  • the yellowness of the polyimide film may be 3.0 or less, the tensile elastic modulus may be 5.0 GPa or more, and the pencil hardness may be H or more.
  • the polyimide resin of the present invention is soluble in a low boiling point solvent such as dichloromethane and does not require heating at a high temperature to reduce the residual solvent, a highly transparent polyimide film can be obtained. Since the polyimide resin of the present invention is soluble in a low boiling point solvent such as dichloromethane and does not require heating at a high temperature to reduce the residual solvent, a highly transparent polyimide film can be obtained. Since the polyimide film of the present invention has high mechanical strength and high transparency even when the film thickness is large, it can be used as a substrate material for a display, a cover window material, or the like.
  • Polyimide resin Polyimide is generally obtained by dehydration cyclization of a polyamic acid obtained by reacting a tetracarboxylic dianhydride (hereinafter, may be simply referred to as "acid dianhydride”) with a diamine. That is, the polyimide has an acid dianhydride-derived structure and a diamine-derived structure.
  • the polyimide resin of the present invention contains an ester group-containing acid dianhydride (bisanhydride trimellitic acid ester) as an acid dianhydride component and an acid dianhydride having an alicyclic structure, and a fluoroalkyl substitution as a diamine component. Contains benzidine.
  • the polyimide of the present invention contains an ester group-containing acid dianhydride represented by the following general formula (1) and an alicyclic acid dianhydride having a cyclobutane structure as the acid dianhydride.
  • R 1 to R 8 are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or fluoroalkyl groups having 1 to 20 carbon atoms. At least one of R 1 to R 4 is a substituent other than a hydrogen atom, and at least one of R 5 to R 8 is a substituent other than a hydrogen atom (that is, an alkyl group or a carbon atom having 1 to 20 carbon atoms). It is a fluoroalkyl group of number 1 to 20).
  • the content of the acid dianhydride represented by the above general formula (1) is 40 to 85 mol%, preferably 40 to 80 mol%, and 40 to 75 mol%. More preferably, it may be 45 to 70 mol% or 50 to 65 mol%.
  • the content of the acid dianhydride represented by the general formula (1) is within the above range, significant thickening and gelation are suppressed during the polymerization reaction of the polyamic acid and the imidization reaction in the solution. At the same time, the solubility of the polyimide resin in a low boiling point solvent can be ensured. Further, when the content of the acid dianhydride represented by the general formula (1) is within the above range, the mechanical strength of the polyimide film tends to be improved.
  • the acid dianhydride represented by the general formula (1) is an ester of trimellitic anhydride and a biphenol having a substituent. Since the acid dianhydride represented by the general formula (1) has a biphenyl structure, the ultraviolet resistance property of polyimide is enhanced, and the decrease in transparency (increase in yellowness YI) due to ultraviolet irradiation tends to be suppressed. is there.
  • Substituents R 1 to R 8 in the general formula (1) are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or fluoroalkyl groups having 1 to 20 carbon atoms.
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group and cyclopentyl group.
  • Groups, n-hexyl groups, cyclohexyl groups and the like can be mentioned.
  • fluoroalkyl group examples include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group and the like.
  • a perfluoroalkyl group such as a trifluoromethyl group or a pentafluoroethyl group is preferable.
  • At least one of R 1 to R 4 is a substituent other than a hydrogen atom
  • at least one of R 5 to R 8 is a substituent other than a hydrogen atom.
  • at least one of R 2 and R 3 and at least one of R 6 and R 7 are substituents other than hydrogen atoms. If these are substituents other than hydrogen atoms, the bond between the two benzene rings of biphenyl is twisted due to steric hindrance and the flatness of the ⁇ -conjugated system is reduced, so that the absorption edge wavelength is shifted by a short wavelength, and the polyimide Coloring tends to be reduced.
  • R 2 and R 6 are methyl groups and R 3 and R 7 are hydrogen atoms.
  • R 1, R 4, R 5 and bis R 8 is represented by the following formula is a methyl group (2) (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 2, 2', 3,3', 5,5'-hexamethylbiphenyl-4,4'-diyl (TAHMBP) is preferred.
