WO2021189723A1 - 聚酰亚胺无色透明薄膜及其制备方法、光学pi膜 - Google Patents

聚酰亚胺无色透明薄膜及其制备方法、光学pi膜 Download PDF

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WO2021189723A1
WO2021189723A1 PCT/CN2020/101893 CN2020101893W WO2021189723A1 WO 2021189723 A1 WO2021189723 A1 WO 2021189723A1 CN 2020101893 W CN2020101893 W CN 2020101893W WO 2021189723 A1 WO2021189723 A1 WO 2021189723A1
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dianhydride
film
tetraacid
solution
colorless
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PCT/CN2020/101893
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English (en)
French (fr)
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曾彩萍
金鹰
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中天电子材料有限公司
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Priority to US16/929,366 priority Critical patent/US20210301132A1/en
Publication of WO2021189723A1 publication Critical patent/WO2021189723A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to the technical field of materials, in particular to a colorless and transparent polyimide film, a preparation method thereof, and an optical PI film.
  • Polyimide (PI) films are widely used in flexible printed circuits, flexible photoelectric displays, aerospace and other fields because of their high strength, high heat resistance, low dielectric constant and loss.
  • the adhesive layer is combined with the metal conductor copper foil to form a single-sided or double-sided copper clad laminate (FCCL), and then a single-sided or double-sided printed circuit is obtained through exposure, etching and other processes (FPC).
  • FCCL copper clad laminate
  • FPC etching and other processes
  • the single-sided or double-sided FPC is laminated with the adhesive film, and a high-density multilayer printed circuit can be obtained by heating and molding. Due to the charge interaction in the resin main chain structure and between the main chain structures, traditional aromatic polyimide films are generally yellow or yellowish brown.
  • Flexible photoelectric display substrates are mainly used to make transparent conductive electrodes (such as indium oxide ITO, etc.) and thin film transistor (TFT) circuits on the surface of a colorless and transparent polyimide film to control pixel switching.
  • transparent conductive electrodes such as indium oxide ITO, etc.
  • TFT thin film transistor
  • polysilicon, polysilicon, oxide, etc. which usually make the TFT circuit layer, have a relatively low coefficient of thermal expansion ( ⁇ 12ppm/°C), and the production process needs to undergo a high temperature impact of 230°C. If the coefficient of thermal expansion between the transparent polyimide film and the TFT is large, it will cause problems such as cracking of the device.
  • the technical solution provided by the present invention is: a colorless and transparent polyimide film, the film is mainly formed by a polycondensation reaction of a fluorine-containing aromatic diamine and one of tetraacid dianhydride and tetraacid dianhydride derivatives
  • Polyamic acid resin solution or polyamide ester resin solution obtained by adding a chemical imidization reagent to the polyamic acid resin solution or the polyamide ester resin solution to react and form a film
  • the tetraacid dianhydride is a fat
  • the tetraacid dianhydride derivative is an alicyclic diacid chloride diester solution generated by esterification and acid chlorination of alicyclic tetraacid dianhydride, A mixed solution of an aromatic diacid chloride diester solution produced by esterification and acid chlorination with aromatic tetraacid dianhydride
  • the light transmittance at the wavelength of 500nm is ⁇ 85%.
  • the film has the following characteristics:
  • the solid content of the polyamic acid resin solution or the polyamide ester resin solution is 15-30%.
  • the moles of the alicyclic tetraacid dianhydride account for 10-50% of the sum of the moles of the alicyclic tetraacid dianhydride and the aromatic tetraacid dianhydride.
  • aromatic tetracarboxylic dianhydride includes pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3 ',4'-Biphenyltetracarboxylic dianhydride ( ⁇ -BPDA), 3,3',4,4'-Diphenylsulfone tetracarboxylic dianhydride (s-DSDA), 2,3,3',4' -One or more of diphenylsulfone tetracarboxylic dianhydride ( ⁇ -DSDA).
  • PMDA pyromellitic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • ⁇ -BPDA 2,3,3 ',4'-Biphenyltetracarboxylic dianhydride
  • s-DSDA 3,3',4,4'
  • the alicyclic tetracarboxylic dianhydride includes 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMBD), 1,4,5,8-Dimethylene bridge-perhydronaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA), bicyclo[2,2,2]octane-2,3,5 ,6-Tetracarboxylic dianhydride (BTAH), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) One or more of them.
  • DMBD 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride
  • DNDA 1,4,5,8-Dimethylene bridge-
  • the fluorine-containing aromatic diamine mainly includes 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFDB), and 1,4-bis(2-trifluoromethyl) -4-aminophenoxy)benzene (6FAPB), 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene (6FMPB), 4,4'-bis(2-trifluoromethyl) Yl-4-aminophenoxy)biphenyl (6FBAB), wherein the moles of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl account for the The total number of moles of the fluorine-containing aromatic diamine is 50% to 90%.
  • TFDB 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl
  • 6FAPB 1,4-bis(2-trifluoromethyl) -4-aminophenoxy)benzene
  • 6FMPB 1,3-bis(2-trifluoromethyl-4
  • a polar aprotic solvent is added to the polycondensation reaction of the fluorine-containing aromatic diamine and the tetraacid dianhydride;
  • the polar aprotic solvent includes N-methylpyrrolidone (NMP), N, One or more of N'-dimethylacetamide (DMAC), N,N'-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).
  • the esterification reaction for obtaining the tetraacid dianhydride derivative also includes an organic solvent
  • the organic solvent includes N-methylpyrrolidone (NMP), N,N'-dimethylacetamide (DMAC), N,N'-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ⁇ -butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate , One or more of butyl acetate.
  • NMP N-methylpyrrolidone
  • DMAC N,N'-dimethylacetamide
  • DMF N,N'-dimethylformamide
  • DMSO dimethyl sulfoxide
  • ⁇ -butyrolactone ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate ,
  • the chemical imidization reagent includes an organic acid anhydride and an organic base
  • the organic acid anhydride includes one or more of acetic anhydride, propionic anhydride, butyric anhydride, phthalic anhydride, and maleic anhydride
  • the organic base includes pyridine , 2-methylpyridine, 3-methylpyridine, and isoquinoline.
  • the present invention also provides a method for preparing the colorless and transparent polyimide film, which includes the following steps:
  • tetraacid dianhydride or a tetraacid dianhydride derivative wherein the tetraacid dianhydride includes an alicyclic tetraacid dianhydride and an aromatic tetraacid dianhydride; the tetraacid dianhydride derivative is an alicyclic tetraacid dianhydride Acid dianhydride and aromatic tetraacid dianhydride are respectively esterified in an organic solvent and then acylated to produce a mixed solution of diacid chloride diester solutions;
  • the fluorine-containing aromatic diamine is added to the polar aprotic solvent to form a homogeneous solution, and then the tetraacid dianhydride is added in batches to form a polyamic acid resin solution through polycondensation reaction, or the fluorine-containing aromatic diamine is added to The polyamide ester resin solution is formed in the tetraacid dianhydride derivative through polycondensation reaction and purification;
  • the semi-cured self-supporting adhesive film is peeled from the surface of the support, and the surrounding is fixed or under the action of biaxial stretching, after high temperature treatment, the imidization reaction is completed; the colorless and transparent polyimide is obtained after cooling film.
  • the alicyclic tetraacid dianhydride and the aromatic tetraacid dianhydride are respectively dissolved with a lower aliphatic alcohol in an organic solvent, and heated to cause an esterification reaction to form an alicyclic diacid diester solution and Aromatic diacid diester solution; then, thionyl chloride is added to convert alicyclic diacid diester and aromatic diacid diester into alicyclic diacid chloride diester solution and aromatic diacid chloride through acylation reaction, respectively Di-ester solution: the tetra-acid dianhydride derivative is obtained by mixing the alicyclic diacid chloride diester solution and the aromatic diacid chloride diester solution.
  • the first resin solid is obtained by precipitating, filtering, and washing the solution after the polycondensation reaction of the fluorine-containing aromatic diamine and the tetraacid dianhydride derivative; and dissolving the resin solid in an organic solvent A homogeneous solution is formed, which is further purified by ion adsorption, and the second resin solid is obtained after precipitation and drying; the second resin solid is dissolved in an organic solvent to form the polyester resin solution.
  • the moles of the alicyclic tetraacid dianhydride account for 10-50% of the sum of the moles of the alicyclic tetraacid dianhydride and the aromatic tetraacid dianhydride.
