US20190233590A1 - Polyamide-imide film and preparation method thereof - Google Patents

Polyamide-imide film and preparation method thereof Download PDF

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US20190233590A1
US20190233590A1 US16/262,472 US201916262472A US2019233590A1 US 20190233590 A1 US20190233590 A1 US 20190233590A1 US 201916262472 A US201916262472 A US 201916262472A US 2019233590 A1 US2019233590 A1 US 2019233590A1
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polyamide
substituted
imide film
unsubstituted
film
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Dawoo JEONG
Sunhwan KIM
Dae Seong OH
Jin Woo Lee
Dong Jin Lim
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SKC Co Ltd
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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
    • C08G73/14—Polyamide-imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/38—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
    • 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
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • B29K2079/085—Thermoplastic polyimides, e.g. polyesterimides, PEI, i.e. polyetherimides, or polyamideimides; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • 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

  • Embodiments relate to a polyamide-imide film that is excellent in mechanical properties and optical properties and that especially secures excellent tensile toughness and elastic restoring force, and a process for preparing the same.
  • PAI polyamide-imide
  • Polyamide-imide is used in various fields.
  • polyamide-imide is made in the form of a powder and used as a coating for a metal or a magnetic wire. It is mixed with other additives depending on the application thereof.
  • polyamide-imide is used together with a fluoropolymer as a painter for decoration and corrosion prevention. It also plays a role of bonding a fluoropolymer to a metal substrate.
  • polyamide-imide is used to coat kitchenware, used as a membrane for gas separation by virtue of its heat resistance and chemical resistance, and used in natural gas wells for filtration of such contaminants as carbon dioxide, hydrogen sulfide, and impurities.
  • polyamide-imide has been developed in the form of a film, which is less expensive and has excellent optical, mechanical, and thermal characteristics.
  • An embodiment aims to provide a polyamide-imide film that is excellent in mechanical properties and optical properties and that especially secures excellent tensile toughness and elastic restoring force.
  • another embodiment aims to provide a process for preparing a polyamide-imide film that secures excellent tensile toughness and elastic restoring force.
  • the polyamide-imide film comprises a polyamide-imide polymer formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound, wherein the area value up to the yield point derived by the 0.2% off-set method on a stress-strain curve of the polyamide-imide film as measured using a universal testing machine (UTM) is 80 to 150 J/m 2 .
  • UPM universal testing machine
  • the process for preparing a polyamide-imide film comprises simultaneously or sequentially mixing and reacting a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent in a polymerization apparatus to prepare a polymer solution; transferring the polymer solution to a tank; casting the polymer solution in the tank and then drying it to prepare a gel-sheet; thermally treating the gel-sheet, while it is moved on a belt, to prepare a cured film; and winding the cured film using a winder, wherein the ratio of the moving speed of the gel-sheet on the belt at the time of thermal treatment to the moving speed of the cured film at the time of winding is 1:0.95 to 1:1.40.
  • the polyamide-imide film according to the embodiments is excellent in mechanical properties and optical properties and is especially capable of securing excellent tensile toughness and elastic restoring force.
  • the process for preparing a polyamide-imide film according to the embodiments is capable of providing a polyamide-imide film that secures excellent tensile toughness and elastic restoring force.
  • FIG. 1 shows a stress-strain curve of the polyamide-imide film according to Example 1.
  • FIG. 2 shows a stress-strain curve of the polyamide-imide film according to Example 2.
  • FIG. 3 shows a stress-strain curve of the polyamide-imide film according to Example 3.
  • FIG. 4 shows a stress-strain curve of the polyamide-imide film according to Comparative Example 1.
  • FIG. 5 shows a stress-strain curve of the polyamide-imide film according to Comparative Example 2.
  • FIG. 6 shows a stress-strain curve of the polyamide-imide film according to Comparative Example 3.
  • FIG. 7 schematically illustrates a process facility for preparing a polyamide-imide film according to an embodiment.
  • substituted means to be substituted with at least one substituent group selected from the group consisting of deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, an ester group, a ketone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl
  • An embodiment provides a polyamide-imide film that is excellent in mechanical properties and optical properties and that especially secures excellent tensile toughness and elastic restoring force.
  • the polyamide-imide film according to an embodiment comprises a polyamide-imide polymer formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound.
  • the polyamide-imide polymer comprises an imide repeat unit derived from the polymerization of the diamine compound and the dianhydride compound and amide repeat units derived from the polymerization of the diamine compound and the dicarbonyl compound.
  • the diamine compound is a compound that forms an imide bond with the dianhydride compound and forms an amide bond with the dicarbonyl compound, to thereby form a copolymer.