  • the content of the acid dianhydride having a cyclobutane structure is 15 to 60 mol%, preferably 15 to 50 mol%, and more preferably 15 to 40 mol%.
  • the content of the acid dianhydride having a cyclobutane structure is 15 mol% or more, the mechanical strength of the polyimide film tends to be improved, and when it is 60 mol% or less, the solubility of the polyimide resin in a low boiling point solvent or the like Tends to improve.
  • acid dianhydride having a cyclobutane structure examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride.
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is preferable.
  • Acid dihydrate components other than the above may be used in combination as long as the solubility in a low boiling point solvent such as dichloromethane is not impaired and the characteristics such as transparency and mechanical strength are not impaired.
  • acid dianhydrides other than the above include 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-.
  • Fluorene dianhydride ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 1,1'-bicyclohexane-3,3', 4,4'-tetracarboxylic acid-3,4: 3', 4'-dianhydride, 3,3', 4,4' -Benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanedianhydride, 2,2- Bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfonate dianhydride
  • the acid dianhydride in addition to the acid dianhydride represented by the general formula (1) and the acid dianhydride having a cyclobutane structure, 2,2-bis (3,4-dicarboxyphenyl) -1 , 1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), by using low dichloromethane and the like.
  • 6FDA 1,1,3,3,3-hexafluoropropane dianhydride
  • BPDA 3,3', 4,4'-biphenyltetracarboxylic dianhydride
  • the content of 6FDA out of 100 mol% of the total amount of the acid dianhydride component is preferably 5 mol% or more, more preferably 10 mol% or more, and may be 15 mol% or more.
  • the content of BPDA in 100 mol% of the total amount of the acid dianhydride component may be 5 mol% or more, 10 mol% or more, or 15 mol% or more.
  • the content of the acid dianhydride represented by the general formula (1) and the acid dianhydride other than the acid dianhydride having a cyclobutane structure is preferably 40 mol% or less. ..
  • the content of 6FDA is preferably 25 mol% or less
  • the content of BPDA is preferably 25 mol% or less.
  • the polyimide of the present invention contains a fluoroalkyl-substituted benzidine as a diamine component.
  • the content of the fluoroalkyl-substituted benzidine is 40 to 100 mol%, preferably 60 mol% or more, and more preferably 70 mol% or more.
  • the content of the fluoroalkyl-substituted benzidine is 40 mol% or more, coloring of the polyimide film is suppressed, and the pencil hardness and elastic modulus tend to be high.
  • fluoroalkyl-substituted benzidines examples include 2,2'-dimethylbenzidine, 2-fluorobenzidine, 3-fluorobenzidine, 2,3-difluorobenzidine, 2,5-difluorobenzidine, 2,6-difluorobenzidine, 2, 3,5-Trifluorobenzidine, 2,3,6-trifluorobenzidine, 2,3,5,6-tetrafluorobenzidine, 2,2'-difluorobenzidine, 3,3'-difluorobenzidine, 2,3' -Difluorobenzidine, 2,2', 3-trifluorobenzidine, 2,3,3'-trifluorobenzidine, 2,2', 5-trifluorobenzidine, 2,2', 6-trifluorobenzidine, 2, 3', 5-trifluorobenzidine, 2,3', 6,-trifluorobenzidine, 2,2', 3,3'-tetrafluorobenzidine, 2,2', 5,5'-tetrafluorobenzidine,
  • a fluoroalkyl-substituted benzidine having a fluoroalkyl group at the 2-position of biphenyl is preferable, and 2,2'-bis (trifluoromethyl) benzidine (hereinafter referred to as "TFMB”) is particularly preferable.
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • Diamines other than the above may be used in combination as long as the solubility in a low boiling point solvent such as dichloromethane is not impaired and the characteristics such as transparency and mechanical strength are not impaired.
  • diamines other than fluoroalkyl-substituted benzidines include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether.
  • diaminodiphenyl sulfone in addition to fluoroalkyl-substituted benzidine as the diamine, the solubility and transparency of the polyimide resin in a solvent may be improved.
