WO2023038321A1 - 폴리아믹산 조성물 및 이로부터 제조되는 폴리이미드 - Google Patents

폴리아믹산 조성물 및 이로부터 제조되는 폴리이미드 Download PDF

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WO2023038321A1
WO2023038321A1 PCT/KR2022/012449 KR2022012449W WO2023038321A1 WO 2023038321 A1 WO2023038321 A1 WO 2023038321A1 KR 2022012449 W KR2022012449 W KR 2022012449W WO 2023038321 A1 WO2023038321 A1 WO 2023038321A1
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Prior art keywords
polyamic acid
acid composition
dianhydride
bis
conductive polymer
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PCT/KR2022/012449
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English (en)
French (fr)
Korean (ko)
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황인환
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피아이첨단소재 주식회사
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Priority to CN202280061249.6A priority Critical patent/CN117916321A/zh
Publication of WO2023038321A1 publication Critical patent/WO2023038321A1/ko

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyamic acid composition and a polyimide prepared therefrom.
  • polyimide (PI) resin refers to a highly heat-resistant resin prepared by solution polymerization of aromatic dianhydride and aromatic diamine or aromatic diisocyanate to prepare a polyamic acid derivative, followed by imidization by curing. refers to
  • Polyimide is a polymer material with thermal stability based on a rigid aromatic main chain, and has mechanical properties such as excellent strength, chemical resistance, weather resistance and heat resistance based on the chemical stability of the imide ring.
  • polyimide is in the limelight as a high-functional polymer material applicable to a wide range of industries such as electronics, communication, and optics due to its excellent electrical properties such as insulating properties and low permittivity.
  • a method for imparting electrical conductivity to polyimide As a method for imparting electrical conductivity to polyimide, a method of dispersing a carbon-based conductive material in a polyimide precursor is known, but polyimide cured from a polyimide precursor in which a carbon-based conductive material is dispersed has low transmittance, such as in the display industry. It is not suitable for applications requiring transparency and has a disadvantage in that an excessive amount of conductive material is required.
  • An object of the present invention is to provide a polyamic acid composition and a polyimide film having high transparency and low surface resistance.
  • Polyimide (PI) resin is prepared by polymerization of aromatic dianhydride and aromatic diamine or aromatic diisocyanate to prepare a polyamic acid derivative, followed by imidization by curing.
  • Polyimide has excellent thermal stability based on a rigid aromatic backbone.
  • the transparency is so low that there is a limit to use in the electronic material field, especially in the display field requiring high transparency.
  • research has been conducted to impart electrical conductivity to polyimide and use it in the electronics industry, but it is more difficult to improve the transparency of polyimide to which a conductive material is added.
  • the polyamic acid composition according to the present invention includes a conjugated conductive polymer having excellent compatibility with a polymer having a dianhydride monomer and a diamine monomer as polymerized units, thereby producing a polyimide having high transmittance and excellent electrical conductivity.
  • the polyamic acid composition according to the present invention has an excellent action effect between the conjugated conductive polymer and the solvent, and the dispersibility of the conjugated conductive polymer is excellent, the polyimide prepared by curing the conjugated conductive polymer has a small amount of the conjugated conductive polymer. It has excellent electrical conductivity even though it contains
  • the polyamic acid composition according to the present invention maintains excellent thermal and mechanical properties unique to polyimide while having high transparency and electrical conductivity as described above.
  • the present invention relates to a polyamic acid composition.
  • the polyamic acid composition includes a polymer having a polymerization unit derived from a dianhydride monomer and a diamine monomer, and a conjugated conductive polymer.
  • the conjugated conductive polymer refers to a polymer having a structure in which multiple bonds are formed by valence electrons centered on one single bond.
  • the conjugated conductive polymer may be a polymer having a chemical structure in which double bonds and single bonds or triple bonds and single bonds are alternately connected.
  • conjugated conductive polymer examples include polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene, polyacetylene, and polyacetylene.
  • polythiophene poly(3,4-ethylenedioxythiophene) (PEDOT), poly(p-phenylene sulfide), polypyrrole, polycarbazole, polyindole, polyazepine or polyaniline.
  • the conjugated conductive polymer is an aromatic ring from the viewpoint of compatibility. or a hetero atom.