  • aromatic tetracarboxylic dianhydride includes pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3 ',4'-Biphenyltetracarboxylic dianhydride ( ⁇ -BPDA), 3,3',4,4'-Diphenylsulfone tetracarboxylic dianhydride (s-DSDA), 2,3,3',4' -One or more of diphenylsulfone tetracarboxylic dianhydride ( ⁇ -DSDA).
  • PMDA pyromellitic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • ⁇ -BPDA 2,3,3 ',4'-Biphenyltetracarboxylic dianhydride
  • s-DSDA 3,3',4,4'
  • the alicyclic tetracarboxylic dianhydride includes 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMBD), 1,4,5,8-Dimethylene bridge-perhydronaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA), bicyclo[2,2,2]octane-2,3,5 ,6-Tetracarboxylic dianhydride (BTAH), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) One or more of them.
  • DMBD 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride
  • DNDA 1,4,5,8-Dimethylene bridge-
  • the fluorine-containing aromatic diamine mainly includes 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFDB), and 1,4-bis(2-trifluoromethyl) -4-aminophenoxy)benzene (6FAPB), 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene (6FMPB), 4,4'-bis(2-trifluoromethyl) Yl-4-aminophenoxy)biphenyl (6FBAB), wherein the moles of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl account for the The total number of moles of the fluorine-containing aromatic diamine is 50% to 90%.
  • TFDB 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl
  • 6FAPB 1,4-bis(2-trifluoromethyl) -4-aminophenoxy)benzene
  • 6FMPB 1,3-bis(2-trifluoromethyl-4
  • a polar aprotic solvent is added to the polycondensation reaction of the fluorine-containing aromatic diamine and the tetraacid dianhydride;
  • the polar aprotic solvent includes N-methylpyrrolidone, N,N'- One or more of dimethylacetamide, N,N'-dimethylformamide, and dimethylsulfoxide.
  • the esterification reaction for obtaining the tetraacid dianhydride derivative also includes an organic solvent, and the organic solvent includes N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-di One or more of methyl formamide, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, and butyl acetate.
  • the chemical imidization reagent includes an organic acid anhydride and an organic base
  • the organic acid anhydride includes one or more of acetic anhydride, propionic anhydride, butyric anhydride, phthalic anhydride, and maleic anhydride
  • the organic base includes pyridine , 2-methylpyridine, 3-methylpyridine, and isoquinoline.
  • the present invention provides an optical PI film, which includes a metal layer, an indium tin oxide transparent electrode, and the colorless transparent polyimide film.
  • the metal layer is deposited on the surface of the activation treatment by ion implantation or magnetron sputtering.
  • Said polyimide colorless transparent film is one side or both sides, said indium tin oxide transparent electrode is vacuum deposited on the surface of said metal layer away from said polyimide colorless transparent film.
  • optical PI film is applied to but not limited to a flexible transparent photoelectric display substrate, a flexible photoelectric display protective film or a flexible electronic packaging substrate.
  • the colorless and transparent polyimide film provided by the present invention not only has excellent light transmittance ( ⁇ 85%@500nm), but also has high modulus (tensile modulus ⁇ 3.8GPa) , Low thermal expansion coefficient ( ⁇ 30ppm/°C, 50-200°C) and other characteristics, which can meet the needs of flexible optoelectronic display devices.
  • the preparation method of the colorless and transparent polyimide film of the present invention includes the following steps:
  • Step S11 Prepare tetraacid dianhydride, wherein the tetraacid dianhydride includes alicyclic tetraacid dianhydride and aromatic tetraacid dianhydride.
  • the moles of the alicyclic tetraacid dianhydride account for 10-50% of the sum of the moles of the alicyclic tetraacid dianhydride and the aromatic tetraacid dianhydride.
  • the aromatic tetracarboxylic dianhydride includes pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4 '-Biphenyltetracarboxylic dianhydride ( ⁇ -BPDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (s-DSDA), 2,3,3',4'-diphenyl One or more of sulfone tetracarboxylic dianhydride ( ⁇ -DSDA).
  • PMDA pyromellitic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • ⁇ -BPDA 2,3,3',4 '-Biphenyltetracarboxylic dianhydride
  • s-DSDA 3,3',4,4'
  • the alicyclic tetracarboxylic dianhydride includes 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMBD), 1,4 ,5,8-Dimethylene bridge-perhydronaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA), bicyclo[2,2,2]octane-2,3,5,6- One of tetracarboxylic dianhydride (BTAH), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) Or multiple.
  • DMBD 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride
  • DNDA 1,4 ,5,8-Dimethylene
  • Step S13 adding the fluorine-containing aromatic diamine to the polar aprotic solvent to form a homogeneous solution, and then adding the tetraacid dianhydride in batches to form a polyamic acid resin solution through polycondensation reaction, the polyamic acid resin solution
  • the solid content is 15-30%. This is because when the solid content is less than 15%, the monomer reactivity will decrease, the molecular weight of the polymer product will be low, and the film will be damaged due to low strength; when the solid content is higher than 30%, the polymer product The apparent viscosity is high, but the intrinsic viscosity is low, and the film is broken due to poor toughness.
  • the fluorine-containing aromatic diamine mainly includes 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFDB), and 1,4-bis(2-trifluoromethyl- 4-aminophenoxy)benzene (6FAPB), 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene (6FMPB), 4,4'-bis(2-trifluoromethyl) -4-aminophenoxy) biphenyl (6FBAB) one or more, wherein the number of moles of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl accounts for the containing 50% to 90% of the total moles of fluoroaromatic diamine; when the moles of TFDB account for less than 50% of the total moles of fluorine-containing aromatic diamine, it will cause stretching die The amount decreases and the CTE value increases; when it is higher than 90%, the light transmittance will decrease.
  • TFDB 2,2'-bistrifluoromethyl-4
  • the polar aprotic solvent includes one or more of N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, and dimethylsulfoxide.
  • the solid content of the polyamic acid resin solution is preferably 18 to 26%. In other embodiments, the solid content of the polyamic acid resin solution is further preferably 20-23%.
  • Step S15 adding a chemical imine reagent to the polyamic acid resin solution, stirring uniformly, vacuum defoaming, coating on the surface of the support, and forming a semi-cured self-supporting adhesive film after heat treatment.
  • the chemical imidization reagent includes an organic acid anhydride and an organic base
  • the organic acid anhydride includes one or more of acetic anhydride, propionic anhydride, butyric anhydride, phthalic anhydride, and maleic anhydride
  • the organic base includes pyridine, One or more of 2-methylpyridine, 3-methylpyridine, and isoquinoline.
  • Step S17 Peel the semi-cured self-supporting adhesive film from the surface of the support, fix it around it or under the action of biaxial stretching, undergo high temperature treatment to complete the imidization reaction; obtain the polyimide after cooling Colorless transparent film.
  • the preparation method of the colorless and transparent polyimide film of the present invention includes the following steps:
  • Step S21 Prepare a tetraacid dianhydride derivative, wherein the tetraacid dianhydride derivative is formed by esterification of an alicyclic tetraacid dianhydride and an aromatic tetraacid dianhydride in an organic solvent and then an acylation reaction. A mixed solution of diacid chloride diester solutions.
  • the alicyclic tetraacid dianhydride and the aromatic tetraacid dianhydride are respectively dissolved with a lower aliphatic alcohol in an organic solvent, and heated to undergo an esterification reaction to form an alicyclic dianhydride, respectively.
  • the tetraacid dianhydride derivative is obtained by mixing the alicyclic diacid chloride diester solution and the aromatic diacid chloride diester solution.
  • the moles of the alicyclic tetraacid dianhydride account for 10-50% of the sum of the moles of the alicyclic tetraacid dianhydride and the aromatic tetraacid dianhydride.
  • the aromatic tetracarboxylic dianhydride includes pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4 '-Biphenyltetracarboxylic dianhydride ( ⁇ -BPDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (s-DSDA), 2,3,3',4'-diphenyl One or more of sulfone tetracarboxylic dianhydride ( ⁇ -DSDA).
  • PMDA pyromellitic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • ⁇ -BPDA 2,3,3',4 '-Biphenyltetracarboxylic dianhydride
  • s-DSDA 3,3',4,4'
  • the alicyclic tetracarboxylic dianhydride includes 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMBD), 1,4 ,5,8-Dimethylene bridge-perhydronaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA), bicyclo[2,2,2]octane-2,3,5,6- One of tetracarboxylic dianhydride (BTAH), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (HPMDA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) Or multiple.
  • DMBD 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride
  • DNDA 1,4 ,5,8-Dimethylene
  • the organic solvent includes N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl lactate, cyclic One or more of pentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, and butyl acetate.