  • diaminodiphenyl sulfones 3,3'-diaminodiphenyl sulfone (3,3'-DDS) and 4,4'-diaminodiphenyl sulfone (4,4'-DDS) are preferable. 3,3'-DDS and 4,4'-DDS may be used together.
  • the content of diaminodiphenylsphon with respect to 100 mol% of the total amount of diamine is preferably 3 mol% or more, more preferably 5 mol% or more, and may be 8 mol% or more or 10 mol% or more.
  • the content of diaminodiphenyl sulfone with respect to 100 mol% of the total amount of diamine is preferably 40 mol% or less, more preferably 30 mol% or less.
  • the polyimide of the present invention contains an acid dianhydride represented by the general formula (1) and an acid dianhydride having a cyclobutane structure as an acid dianhydride component, and a fluoroalkyl-substituted benzidine as a diamine.
  • the acid dianhydride represented by the general formula (1) is preferably TAHMBP represented by the formula (2)
  • the cyclobutane structure-containing acid dianhydride is preferably CBDA
  • the fluoroalkyl-substituted benzidine is preferably TFMB. .
  • the polyimide may further contain 6FDA and / or BPDA as the acid dianhydride component, and may further contain 3,3'-DDS and / or 4,4'-DDS as the diamine component.
  • the amount of TAHMBP is more preferably 40 to 85 mol%, and the amount of CBDA is preferably 15 to 60 mol%. Further, from the viewpoint of improving the solubility of the polyimide resin and improving the transparency of the film, it is preferable to contain 6FDA and / or BPDA as an acid dianhydride component in an amount of 25 mol% or less, respectively.
  • the amount of TFMB is preferably 40 to 100 mol%, more preferably 70 to 95 mol%. Further, it is preferable that the diamine component contains 3,3'-DDS or 4,4'-DDS in an amount of 5 to 30 mol%.
  • the polyimide having the above composition has high solubility in a low boiling solvent such as dichloromethane, the amount of residual solvent in the polyimide film can be easily reduced, and the polyimide film has high transmittance, low yellowness, and high mechanical strength. A polyimide film can be produced.
  • the method for producing the polyimide resin is not particularly limited, but a method in which a diamine and an acid dianhydride are reacted in a solvent to prepare a polyamic acid as a polyimide precursor and imidized by dehydration cyclization of the polyamic acid is preferable.
  • a polyimide solution can be obtained by adding an imidization catalyst and a dehydrating agent to the polyamic acid solution to dehydrate and close the polyamic acid.
  • a polyimide resin is obtained by mixing a polyimide solution and a poor solvent of polyimide to precipitate a polyimide resin and then solid-liquid separation.
  • a polyamic acid solution is obtained by reacting the acid dianhydride with the diamine in a solvent.
  • diamine and acid dianhydride as raw materials, and an organic solvent capable of dissolving polyamic acid as a polymerization product can be used without particular limitation.
  • organic solvent examples include urea solvents such as methyl urea and N, N-dimethylethyl urea; sulfonate solvents such as dimethyl sulfoxide, diphenyl sulfone and tetramethyl sulfone; N, N-dimethylacetamide, N, N- Amido solvents such as dimethylformamide, N, N'-diethylacetamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, hexamethylphosphate triamide; alkyl halide solvents such as chloroform and dichloromethane; benzene, toluene and the like Examples thereof include aromatic hydrocarbon solvents, ether solvents such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethyl ether, diethyl ether, and p-cresol methyl ether.
  • urea solvents such as methyl urea
  • N, N-dimethylacetamide, N, N-dimethylformamide, or N-methylpyrrolidone is preferably used because of its excellent polymerization reactivity and solubility of polyamic acid.
  • Polymerization of polyamic acid proceeds by dissolving diamine and acid dianhydride in an organic solvent.
  • the solid content concentration of the polyamic acid solution (the concentration of diamine and acid dianhydride charged in the reaction solution) is usually about 5 to 40% by weight, preferably 10 to 30% by weight. It is preferable to use an equimolar amount (95: 105 to 105: 95) of the acid dianhydride and the diamine. If either component is excessive, the molecular weights of the polyamic acid and the polyimide may not be sufficiently increased, and the mechanical strength of the polyimide film may be lowered.