  • conjugated conductive polymers include polythiophene, poly(3,4-ethylenedioxythiophene) (PEDOT), poly(p-phenylene sulfide), and polypyrrole. , It includes at least one selected from the group consisting of polycarbazole, polyindole, polyazepine, and polyaniline.
  • the heteroatom of the conjugated conductive polymer is preferably nitrogen from the viewpoint of dispersibility and compatibility
  • the conjugated conductive polymer according to the present invention may be at least one selected from the group consisting of polypyrrole, polycarbazole, polyindole, polyazepine, and polyaniline.
  • a polypyrrole having a low molecular weight and containing a nitrogen atom in an aromatic ring is preferable.
  • the conjugated conductive polymer may have a dried cast film conductivity of 0.005 S/cm or more.
  • the conjugated conductive polymer may have a film conductivity of 0.006 S/cm or more, 0.007 S/cm or more, 0.008 S/cm or more, 0.009 S/cm or more, or 0.01 S/cm or more.
  • the electrical conductivity of the polyamic acid composition including the same may be improved.
  • the conjugated conductive polymer may be included in an amount of 0.01 to 1% by weight based on the total polyamic acid composition.
  • the content of the conjugated conductive polymer is 0.05 to 1% by weight, 0.05 to 0.9% by weight, 0.1 to 1% by weight, 0.1 to 0.7% by weight, 0.2 to 1% by weight, 0.2 to 0.9% by weight, 0.2 to 0.7% by weight. % by weight, 0.3 to 1%, 0.3 to 0.9%, 0.3 to 0.7%, 0.4 to 0.7% or 0.4 to 0.6%.
  • the polyamic acid composition according to the present invention may have excellent transparency and excellent electrical conductivity by including the conjugated conductive polymer in the above content.
  • the polyamic acid composition according to the present invention may have a surface resistance of 1.0 ⁇ 10 13 ⁇ / ⁇ or less as measured according to ASTM D257 after curing.
  • the polyamic acid composition according to the present invention may have an average light transmittance of 50% or more at a thickness of 10 ⁇ m at a wavelength of 380 to 780 nm after curing. Specific measurement methods and measurement conditions of various physical properties described in the present invention are described in detail in the experimental examples to be described later.
  • the polyamic acid composition according to the present invention may have an average light transmittance of 50% or more at a thickness of 10 ⁇ m at a wavelength of 380 to 780 nm after curing.
  • the light transmittance is 52% or more, 54% or more, 56% or more, 58% or more, 60% or more, 62% or more, 64% or more, 66% or more, 68% or more, 70% or more, 75% It may be 80% or more, 82% or more, 84% or more, or 85% or more, and the upper limit is not particularly limited, but may be 90% or less.
  • the light transmittance can be measured using a UV/Vis spectrophotometer.
  • the polyamic acid composition according to the present invention may have a surface resistance of 1.0 ⁇ 10 13 ⁇ / ⁇ or less measured according to ASTM D257.
  • the surface resistance may be 6.0 ⁇ 10 12 ⁇ / ⁇ or less, 2.0 ⁇ 10 12 ⁇ / ⁇ or less, 5.0 ⁇ 10 11 ⁇ / ⁇ or less, or 2.0 ⁇ 10 11 ⁇ / ⁇ or less, specifically, the above
  • the surface resistance is 1.0 ⁇ 10 11 to 1.0 ⁇ 10 13 ⁇ / ⁇ , 1.0 ⁇ 10 11 to 6.0 ⁇ 10 12 ⁇ / ⁇ , 1.0 ⁇ 10 11 to 2.0 ⁇ 10 12 ⁇ / ⁇ or 1.0 ⁇ 10 11 to 1.0 ⁇ 10 It may be 12 ⁇ / ⁇ .
  • the present invention can provide a polyamic acid composition having high transparency and excellent electrical conductivity by simultaneously satisfying the light transmittance and surface resistance as described above.
  • the dianhydride monomer that can be used for preparing the polyamic acid solution may be aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride may be pyromellitic dianhydride (or PMDA), 3,3 ',4,4'-biphenyltetracarboxylic dianhydride (or BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (or a-BPDA), oxydiphthalic Dianhydride (or ODPA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (or DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2 ,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenone
  • the dianhydride monomers may be used alone or in combination of two or more, if necessary, and examples include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracar boxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), 3,3',4,4'-benzophenonetetracar boxylic dianhydride (BTDA), oxydiphthalic dianhydride (ODPA), 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) and p-phenylenebis(trimellitate anhydride) (TAHQ).