  • the lower fatty alcohol may also be, but not limited to, methanol, ethanol, propanol, isopropanol, butanol, and the like.
  • Step S23 adding a fluorine-containing aromatic diamine to the tetraacid dianhydride derivative to form a polyester resin solution through polycondensation reaction and purification.
  • the solid content of the polyamide ester resin solution is 15-30%. This is because when the solid content is less than 15%, the monomer reactivity decreases, the molecular weight of the polymer product is low, and the film will be damaged due to low strength; the solid content is higher than At 30%, the apparent viscosity of the polymerization product is high, but the intrinsic viscosity is low, and the film is broken due to poor toughness.
  • the solid content of the polyester resin solution is preferably 18 to 26%.
  • the solid content of the polyester resin solution is further preferably 20-23%.
  • the fluorine-containing aromatic diamine mainly includes 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFDB), and 1,4-bis(2-trifluoromethyl- 4-aminophenoxy)benzene (6FAPB), 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene (6FMPB), 4,4'-bis(2-trifluoromethyl) -4-aminophenoxy) biphenyl (6FBAB) one or more, wherein the number of moles of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl accounts for the containing
  • the fluoroaromatic diamine has 50% to 90% of the total moles.
  • the tensile modulus When the molar number of TFDB accounts for less than 50% of the total molar number of the fluorinated aromatic diamine, the tensile modulus will decrease and the CTE value will increase; when it exceeds 90%, it will cause light transmission. The rate drops.
  • the purification is performed by precipitating, filtering, and washing the solution after the polycondensation reaction of the fluorine-containing aromatic diamine and the tetraacid dianhydride derivative to obtain the first resin solid; Dissolve in an organic solvent to form a homogeneous solution, further purify by ion adsorption, and obtain a second resin solid after precipitation and drying; and dissolve the second resin solid in an organic solvent to form the polyester resin solution.
  • Step S25 adding a chemical imine reagent to the polyamide ester resin solution, stirring uniformly, vacuum defoaming, coating on the surface of the support, and forming a semi-cured self-supporting adhesive film after heat treatment.
  • the chemical imidization reagent includes an organic acid anhydride and an organic base
  • the organic acid anhydride includes one or more of acetic anhydride, propionic anhydride, butyric anhydride, phthalic anhydride, and maleic anhydride
  • the organic base includes pyridine, One or more of 2-methylpyridine, 3-methylpyridine, and isoquinoline.
  • Step S27 Peel off the semi-cured self-supporting adhesive film from the surface of the support, fix it around it or under the action of biaxial stretching, undergo high temperature treatment to complete the imidization reaction; obtain the polyimide after cooling Colorless transparent film.
  • the colorless and transparent polyimide film formed by the above-mentioned first or second type of implementation has the following characteristics: tensile modulus ⁇ 3.8GPa; thermal expansion coefficient (50-200°C) ⁇ 30ppm/°C; light transmittance (500nm) ⁇ 85%. More specifically, the film has the following characteristics: tensile modulus: 3.8 to 8.5 GPa; thermal expansion coefficient (50-200° C.): 1 to 30 ppm/° C.; light transmittance (500 nm): 85 to 96%.
  • the above-mentioned colorless and transparent polyimide film can be applied to make an optical PI film.
  • the optical PI film includes a metal layer, an indium tin oxide transparent electrode, and the colorless transparent polyimide film.
  • the metal layer is deposited on the activated polyimide by ion implantation or magnetron sputtering.
  • the indium tin oxide transparent electrode is vacuum deposited on the surface of the metal layer away from the colorless transparent polyimide film.
  • the optical PI film is applied to, but not limited to, flexible transparent optoelectronic display substrates, flexible optoelectronic display protective films, or flexible electronic packaging substrates.
  • the present invention will describe the colorless and transparent polyimide film of the present invention, its preparation process and the properties of the final product in combination with specific examples.
  • Example 1 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 200ml DMF, 28.81g TFDB and 4.28g 6FAPB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous Phase solution: Cool the reaction flask to 0-10°C with an ice bath, and add 11.21g HPMDA and 14.71g s-BPDA solid powder to the above homogeneous solution under stirring. After the solids are completely dissolved, continue to stir and react for 10 hours to obtain a viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA viscous homogeneous polyamic acid
  • Example 2 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 14.71g s-BPDA and 9.20g absolute ethanol, 15.82g pyridine and 129g N-methylpyrrolidone (NMP ), stirring at room temperature for 6h, to generate the corresponding aromatic diethyl diacid. At the same time, add 11.21g HPMDA, 9.20g absolute ethanol, 1.60g pyridine and 16g N-methylpyrrolidone (NMP) into a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, and stir at room temperature. 6h, the corresponding aromatic diethyl diacid is generated. The above two products were reacted with 23.79g SOCl 2 at 0-10°C for 2h and at room temperature for 4h to generate the corresponding aromatic diacid chloride diethyl ester.
  • PAE solid resin 20.0g dissolve it in 80.0g ⁇ -butyrolactone to form a homogeneous resin solution with a solid content of 20wt.%, cool it to 0-10°C, add 20g acetic anhydride and Pyridine mixture, mix well, filter, and vacuum degas.
  • Example 3 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 200ml DMAc, 22.41g TFDB and 12.85g 6FAPB were added, and the solids were dissolved under stirring and nitrogen protection to form a homogeneous Phase solution; Cool the reaction flask to 0-10°C with an ice bath, add 11.21g HPMDA and 14.71g s-BPDA solid powder to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h , To obtain a viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA viscous homogeneous polyamic acid
  • Example 4 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, add 200ml DMF, 16.01g TFDB and 21.41g 6FAPB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous Phase solution: Cool the reaction flask to 0-10°C with an ice bath, add 2.24g HPMDA and 19.63g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain Viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA Viscous homogeneous polyamic acid
  • Example 5 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 200ml NMP22.41g TFDB and 12.85g 6FAPB, all the solids are dissolved under stirring and nitrogen protection to form a homogeneous phase Solution; Cool the reaction flask to 0-10°C with an ice bath, add 6.72g HPMDA and 15.27g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain a viscous solution. Thick homogeneous polyamic acid (PAA) resin solution.
  • PAA polyamic acid
  • Example 6 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, add 200ml DMF, 22.41g TFDB and 12.85g 6FAPB, all the solids are dissolved under stirring and nitrogen protection to form a homogeneous phase Solution; Cool the reaction flask to 0-10°C with an ice bath, add 5.88g CBDA and 15.27g PMDA solid powder to the above homogeneous solution in batches under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain a viscous solution. Thick homogeneous polyamic acid (PAA) resin solution.
  • PAA polyamic acid
  • Example 7 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, add 200ml DMF, 28.81g TFDB and 4.28g 6FAPB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous Phase solution; Cool the reaction flask to 0-10°C with an ice bath, add 5.88g CBDA and 15.27g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain Viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA Viscous homogeneous polyamic acid
  • Example 8 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, add 200ml DMF, 28.81g TFDB and 4.28g 6FAPB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous Phase solution; Cool the reaction flask to 0-10°C with an ice bath, add 1.96g CBDA and 19.63g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain Viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA Viscous homogeneous polyamic acid
  • Example 9 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, add 200ml DMF, 22.41g TFDB and 12.85g 6FAPB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous phase.
  • Solution Cool the reaction flask to 0-10°C with an ice bath, add 5.88g CBDA and 22.59g BTDA solid powder to the above homogeneous solution in batches under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain a viscous solution. Thick homogeneous polyamic acid (PAA) resin solution.
  • PAA polyamic acid
  • Example 10 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 200ml DMF, 22.41g TFDB and 15.13g 6FBAB were added, and all the solids were dissolved under stirring and nitrogen protection.
  • Phase solution Cool the reaction flask to 0-10°C with an ice bath, and add 4.53g DNDA, 2.94g CBDA and 20.60g s-BPDA solid powder to the above homogeneous solution under stirring. After the solids are completely dissolved, continue to stir and react for 10 hours to obtain a viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA viscous homogeneous polyamic acid
  • Example 11 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, add 200ml NMP, 22.41g TFDB and 15.13g 6FBAB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous Phase solution: Cool the reaction flask to 0-10°C with an ice bath, and add 7.50g BTAH and 22.60g s-BPDA solid powder to the above homogeneous solution under stirring. After the solid was completely dissolved, the reaction was continued for 10 hours to obtain a viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA viscous homogeneous polyamic acid
  • Comparative Example 1 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 200ml NMP, 30.41g TFDB and 2.14g 6FAPB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous Phase solution; Cool the reaction flask to 0-10°C with an ice bath, add 11.21g HPMDA and 10.91g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain Viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA Viscous homogeneous polyamic acid
  • Comparative Example 2 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 200ml NMP, 1.60g TFDB and 40.68g 6FAPB, all the solids are dissolved under stirring and nitrogen protection to form a homogeneous phase Solution; Cool the reaction flask to 0-10°C with an ice bath, add 11.21g HPMDA and 10.91g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain a viscous solution. Thick homogeneous polyamic acid (PAA) resin solution.