  • the reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and 80 ° C. or lower, and more preferably 20 ° C. or higher and 45 ° C. or lower.
  • the temperature is preferably 0 ° C. or higher and 80 ° C. or lower, and more preferably 20 ° C. or higher and 45 ° C. or lower.
  • the order of adding diamine and acid dianhydride to the organic solvent (reaction system) in the polymerization of polyamic acid is not particularly limited.
  • the arrangement of the monomer components (acid dianhydride-derived structure and diamine-derived structure) in the polyamic acid and the polyimide may be random or block.
  • Random polyamic acid can be obtained by dissolving either the total amount of diamine or the total amount of acid dianhydride in an organic solvent or dispersing it in a slurry form, and then adding the other.
  • the diamine may be dissolved in an organic solvent or dispersed in a slurry to form a diamine solution, and the acid dianhydride may be added to the diamine solution.
  • Diamine may be added to a solution of acid dianhydride in an organic polar solvent.
  • the plurality of types of acid dianhydride and diamine may be added at one time, or may be added in a plurality of times.
  • the diamine and the acid dianhydride may be added in a solid state, dissolved in an organic solvent, or dispersed in a slurry.
  • A a structural unit (repeating unit) in which a specific acid dianhydride and a diamine are bonded by reacting a specific acid dianhydride and a diamine first among a plurality of types of acid dianhydride and a diamine.
  • a polyimide containing a continuous block of structural units in which a specific diamine and a specific acid dianhydride are bonded can be obtained in the molecular structure.
  • the polyimide has a block structure, the mechanical strength and heat resistance of the polyimide film tend to be improved.
  • step (A) by reacting either the acid dianhydride or the diamine as an excess amount, an acid anhydride-terminated or amine-terminated oligomer is formed.
  • the amount of acid dianhydride and diamine charged in the preparation of the oligomer is preferably 70 to 95 mol%, more preferably 75 to 90 mol%, based on the total amount charged (the total amount charged of (A) and (B)). ..
  • the amount of diamine charged is preferably 1.01 to 1.25 times, more preferably 1.03 to 1.2 times, the molar ratio of the amount of acid dianhydride charged. It is preferable, and 1.05 to 1.18 times is more preferable. The closer the ratio of the two is to 1, the larger the molecular weight of the oligomer tends to be.
  • fluoroalkyl-substituted benzidines such as TFMB are included as diamines, acid dianhydrides represented by the general formula (1) such as TAHMBP and acid dianhydrides containing cyclobutane structures such as CBDA as acid dianhydrides. It is preferable to include. In particular, it is preferable to use only fluoroalkyl-substituted benzidine as the diamine.
  • step (B) by adding the balance of diamine and acid dianhydride so that the total amount of diamine charged and the total amount of acid dianhydride charged are equimolar amounts (95: 105 to 105: 95).
  • the terminal of the oligomer prepared in the above step (A) reacts with the monomer added in the step (B) to obtain a polyamic acid having an alternating block structure.
  • a polyimide containing a continuous block of structural units in which a specific diamine and a specific acid dianhydride are bonded can be obtained in the molecular structure.
  • step (B) the remaining acid dianhydride and diamine may be added at the same time or sequentially.
  • the oligomer obtained by reacting the remaining acid dianhydride with diamine in advance may be added to the solution of the oligomer prepared in (A).
  • Polyimide can be obtained by dehydration cyclization of polyamic acid.
  • a chemical imidization method in which a dehydrating agent, an imidization catalyst, or the like is added to the polyamic acid solution is suitable.
  • the polyamic acid solution may be heated to accelerate the progress of imidization.
  • a tertiary amine is used as the imidization catalyst.
  • a heterocyclic tertiary amine is preferable.
  • Specific examples of the heterocyclic tertiary amine include pyridine, picoline, quinoline, isoquinoline and the like.
  • carboxylic acid anhydride is used, and specific examples thereof include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic acid anhydride, and trifluoroacetic anhydride.