  • PMDA pyromellitic dianhydride
  • s-BPDA 3,3',4,4'-biphenyltetracar boxylic dianhydride
  • a-BPDA 2,3,3',4'-biphen
  • the dianhydride monomer may include a dianhydride monomer having one benzene ring and a dianhydride monomer having two or more benzene rings. 20 to 60 mol% and 40 to 90 mol% of the dianhydride monomer having one benzene ring and the dianhydride monomer having two or more benzene rings, respectively; 25 to 55% by mole and 45 to 80% by mole; Or it may be included in a molar ratio of 35 to 53 mol% and 48 to 75 mol%.
  • the dianhydride monomer by including the dianhydride monomer, it is possible to realize a desired level of mechanical properties while having excellent adhesive strength.
  • diamine monomers that can be used in preparing the polyamic acid solution are aromatic diamines, and can be classified and exemplified as follows.
  • 1,4-diaminobenzene or paraphenylenediamine, PDA
  • 1,3-diaminobenzene 2,4-diaminotoluene
  • 2,6-diaminotoluene or 3,5-diaminobenzo diamines having a relatively rigid structure as diamines having one benzene nucleus in structure, such as acid acid (or DABA);
  • the diamine monomer according to the present invention is 1,4-diaminobenzene (PPD), 1,3-diaminobenzene (MPD), 2,4-diaminotoluene, 2,6-diaminotoluene, 4 ,4'-diaminodiphenyl ether (ODA), 4,4'-methylenediamine (MDA), 4,4-diaminobenzanilide (4,4-DABA), N,N-bis(4-amino Phenyl)benzene-1,4-dicarboxamide (BPTPA), 2,2-dimethylbenzidine (M-TOLIDINE), 2,2-bis(trifluoromethyl)benzidine (TFDB), 1,4-bisaminophenoxy Consisting of benzene (TPE-Q), bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP) and 2,2-bisaminophenoxyphenylhe
  • the polyamic acid composition according to the present invention includes a solvent, and the solvent may be an organic solvent.
  • Solvents compatible with the polyimide precursor include N,N-diethylacetamide (DEAC), N,N-dimethylpropionamide (DMPA), 3-methoxy-N,N-dimethylpropanamide (KJCMPA) , At least one selected from the group consisting of N-methyl-2pyrrolidone (NMP), gamma butyrolactone (GBL), and diglyme may be selected.
  • N,N-diethylacetamide (DEAC), N,N-dimethylpropionamide (DMPA) and N-methyl-2-pyrrolidone (NMP)
  • DEAC N,N-diethylacetamide
  • DMPA N,N-dimethylpropionamide
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • DEAC N,N-diethylacetamide
  • DMPA N,N-dimethylpropionamide
  • the molar ratio of methyl-2-pyrrolidone (NMP) and N,N-diethylacetamide (DEAC) or N,N-dimethylpropionamide (DMPA) with respect to the total solvent is 3:7 to 7:3
  • the molar ratio of methyl-2-pyrrolidone (NMP) to N,N-diethylacetamide (DEAC) or N,N-dimethylpropionamide (DMPA) is 6:4 to 4:6 or 4.5:5.5 to 5.5:4.5.
  • the solvent of the polyamic acid composition according to the present invention may have a boiling point of 150°C or higher.
  • the solvent of the polyamic acid composition may have a boiling point of 160°C or higher or 170°C or higher.
  • the lower limit of the boiling point of the solvent may be, for example, 155 ° C, 160 ° C, 165 ° C, 170 ° C, 175 ° C, 180 ° C, 185 ° C, 190 ° C, 195 ° C, 200 ° C or 201 ° C or higher
  • the upper limit may be, for example, 500°C, 450°C, 300°C, 280°C, 270°C, 250°C, 240°C, 230°C, 220°C, 210°C or 205°C or less.
  • the polyamic acid composition of the present invention may include a filler for the purpose of improving various properties of the film, such as sliding properties, thermal conductivity, conductivity, corona resistance, and loop hardness.
  • the filler added is not particularly limited, but examples thereof include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
  • the particle diameter of the filler is not particularly limited, and may be determined according to the film properties to be modified and the type of filler to be added.