  • PAA polyamic acid
  • Comparative Example 3 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 200ml NMP, 16.01g TFDB and 21.41g 6FAPB. Under stirring and nitrogen protection, all the solids are dissolved to form a homogeneous Phase solution; Cool the reaction flask to 0-10°C with an ice bath, add 21.29g HPMDA and 1.09g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain Viscous homogeneous polyamic acid (PAA) resin solution.
  • PAA Viscous homogeneous polyamic acid
  • Comparative Example 4 In a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 200ml NMP, 16.01g TFDB and 21.41g 6FAPB, all the solids are dissolved under stirring and nitrogen protection to form a homogeneous phase Solution: Cool the reaction flask to 0-10°C with an ice bath, add 1.12g HPMDA and 20.72g PMDA solid powder in batches to the above homogeneous solution under stirring; after the solid is completely dissolved, continue to stir and react for 10h to obtain a viscous solution. Thick homogeneous polyamic acid (PAA) resin solution.
  • PAA polyamic acid
  • the polyimide colorless transparent film disclosed in the present invention not only has excellent transparency, its light transmittance at 500nm is ⁇ 85%, but also has a high modulus (tensile modulus ⁇ 3.5GPa) and low CTE ( ⁇ 35ppm/°C, 50-200°C) and other characteristics, with excellent comprehensive performance.
  • the polyimide film prepared by the comparative example either has a higher modulus, but has a higher CTE and lower light transmittance (Comparative Examples 1 and 2); or has a high light transmittance, but a higher CTE, and The amount is lower (Comparative Examples 2 and 3).
  • the molar number of TFDB accounts for less than 50% of the total molar number of fluorinated aromatic diamine, it will cause a decrease in tensile modulus and an increase in CTE value; when it is higher than 90%, it will cause light transmission The rate drops.
  • the ratio of the moles of alicyclic tetraacid dianhydride to the total moles of the tetraacid dianhydride is less than 10%, the light transmittance will decrease significantly; when it is higher than 50%, the tensile modulus will decrease, The CTE value rises.
  • the fluorine-containing aromatic diamine may also be a mixture of TFDB and 6FMPB, or a mixture of TFDB and 6FAPB, 6FBAB, and 6FMPB.
  • the alicyclic tetracarboxylic dianhydride may also be DMBD, or a mixture of HPMDA, CBDA, DNDA, BTAH, and DMBD.
  • the aromatic tetraacid dianhydride can also be ⁇ -BPDA, ⁇ -DSDA or s-DSDA, or PMDA, s-BPDA, ⁇ -BPDA, ⁇ -DSDA, s-DSDA mixture.
  • the polar aprotic solvent or organic solvent is not limited to the situations listed in the foregoing embodiments, and will not be repeated here.
  • the colorless and transparent polyimide film of the present invention not only has excellent transparency, its light transmittance at 500nm is ⁇ 85%, but also has high modulus (tensile modulus ⁇ 3.8GPa) and low CTE ( ⁇ 30ppm/°C, 50-200°C) and other characteristics, with excellent comprehensive performance, can meet the needs of flexible optoelectronic display devices.

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Abstract

本发明提供一种聚酰亚胺无色透明薄膜及其制备方法、光学PI膜。所述聚酰亚胺无色透明薄膜不但具有优良的透光性(≥85％@500nm)，同时具有高模量(拉伸模量≥3.8GPa)、低热膨胀系数(≤30ppm/℃，50-200℃)等特点，可满足柔性光电显示器件的使用需求。

Description

聚酰亚胺无色透明薄膜及其制备方法、光学PI膜 技术领域
本发明涉及材料技术领域，特别是指一种聚酰亚胺无色透明薄膜及其制备方法、光学PI膜。
背景技术
聚酰亚胺(PI)薄膜由于具有高强韧、高耐热、低介电常数及损耗等特点，广泛应用于挠性印制电路、柔性光电显示、航天航空等领域。在聚酰亚胺薄膜的单面或双面通过粘结层与金属导体铜箔复合形成单面或双面覆铜板(FCCL)，然后通过曝光、蚀刻等工艺得到单面或双面印制电路(FPC)。将单面或双面FPC与粘结膜叠合，通过加热模压可得到高密度多层印制电路。由于树脂主链结构中及主链结构间的电荷相互作用，传统芳香族聚酰亚胺薄膜一般都呈黄色或黄褐色。近年来，柔性光电显示器也对透明性聚酰亚胺薄膜提出了迫切的使用需求。柔性光电显示基板主要是在聚酰亚胺无色透明薄膜表面制作透明导电电极(如氧化铟ITO等)和薄膜晶体管(TFT)线路，用于控制像素开关。由于通常制作TFT线路层的多晶硅、多硅、氧化物等具有较低的热膨胀系数(<12ppm/℃)，而且制作工艺需要经过230℃的高温冲击。如果透明性聚酰亚胺薄膜与TFT的热膨胀系数相差较大，则会引起器件的开裂等问题。
为了适应柔性光电显示基板的使用需求，人们通过在树脂主链结 构中引入大体积的侧链、引入含氟基团、引入柔性链段等，以破坏树脂的电荷相互作用，实现聚酰亚胺薄膜的无色透明化。但是，现有报道的无色透明聚酰亚胺薄膜虽然具有优良的透光性，但普遍存在模量低、断裂伸长率低、热膨胀系数高等缺点，严重制约着这类材料在柔性光电显示器的广泛使用。
发明内容
鉴于以上内容，有必要提供一种改进的聚酰亚胺无色透明薄膜及其制备方法、光学PI膜。