  • the diamine compound is not particularly limited, but it may be, for example, an aromatic diamine compound that contains an aromatic structure.
  • the diamine compound may be a compound represented by the following Formula 1.
  • E may be selected from a substituted or unsubstituted divalent C 6 -C 30 aliphatic cyclic group, a substituted or unsubstituted divalent C 4 -C 30 heteroaliphatic cyclic group, a substituted or unsubstituted divalent C 6 -C 30 aromatic cyclic group, a substituted or unsubstituted divalent C 4 -C 30 heteroaromatic cyclic group, a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 2 -C 30 alkenylene group, a substituted or unsubstituted C 2 -C 30 alkynylene group, —O—, —S—, —C( ⁇ O)—, —CH(OH)—, —S( ⁇ O) 2 —, —Si(CH 3 ) 2 —, —C(CH 3 ) 2 —, and —C(CF 3
  • e is selected from integers of 1 to 5. When e is 2 or more, E may be the same as, or different from, each other.
  • (E) e in the above Formula 1 may be selected from the groups represented by the following Formulae 1-1a to 1-14a.
  • (E) e in the above Formula 1 may be selected from the groups represented by the following Formulae 1-1b to 1-13b, but it is not limited thereto.
  • (E) e in the above Formula 1 may be the group represented by the above Formula 1-6b.
  • the dianhydride compound may comprise a compound having a fluorine-containing substituent.
  • the dianhydride compound may be composed of a compound having a fluorine-containing substituent.
  • the fluorine-containing substituent may be a fluorinated hydrocarbon group and specifically may be a trifluoromethyl group. But it is not limited thereto.
  • one kind of diamine compound may be used as the diamine compound. That is, the diamine compound may be composed of a single component.
  • the diamine compound may comprise 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB) represented by the following formula, but it is not limited thereto.
  • TFDB 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl
  • the dianhydride compound is a compound that has a low birefringence value, so that it can contribute to enhancements in the optical properties such as transmittance of the polyamide-imide film.
  • the dianhydride compound is not particularly limited, but it may be, for example, an aromatic dianhydride compound that contains an aromatic structure.
  • the aromatic dianhydride compound may be a compound represented by the following Formula 2.
  • G is bonded by a bonding group selected from a substituted or unsubstituted tetravalent C 6 -C 30 aliphatic cyclic group, a substituted or unsubstituted tetravalent C 4 -C 30 heteroaliphatic cyclic group, a substituted or unsubstituted tetravalent C 6 -C 30 aromatic cyclic group, a substituted or unsubstituted tetravalent C 4 -C 30 heteroaromatic cyclic group, wherein the aliphatic cyclic group, the heteroaliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group may be present alone or may be bonded to each other to form a condensed ring, a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 2 -C 30 alkenylene group, a substituted or unsubstituted C 2 -
  • G in the above Formula 2 may be selected from the groups represented by the following Formulae 2-1a to 2-9a, but it is not limited thereto.
  • G in the above Formula 2 may be the group represented by the above Formula 2-8a.
  • the dianhydride compound may comprise a compound having a fluorine-containing substituent.
  • the dianhydride compound may be composed of a compound having a fluorine-containing substituent.
  • the fluorine-containing substituent may be a fluorinated hydrocarbon group and specifically may be a trifluoromethyl group. But it is not limited thereto.
  • the dianhydride compound may be composed of a single component or a mixture of two components.
  • the dianhydride compound may comprise 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA) represented by the following formula, but it is not limited thereto.
  • the diamine compound and the dianhydride compound may be polymerized to form a polyamic acid.
  • the polyamic acid may be converted to a polyimide through a dehydration reaction, and the polyimide comprises an imide repeat unit.
  • the polyimide may form a repeat unit represented by the following Formula A.
  • the polyimide may comprise a repeat unit represented by the following Formula A-1, but it is not limited thereto.
  • n is an integer of 1 to 400.
  • the dicarbonyl compound is not particularly limited, but it may be, for example, a compound represented by the following Formula 3.
  • J may be selected from a substituted or unsubstituted divalent C 6 -C 30 aliphatic cyclic group, a substituted or unsubstituted divalent C 4 -C 30 heteroaliphatic cyclic group, a substituted or unsubstituted divalent C 6 -C 30 aromatic cyclic group, a substituted or unsubstituted divalent C 4 -C 30 heteroaromatic cyclic group, a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 2 -C 30 alkenylene group, a substituted or unsubstituted C 2 -C 30 alkynylene group, —O—, —S—, —C( ⁇ O)—, —CH(OH)—, —S( ⁇ O) 2 —, —Si(CH 3 ) 2 —, —C(CH 3 ) 2 —, and —C(CF 3
  • j is selected from integers of 1 to 5. When j is 2 or more, J may be the same as, or different from, each other.