  • the average particle diameter may be 0.05 to 20 ⁇ m, 0.1 to 10 ⁇ m, 0.1 to 5 ⁇ m, or 0.1 to 3 ⁇ m.
  • the average particle diameter may be an average particle diameter measured according to D50 particle size analysis unless otherwise specified. In the present invention, by adjusting the particle diameter range, it is possible to sufficiently maintain the modification effect without damaging the surface properties and not deteriorating the mechanical properties.
  • the present invention is not particularly limited to the addition amount of the filler, and it can be determined by the film properties to be modified or the particle size of the filler.
  • the added amount of the filler may be 0.01 to 10 parts by weight, 0.01 to 5 parts by weight, or 0.02 to 1 part by weight based on 100 parts by weight of the composition.
  • by adjusting the content the mechanical properties of the film may not be damaged while sufficiently maintaining the modifying effect of the filler.
  • the method of adding the filler is not particularly limited, and a known method in the same industry may be used.
  • the polyamic acid composition according to the present invention may have a solid content in the range of 5 to 30% by weight.
  • the solids content may be 7% by weight or more, 9% by weight or more, 10% by weight or more, 13% by weight or more, 15% by weight or more, or 17% by weight or more, and the upper limit is, for example, 30% by weight or less, 26% by weight or less % or less, 24% or less, 20% or less, or 19% or less.
  • the present invention controls the increase in viscosity while maintaining the physical properties after curing at a desired level by adjusting the solid content of the polyamic acid composition to be relatively high, and prevents the increase in manufacturing cost and process time required to remove a large amount of solvent during the curing process. can do.
  • the present invention provides a method for preparing a polyamic acid composition.
  • the method for preparing a polyamic acid composition according to the present invention includes polymerizing a dianhydride monomer and a diamine monomer.
  • a conventional polyimide precursor polymerization method such as solution polymerization may be used.
  • the method for preparing a polyamic acid composition according to the present invention includes mixing a diamine monomer with a solvent; mixing a conjugated conductive polymer with the mixture; and mixing a dianhydride monomer with the mixture.
  • the electrical conductivity and transparency of the polyamic acid composition prepared by improving the dispersibility of the conjugated conductive polymer and the polyimide cured therefrom can be improved. there is.
  • the conjugated conductive polymer may be included in an amount of 0.01 to 1% by weight based on the total composition.
  • the content of the conjugated conductive polymer is 0.05 to 1% by weight, 0.05 to 0.9% by weight, 0.1 to 1% by weight, 0.1 to 0.7% by weight, 0.2 to 1% by weight, 0.2 to 0.9% by weight, 0.2 to 0.7% by weight. % by weight, 0.3 to 1%, 0.3 to 0.9%, 0.3 to 0.7%, 0.4 to 0.7% or 0.4 to 0.6%.
  • the polyamic acid composition according to the present invention may have excellent transparency and excellent electrical conductivity by including the conjugated conductive polymer in the above content.
  • the polyamic acid composition according to the present invention may have a coefficient of thermal expansion (CTE) of 10 ppm/°C or less after curing.
  • CTE coefficient of thermal expansion
  • the upper limit of the CTE may be 9 ppm/°C, 8 ppm/°C, 7 ppm/°C, 6 ppm/°C, 5 ppm/°C or 4 ppm/°C or less
  • the lower limit may be, for example, 0.1 ppm /°C, 1 ppm/°C, 2.0 ppm/°C or 3.0 ppm/°C or higher.
  • the thermal expansion coefficient may be measured at 100 to 450 °C.
  • the CTE can use TA's thermomechanical analyzer Q400 model, and after manufacturing polyimide into a film, cutting it into a width of 2 mm and a length of 10 mm, applying a tension of 0.05 N in a nitrogen atmosphere, 10 ° C / After raising the temperature from room temperature to 500 ° C at a rate of min, the slope of the section from 100 ° C to 450 ° C can be measured while cooling again at a rate of 10 ° C / min.
  • the polyamic acid composition according to the present invention may have a glass transition temperature of 400° C. or more after curing, and for example, the lower limit of the glass transition temperature is 403° C. or more, 405° C. or more, 410° C. or more, or 420° C. °C or higher, 430 °C or higher, 440 °C or higher or 450 °C or higher.
  • the upper limit may be 600° C. or less.