本发明提供的技术方案为：一种聚酰亚胺无色透明薄膜，所述薄膜主要由含氟芳香族二胺与四酸二酐、四酸二酐衍生物中的一者通过缩聚反应形成聚酰胺酸树脂溶液或聚酰胺酯树脂溶液，所述聚酰胺酸树脂溶液或所述聚酰胺酯树脂溶液中加入化学亚胺化试剂反应、成膜处理后得到；所述四酸二酐为脂环族四酸二酐和芳香族四酸二酐的混合物；所述四酸二酐衍生物为脂环族四酸二酐经酯化、酰氯化反应生成的脂环族二酰氯二酯溶液，与芳香族四酸二酐经酯化、酰氯化反应生成的芳香族二酰氯二酯溶液的混合溶液；该薄膜具备以下特征：
拉伸模量≥3.8GPa；
50～200℃下的热膨胀系数≤30ppm/℃；
在波长500nm处的透光率≥85％。
进一步的，所述薄膜具备以下特征：
拉伸模量：3.8～8.5GPa；
50～200℃下的热膨胀系数：1～30ppm/℃；
在波长500nm处的透光率：85～96％。
进一步的，所述聚酰胺酸树脂溶液或所述聚酰胺酯树脂溶液的固含量为15～30％。
进一步的，所述脂环族四酸二酐的克分子数占所述脂环族四酸二酐和所述芳香族四酸二酐的克分子数之和的10～50％。
进一步的，所述芳香族四酸二酐包括均苯四甲酸二酐(PMDA)、3,3',4,4'-联苯四羧酸二酐(s-BPDA)、2,3,3',4'-联苯四羧酸二酐(α-BPDA)、3,3',4,4'-二苯砜四甲酸二酐(s-DSDA)、2,3,3',4'-二苯砜四甲酸二酐(α-DSDA)中一种或多种。
进一步的，所述脂环族四酸二酐包括1,8-二甲基双环[2,2,2]辛-7-烯-2,3,5,6-四甲酸二酐(DMBD)，1,4,5,8-二亚甲基桥-全氢萘-2,3,6,7-四甲酸二酐(DNDA)、双环[2,2,2]辛烷-2,3,5,6-四甲酸二酐(BTAH)，环己烷-1,2,4,5-四甲酸二酐(HPMDA)、环丁烷-1,2,3,4-四甲酸二酐(CBDA)中一种或多种。
进一步的，所述含氟芳香族二胺主要包括2,2’-双三氟甲基-4,4’-二氨基联苯(TFDB)，与1,4-双(2-三氟甲基-4-氨基苯氧基)苯(6FAPB)、1,3-双(2-三氟甲基-4-氨基苯氧基)苯(6FMPB)，4,4’-双(2-三氟甲基-4-氨基苯氧基)联苯(6FBAB)中的一种或多种，其中2,2’-双三氟甲基-4,4’-二氨基联苯的克分子数占所述含氟芳香族二胺的克分子数总量的50％～90％。
进一步的，所述含氟芳香族二胺与所述四酸二酐的缩聚反应中还添加有极性非质子溶剂；所述极性非质子溶剂包括N-甲基吡咯烷酮(NMP)、N,N’-二甲基乙酰胺(DMAC)、N,N’-二甲基甲酰胺(DMF)、二 甲基亚砜(DMSO)中一种或多种。
进一步的，得到所述四酸二酐衍生物的酯化反应中还包括有机溶剂，所述有机溶剂包括N-甲基吡咯烷酮(NMP)、N,N’-二甲基乙酰胺(DMAC)、N,N’-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、γ-丁内酯、乳酸乙酯、环戊酮、环己酮、甲基乙基酮、乙酸乙酯、乙酸丁酯中的一种或多种。
进一步的，所述化学亚胺化试剂包括有机酸酐和有机碱，所述有机酸酐包括乙酸酐、丙酸酐、丁酸酐、苯酸酐、马来酸酐中一种或多种；所述有机碱包括吡啶、2-甲基吡啶、3-甲基吡啶、异喹啉中一种或多种。
本发明还提供一种所述的聚酰亚胺无色透明薄膜的制备方法，包括以下步骤：
准备四酸二酐或四酸二酐衍生物，其中，所述四酸二酐包括脂环族四酸二酐和芳香族四酸二酐；所述四酸二酐衍生物为脂环族四酸二酐和芳香族四酸二酐分别在有机溶剂中酯化后再酰氯化反应生成的二酰氯二酯溶液的混合溶液；
将含氟芳香族二胺加入到极性非质子溶剂中形成均相溶液，然后分批加入所述四酸二酐通过缩聚反应形成聚酰胺酸树脂溶液，或者将含氟芳香族二胺加入到所述四酸二酐衍生物中通过缩聚反应、提纯形成聚酰胺酯树脂溶液；
在所述聚酰胺酸树脂溶液或所述聚酰胺酯树脂溶液中加入化学亚胺试剂，搅拌均匀、真空脱泡后，涂敷在支撑物表面上，加热处理后形成半固化自支撑胶膜；
将所述半固化自支撑胶膜从支撑物表面上剥离，将其四周固定或在双向拉伸作用下,经高温处理，完成亚胺化反应；降温后得到所述聚酰亚胺无色透明薄膜。
进一步的，将所述脂环族四酸二酐和所述芳香族四酸二酐分别与低级脂肪醇溶解于有机溶剂中，加热发生酯化反应，分别形成脂环族二酸二酯溶液和芳香族二酸二酯溶液；然后，加入氯化亚砜通过酰氯化反应将脂环族二酸二酯和芳香族二酸二酯分别转化成脂环族二酰氯二酯溶液和芳香族二酰氯二酯溶液；将脂环族二酰氯二酯溶液和芳香族二酰氯二酯溶液混合后得到所述四酸二酐衍生物。
进一步的，所述提纯通过将所述含氟芳香族二胺和所述四酸二酐衍生物缩聚反应后的溶液沉淀析出、过滤、洗涤得到第一树脂固体；将树脂固体溶于有机溶剂中形成均相溶液，通过离子吸附进一步纯化，析出、干燥后得到第二树脂固体；将第二树脂固体溶解于有机溶剂中形成所述聚酰胺酯树脂溶液。
进一步的，所述脂环族四酸二酐的克分子数占所述脂环族四酸二酐和所述芳香族四酸二酐的克分子数之和的10～50％。
进一步的，所述芳香族四酸二酐包括均苯四甲酸二酐(PMDA)、3,3',4,4'-联苯四羧酸二酐(s-BPDA)、2,3,3',4'-联苯四羧酸二酐(α-BPDA)、3,3',4,4'-二苯砜四甲酸二酐(s-DSDA)、2,3,3',4'-二苯砜四甲酸二酐(α-DSDA)中一种或多种。
进一步的，所述脂环族四酸二酐包括1,8-二甲基双环[2,2,2]辛-7-烯-2,3,5,6-四甲酸二酐(DMBD)，1,4,5,8-二亚甲基桥-全氢萘-2,3,6,7-四甲酸二酐(DNDA)、双环[2,2,2]辛烷-2,3,5,6-四甲酸二酐(BTAH)，环 己烷-1,2,4,5-四甲酸二酐(HPMDA)、环丁烷-1,2,3,4-四甲酸二酐(CBDA)中一种或多种。
进一步的，所述含氟芳香族二胺主要包括2,2’-双三氟甲基-4,4’-二氨基联苯(TFDB)，与1,4-双(2-三氟甲基-4-氨基苯氧基)苯(6FAPB)、1,3-双(2-三氟甲基-4-氨基苯氧基)苯(6FMPB)，4,4’-双(2-三氟甲基-4-氨基苯氧基)联苯(6FBAB)中的一种或多种，其中2,2’-双三氟甲基-4,4’-二氨基联苯的克分子数占所述含氟芳香族二胺的克分子数总量的50％～90％。
进一步的，所述含氟芳香族二胺与所述四酸二酐的缩聚反应中还添加有极性非质子溶剂；所述极性非质子溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜中一种或多种。
进一步的，得到所述四酸二酐衍生物的酯化反应中还包括有机溶剂，所述有机溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜、γ-丁内酯、乳酸乙酯、环戊酮、环己酮、甲基乙基酮、乙酸乙酯、乙酸丁酯中的一种或多种。
进一步的，所述化学亚胺化试剂包括有机酸酐和有机碱，所述有机酸酐包括乙酸酐、丙酸酐、丁酸酐、苯酸酐、马来酸酐中一种或多种；所述有机碱包括吡啶、2-甲基吡啶、3-甲基吡啶、异喹啉中一种或多种。
本发明提供一种光学PI膜，包括金属层、铟锡氧化物透明电极和所述的聚酰亚胺无色透明薄膜，所述金属层通过离子注入或磁控溅射沉积在活化处理的所述聚酰亚胺无色透明薄膜的单面或双面，所述铟锡氧化物透明电极真空沉积在所述金属层背离所述聚酰亚胺无色 透明薄膜的表面上。
进一步的，所述光学PI膜应用于但不限于柔性透明光电显示基板、柔性光电显示保护膜或柔性电子封装基板。
与现有技术相比，本发明提供的一种聚酰亚胺无色透明薄膜不但具有优良的透光性(≥85％@500nm)，同时具有高模量(拉伸模量≥3.8GPa)、低热膨胀系数(≤30ppm/℃，50-200℃)等特点，可满足柔性光电显示器件的使用需求。
具体实施方式
为了能够更清楚地理解本发明实施例的上述目的、特征和优点，下面结合具体实施方式对本发明进行详细描述。需要说明的是，在不冲突的情况下，本申请的实施方式中的特征可以相互组合。
在下面的描述中阐述了很多具体细节以便于充分理解本发明实施例，所描述的实施方式仅是本发明一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本发明实施例保护的范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明实施例的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本发明实施例。
在第一类实施方式中，本发明中聚酰亚胺无色透明薄膜的制备方法，包括以下步骤：
步骤S11：准备四酸二酐，其中，所述四酸二酐包括脂环族四酸二酐和芳香族四酸二酐。其中，所述脂环族四酸二酐的克分子数占所述脂环族四酸二酐和所述芳香族四酸二酐的克分子数之和的10～50％。所述芳香族四酸二酐包括均苯四甲酸二酐(PMDA)、3,3',4,4'-联苯四羧酸二酐(s-BPDA)、2,3,3',4'-联苯四羧酸二酐(α-BPDA)、3,3',4,4'-二苯砜四甲酸二酐(s-DSDA)、2,3,3',4'-二苯砜四甲酸二酐(α-DSDA)中一种或多种。所述脂环族四酸二酐包括1,8-二甲基双环[2,2,2]辛-7-烯-2,3,5,6-四甲酸二酐(DMBD)，1,4,5,8-二亚甲基桥-全氢萘-2,3,6,7-四甲酸二酐(DNDA)、双环[2,2,2]辛烷-2,3,5,6-四甲酸二酐(BTAH)，环己烷-1,2,4,5-四甲酸二酐(HPMDA)、环丁烷-1,2,3,4-四甲酸二酐(CBDA)中一种或多种。脂环族四酸二酐的克分子数占四酸二酐克分子数总量的比例低于10％时，透光率明显下降；高于50％时，会导致拉伸模量下降、CTE值(coefficient of thermal expansion，热膨胀系数)升高。
