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WO2023055133A1 - Film de polyimide présentant une résistance mécanique et une résistance à la chaleur améliorées et son procédé de fabrication - Google Patents

Film de polyimide présentant une résistance mécanique et une résistance à la chaleur améliorées et son procédé de fabrication Download PDF

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Publication number
WO2023055133A1
WO2023055133A1 PCT/KR2022/014670 KR2022014670W WO2023055133A1 WO 2023055133 A1 WO2023055133 A1 WO 2023055133A1 KR 2022014670 W KR2022014670 W KR 2022014670W WO 2023055133 A1 WO2023055133 A1 WO 2023055133A1
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mol
dianhydride
polyimide film
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Korean (ko)
Inventor
여문진
이길남
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PI Advanced Materials Co Ltd
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PI Advanced Materials Co Ltd
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Priority to CN202280063493.6A priority Critical patent/CN117980384A/zh
Priority to JP2024519122A priority patent/JP7741975B2/ja
Publication of WO2023055133A1 publication Critical patent/WO2023055133A1/fr
Anticipated expiration legal-status Critical
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide film having excellent mechanical strength and heat resistance and a manufacturing method thereof.
  • Polyimide (PI) is a polymer material that has the highest level of chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials, based on an imide ring having excellent chemical stability along with a rigid aromatic main chain.
  • Such a thin circuit board tends to use a structure in which a circuit including a metal foil is formed on a polyimide film that has excellent heat resistance, low temperature resistance, and insulation characteristics and is easily bent.
  • a flexible metal clad laminate is mainly used, and as an example, a flexible copper clad laminate (FCCL) using a thin copper plate as a metal foil is included.
  • FCCL flexible copper clad laminate
  • polyimide is also used as a protective film or insulating film for thin circuit boards.
  • the conventional polyimide film has a disadvantage of relatively low heat resistance to be used in the latest circuit boards.
  • Various previous studies have been conducted to improve heat resistance, but the improvement in heat resistance is due to the need for thermal properties such as mechanical strength or glass transition temperature. accompanied by a decline.
  • Patent Document 1 Korean Patent Registration No. 10-1004429
  • An object of the present invention is to provide a polyimide film having excellent heat resistance and mechanical properties and a manufacturing method thereof.
  • an object of the present invention is to provide a polyimide film having high high temperature stability and excellent elastic modulus, tensile strength and elongation properties, and a manufacturing method thereof.
  • the present invention has a practical purpose to provide specific embodiments thereof.
  • biphenyltetracarboxylic dianhydride (3,3 ', 4,4'-Biphenyltetracarboxylic dianhydride, BPDA)
  • pyromellitic dianhydride Pyromellitic dianhydride (PMDA)
  • dianhydride components including benzophenonetetracarboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA); and
  • Diamines including 4,4′-Oxydianiline (ODA), p-Phenylenediamine (PPD) and 4,4′-Diaminobenzanilide (DABA) It provides a polyimide film prepared by imidizing a polyamic acid solution containing; component.
  • ODA 4,4′-Oxydianiline
  • PPD p-Phenylenediamine
  • DABA 4,4′-Diaminobenzanilide
  • the content of oxydianiline is 23 mol% or more and 43 mol% or less
  • the content of paraphenylene diamine is 50 mol% or more and 60 mol% % or less
  • the content of the 4,4'-diaminobenzanilide may be 10 mol% or more and 30 mol% or less.
  • the content of the biphenyltetracarboxylic dianhydride is 15 mol% or more and 30 mol% or less
  • the content of the pyromellitic dianhydride is 50 mol%. % or more and 65 mol% or less
  • the content of the benzophenone tetracarboxylic dianhydride may be 10 mol% or more and 35 mol% or less.
  • the polyimide film may include a block copolymer composed of two or more blocks.
  • the polyimide film may have an elastic modulus of 5 GPa or more, strength of 340 MPa or more, a glass transition temperature (Tg) of 360° C. or more, and an elongation of 60% or more.
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • BTDA benzophenonetetracarboxylic dianhydride
  • a method for producing a polyimide film is provided.