  • the glass transition temperature may be measured at 10 °C/min using TMA for polyimide prepared by curing the polyamic acid composition.
  • the polyamic acid composition according to the present invention may have a thermal decomposition temperature of 500° C. or higher at 1% by weight.
  • the thermal decomposition temperature can be measured using TA's thermogravimetric analysis Q50 model.
  • the polyimide obtained by curing the polyamic acid is heated to 150° C. at a rate of 10° C./min under a nitrogen atmosphere and maintained at an isothermal temperature for 30 minutes to remove moisture. Thereafter, the temperature may be raised to 600° C. at a rate of 10° C./min to measure the temperature at which a weight loss of 1% occurs.
  • the lower limit of the thermal decomposition temperature may be, for example, 505 °C or higher, 510 °C or higher, 520 °C or higher, 530 °C or higher, 540 °C or higher, 550 °C or higher, 560 °C or higher, or 570 °C or higher.
  • the upper limit may be, for example, 800°C, 750°C, 700°C, 650°C or 630°C or less.
  • the polyamic acid composition according to the present invention may have a dielectric constant of 3.8 F/m or more at 120 Hz after curing.
  • the polyamic acid composition may have a dielectric constant of 3.9 F/m or more, 4.0 F/m or more, 4.1 F/m or more, 4.2 F/m or more, or 4.3 F/m or more at 120 Hz after curing, with an upper limit of 5.0 Can be less than /m.
  • a dielectric constant in the above range a sufficient antistatic effect can be provided when using a polyamic acid composition or a polyamic acid prepared therefrom in an electronic device or electronic industry.
  • the polyamic acid composition may have an elongation of 10% or more after curing, for example, 11% or more, 12% or more, 15% or more, 20% or more, or 25% or more.
  • the upper limit is not particularly limited, but may be 40% or less.
  • the elongation can be measured by the ASTM D-882 method using Instron 5564 UTM equipment after curing the polyamic acid composition into a polyimide film, cutting it into a width of 10 mm and a length of 40 mm.
  • the polyamic acid composition of the present invention may have an elastic modulus of 5.0 GPa or more after curing.
  • the lower limit of the elastic modulus may be, for example, 6.0 GPa or more, 7.0 GPa or more, 8.0 GPa or more, or 9.0 GPa or more.
  • the upper limit is not particularly limited, but may be 15 GPa or less.
  • the polyamic acid composition may have a tensile strength of 180 MPa or more after curing.
  • the lower limit of the tensile strength may be, for example, 190 MPa or more, 200 MPa or more, 300 MPa or more, 400 MPa or more, 410 MPa or more, 420 MPa or more or 440 MPa or more, and the upper limit may be, for example, 550 MPa or less or It may be 530 MPa or less.
  • the elastic modulus and tensile strength were measured by the ASTM D-882 method using Instron 5564 UTM equipment after curing the polyamic acid composition to prepare a polyimide film, cutting it into a width of 10 mm and a length of 40 mm, and Tensile strength can be measured. The cross head speed at this time can be measured under the condition of 50 mm/min.
  • the polyamic acid composition may be a composition having low viscosity.
  • the polyamic acid composition of the present invention has a viscosity of 10,000 cP or less, 5,000 cP or less, 4,000 cP or less, 3,500 cP or less, 3,300 cP or less, 3,200 cP or less, or 3,100 cP or less, measured under conditions of a temperature of 23 ° C and a shear rate of 1 s -1 .
  • the lower limit is not particularly limited, but may be 500 cP or more or 1,000 cP or more.
  • the viscosity may be measured using, for example, Haake's Rheostress 600, and may be measured under conditions of a shear rate of 1/s, a temperature of 23° C., and a plate gap of 1 mm.
  • the present invention can provide a precursor composition having excellent processability by adjusting the viscosity range.
  • the present invention provides a method for producing a polyimide, comprising forming a polyamic acid composition prepared according to the method for producing a polyamic acid composition on a support and drying to prepare a gel, and curing the gel.
  • the method for producing a polyimide of the present invention may include forming a film of the polyamic acid composition on a support, drying the film to prepare a gel, and curing the gel.