  • the amount of the imidization catalyst added is preferably 0.5 to 5.0 times the molar equivalent, more preferably 0.7 to 2.5 times the molar equivalent, and 0.8 to 2 times the molar equivalent of the amide group of the polyamic acid. A 0-fold molar equivalent is more preferred.
  • the amount of the dehydrating agent added is preferably 0.5 to 10.0 times the molar equivalent, more preferably 0.7 to 5.0 times the molar equivalent, and 0.8 to 3.0 times the amide group of the polyamic acid. Double molar equivalents are more preferred.
  • the polyimide solution obtained by imidization of the polyamic acid can be used as it is as a doping for film formation, but it is preferable to once precipitate the polyimide resin as a solid substance.
  • impurities and residual monomer components generated during the polymerization of polyamic acid, a dehydrating agent, an imidization catalyst, and the like can be washed and removed. Therefore, a polyimide film having excellent transparency and mechanical properties can be obtained.
  • the polyimide resin is precipitated by mixing the polyimide solution and the poor solvent.
  • the poor solvent is a poor solvent of the polyimide resin, preferably one that is mixed with a solvent in which the polyimide resin is dissolved, and examples thereof include water and alcohols.
  • alcohols include methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol, t-butyl alcohol and the like.
  • Alcohols such as isopropyl alcohol, 2-butyl alcohol, 2-pentyl alcohol, phenol, cyclopentyl alcohol, cyclohexyl alcohol, and t-butyl alcohol are preferable, and isopropyl alcohol is particularly preferable, because ring opening of polyimide is unlikely to occur.
  • a polyimide film can be produced by applying a polyimide solution (a dope for film formation) in which a polyimide resin is dissolved in an organic solvent onto a substrate and drying and removing the solvent.
  • the organic solvent for dissolving the polyimide resin is not particularly limited as long as it is soluble and soluble in the above-mentioned polyimide resin.
  • Low boiling point solvents such as dichloromethane, methyl acetate, tetrahydrofuran, acetone, and 1,3-dioxolane are preferable, and dichloromethane is particularly preferable, because the solvent can be easily removed by drying and the amount of residual solvent in the polyimide film can be reduced. preferable.
  • dichloromethane is particularly preferable, because the solvent can be easily removed by drying and the amount of residual solvent in the polyimide film can be reduced.
  • a polyimide showing high solubility in a low boiling point solvent such as dichloromethane can be obtained.
  • the solid content concentration of the polyimide solution may be appropriately set according to the molecular weight of the polyimide, the thickness of the film, the film forming environment, and the like.
  • the solid content concentration is preferably 5 to 30% by weight, more preferably 8 to 20% by weight.
  • the polyimide solution may contain a resin component or an additive other than polyimide.
  • the additive include an ultraviolet absorber, a cross-linking agent, a dye, a surfactant, a leveling agent, a plasticizer, fine particles and the like.
  • the content of the polyimide resin with respect to 100 parts by weight of the solid content of the polyimide solution (film-forming dope) is preferably 60 parts by weight or more, more preferably 70 parts by weight or more, and further preferably 80 parts by weight or more.
  • a method of applying the polyimide solution to the substrate a known method can be used, and for example, it can be applied by a bar coater or a comma coater.
  • a glass substrate, a metal substrate such as SUS, a metal drum, a metal belt, a plastic film, or the like can be used as the base material on which the polyimide solution is applied.
  • a material that does not dissolve in a film-forming dope solvent may be appropriately selected, and as the plastic material, polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate or the like is used.
  • the heating temperature is not particularly limited, but is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, from the viewpoint of suppressing coloring.
  • the heating temperature may be gradually increased.
  • the impression of the solvent may be given under reduced pressure. Since the above-mentioned polyimide resin is soluble in a low boiling point solvent such as dichloromethane, the residual solvent can be easily reduced even by heating at 200 ° C. or lower.
  • the residual solvent amount of the polyimide film (mass of the solvent contained in the film with respect to the mass of the film) is preferably 1.5% or less, more preferably 1.0% or less. When the amount of residual solvent is in this range, the mechanical strength of the polyimide film tends to be improved.