  • X is a halogen atom. Specifically, X may be F, Cl, Br, I, or the like. More specifically, X may be Cl, but it is not limited thereto.
  • (J) j in the above Formula 3 may be selected from the groups represented by the following Formulae 3-1a to 3-14a, but it is not limited thereto.
  • (J) j in the above Formula 3 may be selected from the groups represented by the following Formulae 3-1b to 3-8b, but it is not limited thereto.
  • (J) j in the above Formula 3 may be the group represented by the above Formula 3-2b or 3-3b.
  • a mixture of at least two kinds of dicarbonyl compounds different from each other may be used as the dicarbonyl compound. If two or more dicarbonyl compounds are used, at least two dicarbonyl compound in which (J) j in the above Formula 3 is selected from the groups represented by the above Formulae 3-1b to 3-8b may be used as the dicarbonyl compound.
  • the dicarbonyl compound may be an aromatic dicarbonyl compound that contains an aromatic structure.
  • the dicarbonyl compound may comprise a first dicarbonyl compound and/or a second dicarbonyl compound.
  • the first dicarbonyl compound and the second dicarbonyl compound may be an aromatic dicarbonyl compound, respectively.
  • the first dicarbonyl compound and the second dicarbonyl compound may be compounds different from each other.
  • first dicarbonyl compound and the second dicarbonyl compound may be aromatic dicarbonyl compounds different from each other, but they are not limited thereto.
  • first dicarbonyl compound and the second dicarbonyl compound are an aromatic dicarbonyl compound, respectively, they comprise a benzene ring. Thus, they can contribute to improvements in the mechanical properties such as surface hardness and tensile strength of the polyamide-imide film thus produced.
  • the dicarbonyl compound may comprise terephthaloyl chloride (TPC), 1,1′-biphenyl-4,4′-dicarbonyl dichloride (BPDC), as represented by the following formulae, or a combination thereof. But it is not limited thereto.
  • TPC terephthaloyl chloride
  • BPDC 1,1′-biphenyl-4,4′-dicarbonyl dichloride
  • the first dicarbonyl compound may comprise BPDC
  • the second dicarbonyl compound may comprise TPC, but they are not limited thereto.
  • the polyamide-imide film thus produced may have high oxidation resistance.
  • the diamine compound and the dicarbonyl compound may be polymerized to form a repeat unit represented by the following Formula B.
  • the diamine compound and the dicarbonyl compound may be polymerized to form amide repeat units represented by the following Formulae B-1 and B-2.
  • x is an integer of 1 to 400.
  • y is an integer of 1 to 400.
  • the polyamide-imide polymer may comprise a repeat unit represented by the following Formula A and a repeat unit represented by the following Formula B:
  • the polyamide-imide polymer comprises an imide repeat unit and an amide repeat unit.
  • the molar ratio of the imide repeat unit to the amide repeat unit may be 20:80 to 80:20, for example, 20:80 to 50:50.
  • the imide repeat unit may be a repeat unit represented by the above Formula A
  • the amide repeat unit may be a repeat unit represented by the above Formula B.
  • the molar ratio satisfies the above range, it is easy to control the viscosity of the polymer solution by using the monomers as described above for preparing the same. As a result, it is easy to produce a uniform film without defects on the surface thereof from the gel-sheet and the cured film. In addition, it is possible to produce a film that secures excellent tensile toughness and elastic restoring force.
  • the area value up to the yield point derived by the 0.2% off-set method on a stress-strain curve of the polyamide-imide film as measured using a universal testing machine (UTM) is 80 to 150 J/m 2 .
  • the area value up to the yield point derived by the 0.2% off-set method on a stress-strain curve of the polyamide-imide film as measured using a universal testing machine (UTM) may be 100 to 140 J/m 2 , 110 to 130 J/m 2 , or 120 to 130 J/m 2 , but it is not limited thereto.
  • the area up to the yield point refers to the area of the elastic region, which stands for a measure of how well the material can store energy prior to plasticization.
  • the polyamide-imide film has a modulus of 5.0 GPa or more when measured at room temperature.
  • the modulus may be 5 GPa to 10 GPa, 6 GPa to 10 GPa, or 7 to 10 GPa.
  • the polyamide-imide film has a surface hardness of HB or higher.
  • the surface hardness may be H or higher, or 2H or higher, but it is not limited thereto.