  • the polyamic acid composition formed on the support is dried at a temperature of 20 to 120 ° C. for 5 to 60 minutes to prepare a gel film, and the gel film is dried at 30 to 500 ° C. It may be performed through a process of raising the temperature at a rate of °C/min, heat-treating at 450 to 500 °C for 5 to 60 minutes, and cooling at a rate of 1 to 8 °C/min to 20 to 120 °C.
  • Curing the gel film may be performed at 30 to 500 °C.
  • the step of curing the gel film is 30 to 400 ° C, 30 to 300 ° C, 30 to 200 ° C, 30 to 100 ° C, 100 to 500 ° C, 100 to 300 ° C, 200 to 500 ° C, or 400 to 500 ° C. may be performed at °C.
  • the polyimide film may have a thickness of 5 to 20 ⁇ m.
  • the polyimide film may have a thickness of 5 to 18 ⁇ m, 6 to 16 ⁇ m, 7 to 14 ⁇ m, 8 to 12 ⁇ m, or 9 to 11 ⁇ m.
  • the support may be, for example, an inorganic substrate, and the inorganic substrate may include a glass substrate or a metal substrate, but it is preferable to use a glass substrate, and the glass substrate may be soda lime glass, borosilicate glass, or alkali-free glass. and the like may be used, but are not limited thereto.
  • the polyimide according to the present invention has excellent heat resistance, transparency, and electrical conductivity, it is widely used in high-tech core mechanical parts that require high heat resistance, such as electric and electronic, flat panel display, semiconductor, and solar cell industries, which are sensitive to static electricity problems. can be utilized Specifically, it can be usefully used for a high-K transistor, a polyimide substrate for oxide-TFT, or a polyimide substrate for LTPS-TFT.
  • the polyamic acid composition according to the present invention and the polyimide prepared therefrom have excellent electrical conductivity while having high transparency.
  • the polyamic acid composition according to the present invention and the polyimide prepared therefrom maintain excellent thermal properties and mechanical properties unique to polyimide while having high transparency and electrical conductivity as described above.
  • N,N-dimethylpropionamide (DMPA) was introduced as a solvent while nitrogen was injected into a 500 ml reactor equipped with a stirrer and a nitrogen injection discharge pipe.
  • a polyamic acid composition was prepared in the same manner as in Example 1, except for adjusting the monomer component and content ratio and the solvent component and content ratio.
  • a polyamic acid solution was prepared in the same manner as in Example 1, except that the components and contents of the conductive polymer were adjusted as shown in Table 1 below.
  • Example 1 100 100 polypyrrole 0.1 0 One 3100
  • Example 2 100 100 polypyrrole 0.3 0 One 3100
  • Example 3 100 100 polypyrrole 0.5 0 One 3100
  • Example 5 100 70 30 polypyrrole 0.3 0 One 3800
  • Example 6 100 70 30 polypyrrole 0.5 0 One 3800
  • Example 7 100 50 50 polypyrrole 0.5 0 One 4400
  • Example 8 100 polypyrrole 0.5 5 5 3300
  • Air bubbles were removed from the polyamic acid solutions prepared in Examples and Comparative Examples by high-speed rotation of 1,500 rpm or more. Then, the degassed polyamic acid solution was applied to the glass substrate using a spin coater. Thereafter, a gel film was prepared by drying at a temperature of 120 ° C. for 30 minutes under a nitrogen atmosphere, and the gel film was heated up to 450 ° C. at a rate of 2 ° C. / min. After heat treatment at 450 ° C. for 60 minutes, 30 ° C. It was cooled at a rate of 2° C./min to obtain a 10 ⁇ m polyimide film.
  • the polyimide film was peeled from the glass substrate by dipping in distilled water.
  • the physical properties of the prepared polyimide film were measured using the following method, and the results are shown in Tables 2 and 3 below.
  • Viscosity of the polyamic acid solutions prepared in Examples and Comparative Examples was measured using Haake's Rheostress 600 under conditions of a shear rate of 1/s, a temperature of 23° C., and a plate gap of 1 mm.
  • the thickness of the prepared polyimide film was measured using Anritsu's Electric Film thickness tester.
  • a Lambda 465 model was used as a UV-Vis Spectrophotometer from Perkin Elmer, and transmittance The transmittance at 470 nm was measured in the mode.
  • the permittivity at 120 Hz of the polyimide films prepared in Examples and Comparative Examples was measured using Keysight's SPDR measuring instrument.