步骤S13：将含氟芳香族二胺加入到极性非质子溶剂中形成均相溶液，然后分批加入所述四酸二酐通过缩聚反应形成聚酰胺酸树脂溶液，所述聚酰胺酸树脂溶液的固含量为15～30％，这是因为固含量低于15％时，单体反应活性下降，聚合产物分子量低，薄膜会因强度低而破损；固含量高于30％时，聚合产物表观粘度高，但特性粘度低，薄膜因韧性差而破损。其中，所述含氟芳香族二胺主要包括2,2’-双三氟甲基-4,4’-二氨基联苯(TFDB)，与1,4-双(2-三氟甲基-4-氨基苯氧基)苯(6FAPB)、1,3-双(2-三氟甲基-4-氨基苯氧基)苯(6FMPB)，4,4’-双(2-三氟甲基-4-氨基苯氧基)联苯(6FBAB)中的一种或多种，其中 2,2’-双三氟甲基-4,4’-二氨基联苯的克分子数占所述含氟芳香族二胺的克分子数总量的50％～90％；TFDB的克分子数在含氟芳香族二胺的克分子数总量的占比低于50％时，会导致拉伸模量降低、CTE值升高；高于90％时，会导致透光率下降。所述极性非质子溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜中一种或多种。在一些实施例中，所述聚酰胺酸树脂溶液的固含量优选为18～26％。在另一些实施例中，所述聚酰胺酸树脂溶液的固含量进一步优选为20～23％。
步骤S15：在所述聚酰胺酸树脂溶液中加入化学亚胺试剂，搅拌均匀、真空脱泡后，涂敷在支撑物表面上，加热处理后形成半固化自支撑胶膜。其中，所述化学亚胺化试剂包括有机酸酐和有机碱，所述有机酸酐包括乙酸酐、丙酸酐、丁酸酐、苯酸酐、马来酸酐中一种或多种；所述有机碱包括吡啶、2-甲基吡啶、3-甲基吡啶、异喹啉中一种或多种。
步骤S17：将所述半固化自支撑胶膜从支撑物表面上剥离，将其四周固定或在双向拉伸作用下,经高温处理，完成亚胺化反应；降温后得到所述聚酰亚胺无色透明薄膜。
在第二类实施方式中，本发明的聚酰亚胺无色透明薄膜的制备方法，包括以下步骤：
步骤S21：准备四酸二酐衍生物，其中，所述四酸二酐衍生物为脂环族四酸二酐和芳香族四酸二酐分别在有机溶剂中酯化后再酰氯化反应生成的二酰氯二酯溶液的混合溶液。
在具体实施方式中，将所述脂环族四酸二酐和所述芳香族四酸二酐分别与低级脂肪醇溶解于有机溶剂中，加热发生酯化反应，分别形成脂环族二酸二酯溶液和芳香族二酸二酯溶液；然后，加入氯化亚砜通过酰氯化反应将脂环族二酸二酯和芳香族二酸二酯分别转化成脂环族二酰氯二酯溶液和芳香族二酰氯二酯溶液；将脂环族二酰氯二酯溶液和芳香族二酰氯二酯溶液混合后得到所述四酸二酐衍生物。其中，所述脂环族四酸二酐的克分子数占所述脂环族四酸二酐和所述芳香族四酸二酐的克分子数之和的10～50％。所述芳香族四酸二酐包括均苯四甲酸二酐(PMDA)、3,3',4,4'-联苯四羧酸二酐(s-BPDA)、2,3,3',4'-联苯四羧酸二酐(α-BPDA)、3,3',4,4'-二苯砜四甲酸二酐(s-DSDA)、2,3,3',4'-二苯砜四甲酸二酐(α-DSDA)中一种或多种。所述脂环族四酸二酐包括1,8-二甲基双环[2,2,2]辛-7-烯-2,3,5,6-四甲酸二酐(DMBD)，1,4,5,8-二亚甲基桥-全氢萘-2,3,6,7-四甲酸二酐(DNDA)、双环[2,2,2]辛烷-2,3,5,6-四甲酸二酐(BTAH)，环己烷-1,2,4,5-四甲酸二酐(HPMDA)、环丁烷-1,2,3,4-四甲酸二酐(CBDA)中一种或多种。脂环族四酸二酐的克分子数比占四酸二酐的克分子数总量的比例低于10％时，透光率明显下降；高于50％时，会导致拉伸模量下降、CTE值升高。所述有机溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜、γ-丁内酯、乳酸乙酯、环戊酮、环己酮、甲基乙基酮、乙酸乙酯、乙酸丁酯中的一种或多种。在一些实施方式中，所述低级脂肪醇还可以是但不限于甲醇、乙醇、丙醇、异丙醇、丁醇等。
步骤S23：将含氟芳香族二胺加入到所述四酸二酐衍生物中通过 缩聚反应、提纯形成聚酰胺酯树脂溶液。所述聚酰胺酯树脂溶液的固含量为15～30％，这是因为固含量低于15％时，单体反应活性下降，聚合产物分子量低，薄膜会因强度低而破损；固含量高于30％时，聚合产物表观粘度高，但特性粘度低，薄膜因韧性差而破损。在一些实施例中，所述聚酰胺酯树脂溶液的固含量优选为18～26％。在另一些实施例中，所述聚酰胺酯树脂溶液的固含量进一步优选为20～23％。其中，所述含氟芳香族二胺主要包括2,2’-双三氟甲基-4,4’-二氨基联苯(TFDB)，与1,4-双(2-三氟甲基-4-氨基苯氧基)苯(6FAPB)、1,3-双(2-三氟甲基-4-氨基苯氧基)苯(6FMPB)，4,4’-双(2-三氟甲基-4-氨基苯氧基)联苯(6FBAB)中的一种或多种，其中2,2’-双三氟甲基-4,4’-二氨基联苯的克分子数占所述含氟芳香族二胺的克分子数总量的50％～90％。TFDB的克分子数在含氟芳香族二胺的克分子数总量的占比低于50％时，会导致拉伸模量降低、CTE值升高；高于90％时，会导致透光率下降。
在具体实施方式中，所述提纯通过将所述含氟芳香族二胺和所述四酸二酐衍生物缩聚反应后的溶液沉淀析出、过滤、洗涤得到第一树脂固体；将第一树脂固体溶于有机溶剂中形成均相溶液，通过离子吸附进一步纯化，析出、干燥后得到第二树脂固体；将第二树脂固体溶解于有机溶剂中形成所述聚酰胺酯树脂溶液。
步骤S25：在所述聚酰胺酯树脂溶液中加入化学亚胺试剂，搅拌均匀、真空脱泡后，涂敷在支撑物表面上，加热处理后形成半固化自支撑胶膜。其中，所述化学亚胺化试剂包括有机酸酐和有机碱，所述有机酸酐包括乙酸酐、丙酸酐、丁酸酐、苯酸酐、马来酸酐中一种或 多种；所述有机碱包括吡啶、2-甲基吡啶、3-甲基吡啶、异喹啉中一种或多种。
步骤S27：将所述半固化自支撑胶膜从支撑物表面上剥离，将其四周固定或在双向拉伸作用下,经高温处理，完成亚胺化反应；降温后得到所述聚酰亚胺无色透明薄膜。
采用上述第一类或第二类实施方式形成的聚酰亚胺无色透明薄膜，具备以下特征：拉伸模量≥3.8GPa；热膨胀系数(50-200℃)≤30ppm/℃；透光率(500nm)≥85％。更具体地，所述薄膜具备以下特征：拉伸模量：3.8～8.5GPa；热膨胀系数(50-200℃)：1～30ppm/℃；透光率(500nm)：85～96％。
上述聚酰亚胺无色透明薄膜可应用制成一种光学PI膜。该光学PI膜包括金属层、铟锡氧化物透明电极和所述的聚酰亚胺无色透明薄膜，所述金属层通过离子注入或磁控溅射沉积在活化处理的所述聚酰亚胺无色透明薄膜的单面或双面，所述铟锡氧化物透明电极真空沉积在所述金属层背离所述聚酰亚胺无色透明薄膜的表面上。所述光学PI膜应用于但不限于柔性透明光电显示基板、柔性光电显示保护膜或柔性电子封装基板等。
下面本发明结合具体实施例对本发明的聚酰亚胺无色透明薄膜及其制备过程和最终产品性能进行说明。
实施例1:在一个装有机械搅拌器、温度计和氮气保护装置的 500ml三口圆底烧瓶中，加入200ml DMF，28.81g TFDB和4.28g 6FAPB，在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入11.21g HPMDA和14.71g s-BPDA固体粉末。待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，真空脱泡；将树脂溶液涂敷在不锈钢支撑物表面上，形成具有一定厚度的树脂胶膜；在烘道内或烘箱内逐步加热至80-120℃处理一定时间后，将形成的半固化胶膜从支撑物表面剥离；将半固化胶膜通过针板固定后，施加以双向拉伸张力,然后在最高温度不高于400℃的烘道内进行高温处理，冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为86.5％，热膨胀系数(CTE,50-200℃)为26.1ppm/℃,拉伸模量为6.8GPa。
实施例2：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入14.71g s-BPDA和9.20g无水乙醇、15.82g吡啶和129g N-甲基吡咯烷酮(NMP)，室温搅拌6h，生成相应的芳香族二酸二乙酯。同时，在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入11.21g HPMDA和9.20g无水乙醇、1.60g吡啶和16g N-甲基吡咯烷酮(NMP)，室温搅拌6h，生成相应的芳香族二酸二乙酯。将上述两种产物与23.79g SOCl 2在0-10℃反应2h，室温反应4h，生成相应的芳香族二酰氯二乙酯。
在一个装有机械搅拌器、温度计和氮气保护装置的1L三口圆底 烧瓶中，加入28.81g TFDB、4.28g 6FAPB和158g NMP，搅拌使其溶解形成均相透明溶液；采用冰浴将反应液温度冷却至10℃以下，将上述制备的芳香族二酰氯二乙酯溶液滴加进TFDB和6FAPB的NMP溶液中，滴加时间0.5h；在室温下反应10h后，将反应液倒入5L去离子水中，析出固体、过滤、真空干燥，得到初级聚酰胺酯树脂。将其再溶解于四氢呋喃中形成溶液，通过阴离子和阳离子树脂吸附，除去残余金属或非金属离子，得到高纯度聚酰亚胺前躯体-聚酰胺酯(PAE)树脂。