  • the polyamide-imide film has a yellow index of 5 or less.
  • the yellow index may be 4.5 or less. More specifically, the yellow index may be 4 or less, but it is not limited thereto.
  • the polyamide-imide film has a haze of 2% or less. Specifically, the haze may be 1.8% or less or 1.5% or less. More specifically, the haze may be 1.0% or less or 0.9% or less, but it is not limited thereto.
  • the polyamide-imide film has a light transmittance measured at 550 nm of 85% or more.
  • the light transmittance measured at 550 nm may be 86% or more, 87% or more, or 88% or more, but it is not limited thereto.
  • the polyamide-imide film may have a restoration angle of 60° or more at the time of evaluating the folding restoring force.
  • the restoration angle may be 60° to 180°, 60° to 150°, 60° to 120°, 60° to 90°, 60° to 80°, or 60° to 70°, but it is not limited thereto.
  • the restoration angle at the time of evaluating the folding restoring force refers to the angle at which the film bent and inserted between zigs of a 5 mm interval is restored after 24 hours under the conditions of 85° C. and 85% RH.
  • the polyamide-imide film has a tensile strength of 15 kgf/mm 2 or more.
  • the tensile strength may be 18 kgf/mm 2 or more, 20 kgf/mm 2 or more, 21 kgf/mm 2 or more, or 22 kgf/mm 2 or more, but it is not limited thereto.
  • the polyamide-imide film has an elongation of 15% or more.
  • the elongation may be 16% or more, 17% or more, or 17.5% or more, but it is not limited thereto.
  • the physical properties of the polyamide-imide film as described above are based on a thickness of 40 ⁇ m to 60 ⁇ m.
  • the physical properties of the polyamide-imide film may be based on a thickness of 50 ⁇ m.
  • the polyamide-imide film is prepared by the preparation process as described below such that it is excellent in optical and mechanical properties.
  • the polyamide-imide film may be applicable to various uses that require flexibility and transparency.
  • the polyamide-imide film may be applied to solar cells, displays, semiconductor devices, sensors, and the like.
  • the process for preparing a polyamide-imide film comprises simultaneously or sequentially mixing and reacting a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent in a polymerization apparatus to prepare a polymer solution; transferring the polymer solution to a tank; casting the polymer solution in the tank and then drying it to prepare a gel-sheet; thermally treating the gel-sheet, while it is moved on a belt, to prepare a cured film; and winding the cured film using a winder.
  • the polyamide-imide film is a film that comprises a polyamide-imide resin as a main component.
  • the polyamide-imide resin is a resin that comprises, as a structural unit, an amide repeat unit and an imide repeat unit at a predetermined molar ratio.
  • a polymer solution for preparing the polyamide-imide resin is prepared by simultaneously or sequentially mixing and reacting a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent in a polymerization apparatus.
  • the polymer solution may be prepared by simultaneously mixing and reacting the diamine compound, the dianhydride compound, and the dicarbonyl compound in an organic solvent.
  • the step of preparing the polymer solution may comprise first mixing and reacting the diamine compound and the dianhydride compound to produce a polyamic acid (PAA) solution; and second mixing and reacting the polyamic acid (PAA) solution and the dicarbonyl compound to form an amide bond and an imide bond at the same time.
  • the polyamic acid solution is a solution that comprises a polyamic acid.
  • the step of preparing the polymer solution may comprise first mixing and reacting the diamine compound and the dianhydride compound to produce a polyamic acid solution; subjecting the polyamic acid solution to dehydration to produce a polyimide (PI) solution; and second mixing and reacting the polyimide (PI) solution and the dicarbonyl compound to further form an amide bond.
  • the polyimide solution is a solution that comprises a polymer having an imide repeat unit.
  • the step of preparing the polymer solution may comprise first mixing and reacting the diamine compound and the dicarbonyl compound to produce a polyamide (PA) solution; and second mixing and reacting the polyamide (PA) solution and the dianhydride compound to further form an imide bond.
  • the polyamide solution is a solution that comprises a polymer having an amide repeat unit.
  • the polymer solution thus prepared may be a solution that comprises a polymer containing at least one selected from the group consisting of a polyamic acid (PAA) repeat unit, a polyamide (PA) repeat unit, and a polyimide (PI) repeat unit.
  • PAA polyamic acid
  • PA polyamide
  • PI polyimide
  • the polymer comprised in the polymer solution may comprise an imide repeat unit derived from the polymerization of the diamine compound and the dianhydride compound and an amide repeat unit derived from the polymerization of the diamine compound and the dicarbonyl compound.
  • the step of preparing the polymer solution may further comprise introducing a catalyst.