  • Example 1 18 10 71 3.9 4.43 ⁇ 10 12
  • Example 2 18 10 70 3.9 1.43 ⁇ 10 12
  • Example 3 18 10 68 4.1 1.53 ⁇ 10 11
  • Example 4 18 10 66 4.2 1.13 ⁇ 10 11
  • Example 5 18 10 68 4.0 9.24 ⁇ 10 12
  • Example 6 18 10 67 4.1 5.13 ⁇ 10 12
  • Example 7 18 10 65 4.0 5.78 ⁇ 10 12
  • Example 8 18 10 70 4.1 1.42 ⁇ 10 11
  • Example 9 18 10 70 4.2 1.63 ⁇ 10 11 Comparative Example 1 18 10 56 4.2 1.89 ⁇ 10 11 Comparative Example 2 18 10 54 4.3 4.81 ⁇ 10 12 Comparative Example 3 18 10 55 3.6 8.02 ⁇ 10 13
  • Comparative Example 7 18 10 58 3.6 2.54 ⁇ 10 14
  • thermomechanical analyzer thermomechanical analyzer Q400 model was used, and after cutting the polyimide film into a width of 2 mm and a length of 10 mm, 500° C. After the temperature was raised to °C, the slope of the section from 100 °C to the Tg temperature was measured while cooling at a rate of 10 °C/min again.
  • the rapidly expanding point at 10 °C/min condition was measured as an on-set point using TMA.
  • thermogravimetric analysis Q50 model was used, and the polyimide film was heated up to 150 °C at a rate of 10 °C/min under a nitrogen atmosphere, and then maintained at an isothermal temperature for 30 minutes to remove moisture. Thereafter, the temperature was raised to 600 °C at a rate of 10 °C/min, and the temperature at which a weight loss of 1% occurred was measured.
  • the elongation can be measured by the ASTM D-882 method using Instron 5564 UTM equipment. there is.
  • Polyimide films prepared by curing the polyamic acid solutions of Examples and Comparative Examples were cut into 10 mm wide and 40 mm long, and then the elastic modulus and tensile strength were measured by the ASTM D-882 method using Instron's Instron5564 UTM equipment. can be measured The cross head speed at this time can be measured under the condition of 50 mm/min.
  • Example 1 4 470 572 30 503 9.1
  • Example 2 5 465 573 28 487 9.0
  • Example 3 5 468 568 28 462 8.6
  • Example 4 5 460 565 27 455 8.6
  • Example 6 460 565 22 420 9.4
  • Example 7 3 470 573 31 505 9.0
  • Example 8 5 470 573 31 505 9.0

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060127686A1 (en) * 2004-12-15 2006-06-15 Meloni Paul A Thermally conductive polyimide film composites having high thermal conductivity useful in an electronic device
KR20100124623A (ko) * 2009-05-19 2010-11-29 한국화학연구원 고유전 폴리이미드-폴리아닐린 복합체 및 이의 제조방법
US20150130098A1 (en) * 2013-11-13 2015-05-14 Industrial Technology Research Institute Polyamic acid, polyimide, and method for manufacturing graphite sheet
KR20160098832A (ko) * 2015-02-11 2016-08-19 코오롱인더스트리 주식회사 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름
KR20210055265A (ko) * 2019-11-07 2021-05-17 피아이첨단소재 주식회사 유전특성이 개선된 폴리이미드 필름 및 그 제조방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5789844B2 (ja) * 2011-11-30 2015-10-07 国立大学法人 千葉大学 ポリカルバゾール誘導体含有組成物及び該組成物からなる透明導電体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060127686A1 (en) * 2004-12-15 2006-06-15 Meloni Paul A Thermally conductive polyimide film composites having high thermal conductivity useful in an electronic device
KR20100124623A (ko) * 2009-05-19 2010-11-29 한국화학연구원 고유전 폴리이미드-폴리아닐린 복합체 및 이의 제조방법
US20150130098A1 (en) * 2013-11-13 2015-05-14 Industrial Technology Research Institute Polyamic acid, polyimide, and method for manufacturing graphite sheet
KR20160098832A (ko) * 2015-02-11 2016-08-19 코오롱인더스트리 주식회사 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름
KR20210055265A (ko) * 2019-11-07 2021-05-17 피아이첨단소재 주식회사 유전특성이 개선된 폴리이미드 필름 및 그 제조방법

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