称取适量的PAE固体树脂20.0g,将其溶解于80.0gγ-丁内酯中形成固体含量为20wt.％的均相树脂溶液，冷却至0-10℃，在机械搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，真空脱泡。将其均匀涂覆于玻璃板表面，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上,置于烘箱中进行220℃/5min+400℃/1min的高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率86.5％，热膨胀系数(CTE,50-200℃)为26.1ppm/℃,拉伸模量为6.8GPa。
实施例3:在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml DMAc,22.41g TFDB和12.85g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入11.21g HPMDA和14.71g s-BPDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g马来酸酐与异喹啉混合物，混合均匀，过滤、真空脱泡；将树脂溶液均匀涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上,置于烘箱中进行220℃/5min.+400℃/1min的高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为91.2％，热膨胀系数(CTE,50-200℃)为29.0ppm/℃,拉伸模量为5.0GPa。
实施例4：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml DMF,16.01g TFDB和21.41g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入2.24g HPMDA和19.63g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入40g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min.+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为88.6％,热膨胀系数(CTE,50-200℃)为11.9ppm/℃,拉伸模量6.5GPa。
实施例5:在一个装有机械搅拌器、温度计和氮气保护装置的 500ml三口圆底烧瓶中，加入200ml NMP22.41g TFDB和12.85g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入6.72g HPMDA和15.27g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入40g乙酸酐与吡啶混合物，混合均匀，过滤、真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为90.5％，热膨胀系数(CTE,50-200℃)为14.8ppm/℃,拉伸模量为5.2GPa。
实施例6：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml DMF,22.41gTFDB和12.85g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入5.88g CBDA和15.27g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四 周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为87.9％，热膨胀系数(CTE,50-200℃)为17.8ppm/℃,拉伸模量为6.4GPa。
实施例7：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml DMF,28.81g TFDB和4.28g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入5.88g CBDA和15.27g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为87.0％，热膨胀系数(CTE,50-200℃)为8.0ppm/℃,拉伸模量为7.4GPa。
实施例8：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml DMF,28.81g TFDB和4.28g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入1.96g CBDA和19.63g PMDA固体粉末；待固体完全溶解后，继续搅 拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为86.2％，热膨胀系数(CTE,50-200℃)为4.0ppm/℃,拉伸模量为8.2GPa。
实施例9：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml DMF,22.41gTFDB和12.85g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入5.88g CBDA和22.59g BTDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为85.0％，热膨胀系数(CTE,50-200℃)为30.0ppm/℃,拉伸模量为3.9GPa。
实施例10:在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml DMF,22.41g TFDB和15.13g 6FBAB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入4.53g DNDA、2.94gCBDA和20.60g s-BPDA固体粉末。待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为89.5％，热膨胀系数(CTE,50-200℃)为18.6ppm/℃,拉伸模量为5.4GPa。
实施例11：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml NMP,22.41g TFDB和15.13g 6FBAB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入7.50g BTAH和22.60g s-BPDA固体粉末。待固体完全溶解后，继续搅拌反应10h,得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，真空脱泡；将树 脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为93.5％，热膨胀系数(CTE,50-200℃)为22.0ppm/℃,拉伸模量为5.4GPa。
对比例1：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml NMP,30.41g TFDB和2.14g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入11.21g HPMDA和10.91g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为83.0％，热膨胀系数(CTE,50-200℃)为38.5ppm/℃,拉伸模量为5.3GPa。
对比例2:在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml NMP,1.60gTFDB和40.68g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反 应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入11.21g HPMDA和10.91g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为91.8％，热膨胀系数(CTE,50-200℃)为48.1ppm/℃,拉伸模量为2.8GPa。
对比例3：在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml NMP,16.01g TFDB和21.41g 6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入21.29g HPMDA和1.09g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25 μm)，其500nm处的透光率为90.5％，热膨胀系数(CTE,50-200℃)为52.0ppm/℃,拉伸模量为2.4GPa。