  • the catalyst may include, for example, beta picoline or acetic anhydride, but it is not limited thereto.
  • the further addition of the catalyst may expedite the reaction rate and enhance the chemical bonding force between the repeat units or that within the repeat units.
  • the step of preparing the polymer solution may further comprise adjusting the viscosity of the polymer solution.
  • the step of preparing the polymer solution may comprise (a) simultaneously or sequentially mixing and reacting a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent to prepare a first polymer solution; (b) measuring the viscosity of the first polymer solution and evaluating whether the target viscosity has been reached; and (c) if the viscosity of the first polymer solution does not reach the target viscosity, further adding the dicarbonyl compound to prepare a second polymer solution having the target viscosity.
  • the target viscosity may be about 100,000 cps to about 500,000 cps at room temperature. Specifically, the target viscosity may be about 100,000 cps to about 400,000 cps, about 100,000 cps to about 350,000 cps, or about 100,000 cps to about 300,000 cps, but it is not limited thereto.
  • the content of solids contained in the polymer solution may be 10% by weight to 20% by weight.
  • the content of solids contained in the second polymer solution may be 12% by weight to 18% by weight, but it is not limited thereto.
  • the content of solids contained in the polymer solution is within the above range, a polyamide-imide film can be effectively produced in the extrusion and casting steps.
  • the polyamide-imide film thus produced may have mechanical properties in terms of an improved modulus and the like and optical properties in terms of a low yellow index and the like.
  • the step of preparing the polymer solution may further comprise adjusting the pH of the polymer solution.
  • the pH of the polymer solution may be adjusted to about 4 to about 7, for example about 4.5 to about 7.
  • the pH of the polymer solution may be adjusted by adding a pH adjusting agent.
  • the pH adjusting agent is not particularly limited and may include, for example, amine compounds such as alkoxyamine, alkylamine, and alkanolamine.
  • the pH of the polymer solution is adjusted to the above range, it is possible to prevent the damage to the equipment in the subsequent process, to prevent the occurrence of defects in the film produced from the polymer solution, and to achieve the desired optical properties and mechanical properties in terms of yellow index and modulus.
  • the pH adjusting agent may be employed in an amount of about 0.1% by mole to about 10% by mole based on the total number of moles of monomers in the polymer solution.
  • the step of preparing the polymer solution may further comprise purging the polymer solution with an inert gas.
  • the step of purging the polymer solution with an inert gas may remove moisture, reduce impurities, and increase the reaction yield.
  • the inert gas may be at least one selected from the group consisting of nitrogen, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn), but it is not limited thereto.
  • the inert gas may be nitrogen.
  • the molar ratio of the dianhydride compound to the dicarbonyl compound used to prepare the polymer solution may be 20:80 to 80:20, for example, 20:80 to 50:50. If the dianhydride compound and the dicarbonyl compound are employed in the above molar ratio, it is advantageous to achieve the desired mechanical and optical properties of the polyamide-imide film prepared from the polymer solution.
  • the polymer solution is a solution that comprises a polyamide-imide polymer.
  • the diamine compound, the dianhydride compound, the dicarbonyl compound, and the polyamide-imide polymer are as described above.
  • the polymer solution may comprise a polyamide-imide polymer formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound, wherein the diamine compound may comprise one kind of diamine compound, the dianhydride compound may comprise one kind of dianhydride compound, and the dicarbonyl compound may comprise two kinds of dicarbonyl compound.
  • the diamine compound may be composed of one kind of diamine compound
  • the dianhydride compound may be composed of one kind of dianhydride compound
  • the dicarbonyl compound may be composed of two kinds of dicarbonyl compound.
  • the polyamide-imide resin which is a main component of the polyamide-imide film, is a resin that comprises, as a structural unit, an amide repeat unit and an imide repeat unit at a predetermined molar ratio.
  • the imide repeat unit and the amide repeat unit are as described above.
  • the organic solvent may be at least one selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), m-cresol, tetrahydrofuran (THF), and chloroform.
  • the organic solvent employed in the polymerization solution may be dimethylacetamide (DMAc), but it is not limited thereto.
  • the polymer solution is transferred to a tank.
  • FIG. 7 schematically illustrates a process facility for preparing a polyamide-imide film according to an embodiment.
  • the polymer solution as described above is prepared in a polymerization apparatus ( 10 ), and the polymer solution thus produced is transferred to, and stored, in a tank ( 20 ).
  • the step of transferring the polymer solution to the tank is carried out without any additional steps. Specifically, the polymer solution prepared in the polymerization apparatus is transferred to, and stored in, the tank without any separate precipitation and redissolution steps for removing impurities.