  • the thickness of the polyimide film is not particularly limited and may be appropriately set according to the application.
  • the thickness of the polyimide film is, for example, about 5 to 100 ⁇ m.
  • the thickness of the polyimide film is preferably 30 ⁇ m or more, more preferably 35 ⁇ m or more, still more preferably 40 ⁇ m or more.
  • the polyimide film of the present invention has excellent transparency even when the film thickness is as thick as 40 ⁇ m or more. From the viewpoint of maintaining excellent transparency, the thickness of the polyimide film is preferably 90 ⁇ m or less, more preferably 85 ⁇ m or less.
  • the yellowness (YI) of the polyimide film is preferably 3.0 or less, more preferably 2.5 or less. When the degree of yellowness is 3.0 or less, the film is not colored yellow and can be suitably used as a film for displays and the like.
  • the total light transmittance of the polyimide film is preferably 80% or more, more preferably 85% or more.
  • the light transmittance of the polyimide film at a wavelength of 400 nm is preferably 35% or more, more preferably 40% or more.
  • the tensile elastic modulus of the polyimide film is preferably 4.9 GPa or more, more preferably 5.0 GPa or more, and even more preferably 5.2 GPa or more.
  • the pencil hardness of the polyimide film is preferably HB or higher, more preferably F or higher, from the viewpoint of preventing contact with the roll during roll-to-roll transport and damage to the film due to contact between the films during winding.
  • the pencil hardness of the polyimide film is preferably H or more because scratch resistance against contact from the outside is required.
  • the polyimide film of the present invention has a low yellowness and high transparency, and is suitably used as a display material.
  • a polyimide film having high mechanical strength can be applied to a surface member such as a cover window of a display.
  • the polyimide film of the present invention may be provided with an antistatic layer, an easy-adhesion layer, a hard coat layer, an antireflection layer and the like on the surface.
  • TMHQ p-phenylene bistrimellitic dianhydride
  • TAHMBP bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 2,2', 3,3', 5,5'-hexa Methylbiphenyl-4,4'-diyl 6FDA: 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride
  • BPDA 3,3' , 4,4'-Biphenyltetracarboxylic dianhydride
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • 3,3'-DDS 3,3'-diaminodiphenylsulfone
  • 4,4′-DDS 4,4′-d
  • the polyimide resin was dissolved in dichloromethane (hereinafter referred to as "DCM") to obtain a polyimide solution having a solid content concentration of 10% by weight.
  • DCM dichloromethane
  • Using a bar coater apply the polyimide solution to a non-alkali glass plate and heat it in an air atmosphere for 60 minutes at 40 ° C, 30 minutes at 80 ° C, 30 minutes at 150 ° C, and 30 minutes at 170 ° C to remove the solvent. It was removed to obtain a polyimide film having the thickness shown in Table 1. Since the polyimide resin of Comparative Example 8 was not dissolved in DCM, a film was prepared using a polyimide solution in which the polyimide resin was dissolved in methyl ethyl ketone (MEK).
  • MEK methyl ethyl ketone
  • the yellowness (YI) was measured with a spectrocolorimeter "SC-P" manufactured by Suga Test Instruments Co., Ltd. using a sample having a size of 3 cm square.
  • Total light transmittance The measurement was performed by the method described in JIS K7361-1 using a haze meter "HZ-V3" manufactured by Suga Test Instruments.
  • Amount of residual solvent Using about 8.9 g of 1,3-dioxolane as a solvent, about 0.1 g of a polyimide film and about 1 g of diethylene glycol butyl methyl ether (DEGBME) as an internal standard substance were dissolved to prepare a sample for measurement. This solution was measured using a gas chromatograph device (GC, manufactured by Shimadzu Corporation), and the amount of residual solvent (DCM or MEK) contained in the polyimide film was determined from the GC peak area and the prepared concentration.