对比例4:在一个装有机械搅拌器、温度计和氮气保护装置的500ml三口圆底烧瓶中，加入200ml NMP,16.01g TFDB和21.41g6FAPB,在搅拌和氮气保护下使固体全部溶解，形成均相溶液；将反应烧瓶用冰浴冷却至0-10℃，在搅拌下向上述均相溶液中分批加入1.12g HPMDA和20.72g PMDA固体粉末；待固体完全溶解后，继续搅拌反应10h，得到粘稠的均相聚酰胺酸(PAA)树脂溶液。
取100g上述PAA树脂溶液，放入200ml玻璃烧瓶中，在搅拌下加入20g乙酸酐与吡啶混合物，混合均匀，过滤，抽真空脱泡；将树脂溶液涂敷在玻璃板表面上，加热处理(60℃/1h+120℃/10min.)后,将形成的半固化胶膜从玻璃板表面剥离；然后，将半固化胶膜的四周固定在不锈钢框架上或在双向拉伸条件下,于220℃/5min+400℃/1min条件下高温处理；冷却后得到聚酰亚胺无色透明薄膜(25μm)，其500nm处的透光率为82.7％，热膨胀系数(CTE,50-200℃)为36.1ppm/℃,拉伸模量为3.8GPa。
从实施例表可看出，本发明公开的聚酰亚胺无色透明薄膜不但具有优良的透明性，其在500nm处的透光率≥85％，而且具有高模量(拉伸模量≥3.5GPa)和低CTE(≤35ppm/℃，50-200℃)等特点，具有优良的综合性能。而对比例所制备聚酰亚胺薄膜或者具有较高的模量，但CTE较高，透光率较低(对比例1和2)；或者具有高的透光率，但CTE较高，模量较低(对比例2和3)。TFDB的克分子数在含氟芳香族二胺的克分子数总量的占比低于50％时，会导致拉伸模量降低、CTE 值升高；高于90％时，会导致透光率下降。脂环族四酸二酐的克分子数占四酸二酐的克分子数总量的比例低于10％时，透光率明显下降；高于50％时，会导致拉伸模量下降、CTE值升高。需要说明的是，在本发明设定范围内调控TFDB或/和脂环族四酸二酐的克分子数占比，最终产品的性能会发生变化，且能够在确保透明度的前提下，实现最终产品的低热膨胀和高模量特性设计，产品的设计范围宽广。
实施例表
Figure PCTCN2020101893-appb-000001
在本发明的其他实施例中，含氟芳香族二胺还可以是TFDB与6FMPB的混合物，或者TFDB与6FAPB、6FBAB、6FMPB中多种的混合物。在其他实施例中，脂环族四酸二酐还可以是DMBD，或者是HPMDA、CBDA、DNDA、BTAH、DMBD中多种的混合物。在 其他实施例中，芳香族四酸二酐还可以是α-BPDA、α-DSDA或s-DSDA，或者是PMDA、s-BPDA、α-BPDA、α-DSDA、s-DSDA中多种的混合物。同样，所述极性非质子溶剂或有机溶剂等也不限定为上述实施例中列举的情形，在此不再赘述。
综上，本发明的聚酰亚胺无色透明薄膜不但具有优良的透明性，其在500nm处的透光率≥85％，而且具有高模量(拉伸模量≥3.8GPa)和低CTE(≤30ppm/℃，50-200℃)等特点，具有优良的综合性能，可满足柔性光电显示器件的使用需求。
以上实施方式仅用以说明本发明实施例的技术方案而非限制，尽管参照以上较佳实施方式对本发明实施例进行了详细说明，本领域的普通技术人员应当理解，可以对本发明实施例的技术方案进行修改或等同替换都不应脱离本发明实施例的技术方案的精神和范围。

Claims (15)

  1. 一种聚酰亚胺无色透明薄膜，其特征在于，所述薄膜主要由含氟芳香族二胺与四酸二酐、四酸二酐衍生物中的一者通过缩聚反应形成聚酰胺酸树脂溶液或聚酰胺酯树脂溶液，所述聚酰胺酸树脂溶液或所述聚酰胺酯树脂溶液中加入化学亚胺化试剂反应、成膜处理后得到；所述四酸二酐为脂环族四酸二酐和芳香族四酸二酐的混合物；所述四酸二酐衍生物为脂环族四酸二酐经酯化、酰氯化反应生成的脂环族二酰氯二酯溶液，与芳香族四酸二酐经酯化、酰氯化反应生成的芳香族二酰氯二酯溶液的混合溶液；该薄膜具备以下特征：
    拉伸模量≥3.8GPa；
    50～200℃下的热膨胀系数≤30ppm/℃；
    在波长500nm处的透光率≥85％。
  2. 根据权利要求1所述的聚酰亚胺无色透明薄膜，其特征在于：所述薄膜具备以下特征：
    拉伸模量：3.8～8.5GPa；
    50～200℃下的热膨胀系数：1～30ppm/℃；
    在波长500nm处的透光率：85～96％。
  3. 根据权利要求2所述的聚酰亚胺无色透明薄膜，其特征在于：所述聚酰胺酸树脂溶液或所述聚酰胺酯树脂溶液的固含量为15～30％。
  4. 根据权利要求3所述的聚酰亚胺无色透明薄膜，其特征在于：所述脂环族四酸二酐的克分子数占所述脂环族四酸二酐和所述芳香族四酸二酐的克分子数之和的10～50％。
  5. 根据权利要求3所述的聚酰亚胺无色透明薄膜，其特征在于：所述芳香族四酸二酐包括均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、2,3,3',4'-联苯四羧酸二酐、3,3',4,4'-二苯砜四甲酸二酐、2,3,3',4'-二苯砜四甲酸二酐中一种或多种。
  6. 根据权利要求3所述的聚酰亚胺无色透明薄膜，其特征在于：所述脂环族四酸二酐包括1,8-二甲基双环[2,2,2]辛-7-烯-2,3,5,6-四甲酸二酐，1,4,5,8-二亚甲基桥-全氢萘-2,3,6,7-四甲酸二酐、双环[2,2,2]辛烷-2,3,5,6-四甲酸二酐，环己烷-1,2,4,5-四甲酸二酐、环丁烷-1,2,3,4-四甲酸二酐中一种或多种。
  7. 根据权利要求3所述的聚酰亚胺无色透明薄膜，其特征在于：所述含氟芳香族二胺主要包括2,2’-双三氟甲基-4,4’-二氨基联苯，与1,4-双(2-三氟甲基-4-氨基苯氧基)苯、1,3-双(2-三氟甲基-4-氨基苯氧基)苯，4,4’-双(2-三氟甲基-4-氨基苯氧基)联苯中的一种或多种，其中2,2’-双三氟甲基-4,4’-二氨基联苯的克分子数占所述含氟芳香族二胺的克分子数总量的50％～90％。
  8. 根据权利要求3所述的聚酰亚胺无色透明薄膜，其特征在于：所述含氟芳香族二胺与所述四酸二酐的缩聚反应中还添加有极性非质子溶剂；所述极性非质子溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜中一种或多种。
  9. 根据权利要求3所述的聚酰亚胺无色透明薄膜，其特征在于：得到所述四酸二酐衍生物的酯化反应中还包括有机溶剂，所述有机溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜、γ-丁内酯、乳酸乙酯、环戊酮、环己酮、甲基乙基酮、 乙酸乙酯、乙酸丁酯中的一种或多种。
  10. 根据权利要求3所述的聚酰亚胺无色透明薄膜，其特征在于：所述化学亚胺化试剂包括有机酸酐和有机碱，所述有机酸酐包括乙酸酐、丙酸酐、丁酸酐、苯酸酐、马来酸酐中一种或多种；所述有机碱包括吡啶、2-甲基吡啶、3-甲基吡啶、异喹啉中一种或多种。
  11. 一种根据权利要求1-10中任一项所述的聚酰亚胺无色透明薄膜的制备方法，其特征在于，包括以下步骤：
    准备四酸二酐或四酸二酐衍生物，其中，所述四酸二酐包括脂环族四酸二酐和芳香族四酸二酐；所述四酸二酐衍生物为脂环族四酸二酐和芳香族四酸二酐分别在有机溶剂中酯化后再酰氯化反应生成的二酰氯二酯溶液的混合溶液；
    将含氟芳香族二胺加入到极性非质子溶剂中形成均相溶液，然后分批加入所述四酸二酐通过缩聚反应形成聚酰胺酸树脂溶液，或者将含氟芳香族二胺加入到所述四酸二酐衍生物中通过缩聚反应、提纯形成聚酰胺酯树脂溶液；
    在所述聚酰胺酸树脂溶液或所述聚酰胺酯树脂溶液中加入化学亚胺试剂，搅拌均匀、真空脱泡后，涂敷在支撑物表面上，加热处理后形成半固化自支撑胶膜；
    将所述半固化自支撑胶膜从支撑物表面上剥离，将其四周固定或在双向拉伸作用下,经高温处理，完成亚胺化反应；降温后得到所述聚酰亚胺无色透明薄膜。
  12. 根据权利要求11所述的聚酰亚胺无色透明薄膜的制备方法，其特征在于：将所述脂环族四酸二酐和所述芳香族四酸二酐分别与低 级脂肪醇溶解于有机溶剂中，加热发生酯化反应，分别形成脂环族二酸二酯溶液和芳香族二酸二酯溶液；然后，加入氯化亚砜通过酰氯化反应将脂环族二酸二酯和芳香族二酸二酯分别转化成脂环族二酰氯二酯溶液和芳香族二酰氯二酯溶液；将脂环族二酰氯二酯溶液和芳香族二酰氯二酯溶液混合后得到所述四酸二酐衍生物。
  13. 根据权利要求11所述的聚酰亚胺无色透明薄膜的制备方法，其特征在于：所述提纯通过将所述含氟芳香族二胺和所述四酸二酐衍生物缩聚反应后的溶液沉淀析出、过滤、洗涤得到第一树脂固体；将第一树脂固体溶于有机溶剂中形成均相溶液，通过离子吸附进一步纯化，析出、干燥后得到第二树脂固体；将第二树脂固体溶解于有机溶剂中形成所述聚酰胺酯树脂溶液。
  14. 一种光学PI膜，其特征在于：包括金属层、铟锡氧化物透明电极和如权利要求1-10中任一项所述的聚酰亚胺无色透明薄膜，所述金属层通过离子注入或磁控溅射沉积在活化处理的所述聚酰亚胺无色透明薄膜的单面或双面，所述铟锡氧化物透明电极真空沉积在所述金属层背离所述聚酰亚胺无色透明薄膜的表面上。
  15. 根据权利要求14所述的光学PI膜，其特征在于：所述光学PI膜应用于但不限于柔性透明光电显示基板、柔性光电显示保护膜或柔性电子封装基板。
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