  • the polymer solution thus prepared is purified through a separate step to remove the impurities, and the purified polymer solution is then redissolved in a solvent.
  • impurities such as hydrochloric acid (HCl) generated during the preparation of a polymer solution
  • the preparation process according to an embodiment ultimately minimizes the amount of impurities generated in the step of preparing the polymer solution or properly controls the impurities in the subsequent steps, even if a certain amount of impurities is present, so as not to deteriorate the physical properties of the final film.
  • the process has an advantage in that a film is produced without separate precipitation or redissolution steps.
  • the tank ( 20 ) is a place for storing the polymer solution before forming it into a film, and its internal temperature may be about ⁇ 20° C. to about 0° C. If the temperature of the tank ( 20 ) is controlled to the above range, it is possible to prevent the polymer solution from deteriorating during storage, and it is possible to lower the moisture content to thereby prevent defects of the film produced therefrom.
  • the process for preparing a polyamide-imide film may further comprise carrying out vacuum degassing of the polymer solution transferred to the tank ( 20 ).
  • the vacuum degassing may be carried out for 1 hour to 2 hours after depressurizing the internal pressure of the tank to 0.2 to 0.4 bar.
  • the vacuum degassing under these conditions may reduce bubbles in the polymer solution. As a result, it is possible to prevent surface defects of the film produced therefrom and to achieve excellent optical properties such as haze.
  • the process for preparing a polyamide-imide film may further comprise purging the polymer solution transferred to the tank ( 20 ) with an inert gas.
  • the purging is carried out by purging the tank with an inert gas at an internal pressure of 1 atm to 2 atm.
  • the nitrogen purging under these conditions may reduce bubbles in the polymer solution. As a result, it is possible to prevent surface defects of the film produced therefrom and to achieve excellent optical properties such as haze.
  • the step of vacuum degassing and the step of purging the tank with nitrogen gas are performed in a separate process, respectively.
  • the step of vacuum degassing may be carried out, followed by the step of purging the tank with nitrogen gas, but it is not limited thereto.
  • the step of vacuum degassing and/or the step of purging the tank with nitrogen may improve the physical properties of the surface of the polyamide-imide film thus produced.
  • the process may further comprise storing the polymer solution in the tank ( 20 ) for 12 hours to 60 hours.
  • the temperature inside the tank may be kept at about ⁇ 20° C. to about 0° C.
  • the process for preparing a polyamide-imide film may further comprise casting the polymer solution in the tank and then drying it to prepare a gel-sheet.
  • the polymer solution may be cast onto a casting body such as a casting roll or a casting belt.
  • the polymer solution may be applied onto a casting belt ( 30 ) as a casting body, and it is dried, while it is moved, to be made into a sheet in the form of a gel.
  • the injection amount may be 300 g/min to 700 g/min. If the injection amount of the polymer solution satisfies the above range, the gel-sheet can be uniformly formed to an appropriate thickness.
  • the casting thickness of the polymer solution may be about 200 ⁇ m to about 700 ⁇ m. If the polymer solution is cast to a thickness within the above range, the final film produced after the drying and thermal treatment may have an appropriate and uniform thickness.
  • the polymer solution is cast and then dried at a temperature of 60° C. to 150° C. for 5 minutes to 60 minutes to prepare a gel-sheet.
  • the solvent of the polymer solution is partially or totally volatilized during the drying to prepare the gel-sheet.
  • the viscosity of the polymer solution at room temperature may be 100,000 cps to 500,000 cps, 100,000 cps to 400,000 cps, 100,000 cps to 350,000 cps, or 150,000 cps to 350,000 cps. If the viscosity satisfies the above range, the polymer solution can be cast onto a belt in a uniform thickness without defects.
  • the process for preparing a polyamide-imide film comprises thermally treating the gel-sheet, while it is moved on the belt, to prepare a cured film.
  • the thermal treatment of the gel-sheet may be carried out by passing it through a thermosetting device ( 40 ).
  • the thermal treatment of the gel-sheet may be carried out in a temperature range of about 80° C. to about 500° C. at a temperature elevation rate about of 2° C./min to about 80° C./min for about 5 minutes to about 40 minutes. Specifically, the thermal treatment of the gel-sheet may be carried out in a temperature range of about 80° C. to about 470° C. at a temperature elevation rate of about 10° C./min to about 80° C./min for about 5 minutes to about 30 minutes.
  • the initial temperature of the thermal treatment of the gel-sheet may be about 80° C. or higher, and the maximum temperature in the thermal treatment may be about 300° C. to about 500° C.