  • GC gas chromatograph device
  • composition of the polyimide resins of the above Examples and Comparative Examples (molar ratio of the amount of acid dianhydride and diamine charged in the polymerization of polyamic acid), the solubility in DCM, the solvent used for film formation, and the polyimide film.
  • the evaluation results of are shown in Table 1.
  • the polyimide shows DCM solubility
  • the polyimide film shows a tensile elastic modulus of 5 GPa or more, and it can be seen that both excellent mechanical strength and transparency can be achieved.
  • Comparative Example 1 in which the amount of CBDA was 10 mol% with respect to the total amount of acid dianhydride, the polyimide resin could not be isolated because the solvent solubility of the polyimide was low and the solution gelled during imidization.
  • Comparative Example 2 in which CBDA was not used, Comparative Example 3 in which the amount of TAHMBP was 35 mol%, and Comparative Example 4 in which the amount of TAHMBP was 25 mol%, gelation occurred during imidization as in Comparative Example 1.
  • Comparative Example 8 using a combination of CBDA and 6FDA as the acid dianhydride, gelation did not occur during imidization, but the isolated polyimide did not show DCM solubility.
  • the polyimide film of Comparative Example 8 in which a film was formed using MEK as a solvent showed excellent transparency, but had a tensile elastic modulus of 4.1 GPa, and its mechanical strength was inferior to that of Examples. Further, in Comparative Example 8, the residual solvent amount of MEK was 2.8%, which was larger than that of other examples using DCM.
  • Comparative Example 6 and Comparative Example 7 CBDA was not used as the acid dianhydride, but since the introduction ratio of TAHMBP and 6FDA was increased, a polyimide resin soluble in DCM was obtained. However, the polyimide films of Comparative Examples 6 and 7 had a tensile elastic modulus of less than 5 GPa, and the mechanical strength was insufficient.
  • fluoroalkyl-substituted benzidine as a diamine component, ester of biphenol having a substituent on the benzene ring and trimellitic acid dianhydride as an acid dianhydride, and acid dianhydride having a cyclobutane structure are predetermined. Since the polyimide contained in the ratio of is soluble in a low boiling solvent such as DCM, a film having a small amount of residual solvent can be easily produced, and the mechanical properties and transparency of the polyimide film can be compatible with each other. It turns out that there is.
  • the polyimide having a block structure has a higher elastic modulus than the polyimide having a random structure having the same composition. It can be seen that it shows. In particular, in Examples 1 and 8 in which a block containing only TFMB as a diamine component was formed, the tensile elastic modulus of the polyimide film tended to be improved.

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Abstract

La présente invention concerne une résine de polyimide qui présente une structure dérivée de dianhydride d'acide et une structure dérivée de diamine, qui contient de 40 à 100 % en moles d'une benzidine substituée par fluoroalkyle, en tant que diamine, par rapport à un total de 100 % en moles de la diamine, et qui contient, en tant que dianhydride d'acide, de 40 à 85 % en moles d'un dianhydride d'acide représenté par la formule générale (1) et de 15 à 60 % en moles d'un dianhydride d'acide ayant une structure de cyclobutane, par rapport à un total de 100 % en moles du dianhydride d'acide. Dans la formule générale (1), R1-R8 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle ayant de 1 à 20 atomes de carbone, ou un groupe alkyle perfluoré ayant de 1 à 20 atomes de carbone, et au moins un parmi R1-R4 et au moins un parmi R5-R8 représentent un groupe alkyle ayant de 1 à 20 atomes de carbone, ou un groupe alkyle perfluoré ayant de 1 à 20 atomes de carbone.
PCT/JP2020/021778 2019-06-04 2020-06-02 Résine de polyimide et son procédé de production, et film de polyimide et son procédé de production WO2020246466A1 (fr)

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CN115627000A (zh) * 2022-11-02 2023-01-20 天能新能源(湖州)有限公司 一种耐高温聚酰亚胺隔膜及其制备方法与其在制备锂离子电池中的应用

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CN115627000B (zh) * 2022-11-02 2023-11-10 天能新能源(湖州)有限公司 一种耐高温聚酰亚胺隔膜及其制备方法与其在制备锂离子电池中的应用

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