  • the maximum temperature in the thermal treatment may be 350° C. to 500° C., 380° C. to 500° C., 400° C. to 500° C., 410° C. to 480° C., 410° C. to 470° C., or 410° C. to 450° C.
  • the inlet temperature of the thermosetting device ( 40 ) may be the initial temperature of the thermal treatment, and the temperature of a certain region inside the thermosetting device ( 40 ) may be the maximum temperature in the thermal treatment.
  • the thermal treatment under these conditions may cure the gel-sheet to have appropriate surface hardness and modulus and may secure high light transmittance and low haze of the cured film at the same time.
  • the process for preparing a polyamide-imide film may further comprise, after the preparation of the cured film by thermal treatment, cooling the cured film while it is moved on a belt.
  • the cooling of the cured film is carried out after it has been passed through the thermosetting device ( 40 ). It may be carried out by using a separate cooling chamber (not shown) or by forming an appropriate temperature atmosphere without a separate cooling chamber.
  • the step of cooling the cured film while it is moved on a belt may comprise a first temperature lowering step of reducing the temperature at a rate of 100° C./min to 1,000° C./min and a second temperature lowering step of reducing the temperature at a rate of 40° C./min to 400° C./min.
  • the second temperature lowering step is performed after the first temperature lowering step.
  • the temperature lowering rate of the first temperature lowering step may be faster than the temperature lowering rate of the second temperature lowering step.
  • the maximum rate of the first temperature lowering step is faster than the maximum rate of the second temperature lowering step.
  • the minimum rate of the first temperature lowering step is faster than the minimum rate of the second temperature lowering steps.
  • step of cooling the cured film is carried in such a multistage manner, it is possible to have the physical properties of the cured film further stabilized and to maintain the optical properties and mechanical properties of the film achieved during the curing step more stably for a long period of time.
  • the moving speed of the belt for moving the gel-sheet is the same as the moving speed of the belt for moving the cured film.
  • the process for preparing a polyamide-imide film comprises winding the cooled cured film using a winder.
  • the cooled cured film may be wound by using a roll-shaped winder ( 50 ).
  • the ratio of the moving speed of the gel-sheet on a belt at the time of thermal treatment to the moving speed of the cured film at the time of winding is 1:0.95 to 1:1.40.
  • the ratio of the moving speeds may be 1:0.99 to 1:1.20, 1:0.99 to 1:1.10, or 1:1.10 to 1:1.05, but it is not limited thereto.
  • the ratio of the moving speeds is outside the above range, the mechanical properties of the cured film may be impaired, and the flexibility and elastic properties may be deteriorated.
  • the belt ( 30 ) for moving the gel-sheet and the cured film is a continuous belt on the same line.
  • the moving speed of the belt ( 30 ) may be about 0.1 m/min to about 15 m/min, for example, about 0.5 m/min to about 10 m/min.
  • the thickness variation (%) according to the following Equation 1 may be 3% to 30%, for example, 5% to 20%.
  • Thickness variation (%) ( M 1 ⁇ M 2)/ M 2 ⁇ 100 [Equation 1]
  • M1 is the thickness ( ⁇ m) of the gel-sheet
  • M2 is the thickness ( ⁇ m) of the cooled cured film at the time of winding.
  • the polyamide-imide film prepared by the above preparation process is excellent in mechanical properties and optical properties. It is possible to impart long-term stable mechanical properties on a substrate that requires flexibility in terms of modulus, elongation, tensile characteristics, and elastic restoring force.
  • a polyamide-imide film prepared by the process for preparing a polyamide-imide film.
  • the polyamide-imide film is as described in the above section of ⁇ Polyamide-imide film>.
  • the properties of the polyamide-imide film as described above are the results materialized by combinations of the chemical and physical properties of the components, which constitute the polyamide-imide film, along with the conditions in each step of the process for preparing the polyamide-imide film as described above.
  • a 1 L glass reactor equipped with a temperature-controllable double jacket was charged with 403.2 g of dimethyl acetamide (DMAc) as an organic solvent at 20° C. under a nitrogen atmosphere. Then, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB) as an aromatic diamine was slowly added thereto and dissolved.
  • DMAc dimethyl acetamide
  • TFDB 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl
  • BPDC 1,1′-biphenyl-4,4′-dicarbonyldichloride
  • TPC terephthaloyl chloride
  • the viscosity of the first polymer solution thus prepared was measured. If the measured viscosity did not reach the target viscosity, a TPC solution in a DMAc organic solvent at a concentration of 10% by weight was prepared, and 1 ml of the TPC solution was added to the first polymer solution, followed by stirring the mixture for 30 minutes. This procedure was repeated until the viscosity became about 230,000 cps, thereby preparing a second polymer solution.
  • the second polymer solution was transferred to a tank and stored at ⁇ 10° C.
  • the tank was degassed for 1.5 hours, so that the pressure in the tank was about 0.3 bar. Then, the tank was purged with a nitrogen gas at an internal pressure of 1.5 atm. Upon the purging, the second polymer solution was stored in the tank for 48 hours.
  • the second polymer solution was cast and then dried with hot air at 80° C. for 30 minutes, thereby producing a gel-sheet.
  • the gel-sheet was subjected to thermal treatment in a temperature range of 80° C. to 500° C. at a temperature elevation rate of 2° C./min to 80° C./min for 30 minutes while it was moved on a belt.
  • a first temperature lowering step was carried out by reducing the temperature at a rate of about 800° C./min, followed by a second temperature lowering step by reducing the temperature at a rate of about 100° C./min, thereby obtaining a polyamide-imide film.
  • the film was wound using a winder.
  • the moving speed of the gel-sheet on the belt at the time of thermal treatment was 1 m/s.
  • the ratio of the moving speed of the gel-sheet on the belt at the time of thermal treatment to the moving speed of the film at the time of winding was adjusted as shown in Table 1 below.
  • a 1 L glass reactor equipped with a temperature-controllable double jacket was charged with 518.5 g of dimethyl acetamide (DMAc) as an organic solvent at 20° C. under a nitrogen atmosphere. Then, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFDB) as an aromatic diamine was slowly added thereto and dissolved.
  • DMAc dimethyl acetamide
  • TFDB 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl
  • TPC terephthaloyl chloride
  • dicarbonyl compound a dicarbonyl compound
  • TPC terephthaloyl chloride
  • the viscosity of the first polymer solution thus prepared was measured. If the measured viscosity did not reach the target viscosity, a TPC solution in a DMAc organic solvent at a concentration of 10% by weight was prepared, and 1 mL of the TPC solution was added to the first polymer solution, followed by stirring the mixture for 30 minutes. This procedure was repeated until the viscosity became 100,000 cps to 300,000 cps, thereby preparing a second polymer solution.
  • the second polymer solution was processed by the method described in Example 1 to prepare a polyamide-imide film.
  • the ratio of the moving speed of the gel-sheet on the belt at the time of thermal treatment to the moving speed of the film at the time of winding was adjusted as shown in Table 1 below.
  • a polyamide-imide film was prepared by the same composition and processing method as those of Examples 1 to 3.
  • the ratio of the moving speed of the gel-sheet on the belt at the time of thermal treatment to the moving speed of the film at the time of winding was adjusted as shown in Table 1 below.
  • a PET film of the brand name SH86 produced by SKC was used.
  • the thickness was measured at 5 points in the width direction using a digital micrometer 547-401 manufactured by Mitutoyo Corporation. Their average value was adopted as the thickness.
  • the speed ratio refers to the ratio of the moving speed of the gel-sheet on the belt at the time of thermal treatment to the moving speed of the cured film at the time of winding.
  • the moving speed of the gel-sheet and that of the cured film were measured using a contact type tachometer MS6208A of Optech.
  • a sample was cut out by at least 5 cm in the direction perpendicular to the main shrinkage direction of the film and by 10 cm in the main shrinkage direction. It was fixed by the clips disposed at intervals of 5 cm in a universal testing machine UTM 5566A of Instron. A stress-strain curve was obtained until the sample was fractured while it was stretched at a rate of 5 mm/min at room temperature. The slope of the load with respect to the initial strain on the stress-strain curve was taken as the modulus (GPa).
  • the area value of the elastic region was measured as the integral value for the stress-strain curve from the initial strain to the yield point.
  • the surface hardness was measured with a pencil hardness measuring instrument (CT-PCl, CORE TECH, Korea) with a pencil hardness measuring pencil mounted at an angle of 45° and at a pencil speed of 300 mm/min while a constant load (750 g) was applied.
  • the pencil used was Mitsubishi pencils having a strength of H to 9H, F, HB, B to 6B, and the like.
  • the yellow Index (YI) was measured with a spectrophotometer (UltraScan PRO, Hunter Associates Laboratory) using a CIE colorimetric system.
  • the light transmittance at 550 nm and the haze were measured using a haze meter NDH-5000W manufactured by Nippon Denshoku Kogyo.
  • the film was bent and inserted between zigs of a 5 mm interval, and the angle was measure when it is restored after 24 hours under the conditions of 85° C. and 85% RH.

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