  • Another embodiment of the present invention provides a multilayer film including the polyimide film or a multilayer film including the polyimide film and a thermoplastic resin layer.
  • Another embodiment of the present invention provides a flexible metal-clad laminate including the polyimide film and the electrically conductive metal foil, and an electronic component including the flexible metal-clad laminate.
  • the polyimide film according to the embodiment of the present invention may simultaneously have excellent high heat resistance properties and mechanical properties by using a combination of a specific dianhydride component and a specific diamine component in a specific molar ratio. In addition, adhesion can be improved.
  • the present invention can be usefully applied to electronic parts such as flexible metal clad laminates including the polyimide film as described above.
  • dianhydride acid is intended to include its precursors or derivatives, which technically may not be dianhydride acids, but will nonetheless react with diamines to form polyamic acids, which in turn polyamic acids. can be converted to mead.
  • diamine is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nonetheless react with dianhydrides to form polyamic acids, which in turn will form polyamic acids. can be converted to mead.
  • the polyimide film according to the present invention is biphenyltetracarboxylic dianhydride (3,3',4,4'-Biphenyltetracarboxylic dianhydride, BPDA), pyromellitic dianhydride (PMDA) and benzophenone tetra dianhydride components including carboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA); and oxydianiline (4,4′-Oxydianiline, ODA), p-Phenylenediamine (PPD) and 4,4′-diaminobenzanilide (4,4′-diaminobenzanilide, DABA). It is prepared by imidizing a polyamic acid solution containing; diamine component.
  • BPDA pyromellitic dianhydride
  • PMDA pyromellitic dianhydride
  • benzophenone tetra dianhydride components including
  • the content of oxydianiline is 23 mol% or more and 43 mol% or less
  • the content of paraphenylene diamine is 50 mol% or more 60 mol% % or less
  • the content of the 4,4'-diaminobenzanilide may be 10 mol% or more and 30 mol% or less.
  • the 4,4'-diaminobenzanilide contains an amide group, it greatly contributes to the improvement of excellent heat resistance and mechanical properties of the polyimide film of the present application within the content range of the present application.
  • the content of the biphenyltetracarboxylic dianhydride is 15 mol% or more and 30 mol% or less based on 100 mol% of the total content of the dianhydride component, and the pyromellitic dianhydride The content may be 50 mol% or more and 65 mol% or less, and the content of the benzophenone tetracarboxylic dianhydride may be 10 mol% or more and 35 mol% or less.
  • the polyimide chain derived from biphenyltetracarboxylic dianhydride has a structure called a charge transfer complex (CTC), that is, an electron donor and an electron acceptor are arranged in close proximity to each other. It has a regular linear structure and intermolecular interaction is strengthened.
  • CTC charge transfer complex
  • benzophenonetetracarboxylic dianhydride having a carbonyl group also contributes to the expression of CTC like biphenyltetracarboxylic dianhydride.
  • pyromellitic dianhydride may be additionally included as the dianhydride component.
  • Pyromellitic dianhydride is a dianhydride component having a relatively rigid structure, and is preferable in that it can impart appropriate elasticity to the polyimide film.
  • biphenyltetracarboxylic dianhydride and benzophenonetetracarboxylic dianhydride contain two benzene rings corresponding to the aromatic part, whereas pyromellitic dianhydride has a benzene ring corresponding to the aromatic part contains 1
  • the increase in the pyromellitic dianhydride content in the dianhydride component can be understood as an increase in the imide group in the molecule based on the same molecular weight, which means that the polyimide polymer chain has an imide derived from the pyromellitic dianhydride. It can be understood that the ratio of de groups is increased relative to the imide groups derived from biphenyltetracarboxylic dianhydride and benzophenonetetracarboxylic dianhydride.
  • the content ratio of pyromellitic dianhydride is excessively decreased, the component having a relatively rigid structure is reduced, and mechanical properties of the polyimide film may be lowered to a desired level or less.
  • the polyimide film may include a block copolymer composed of two or more blocks.
  • At least one block of the block copolymer may include a bond between pyromellitic dianhydride and 4,4'-diaminobenzanilide.
  • the glass transition temperature of the polyimide film can be increased, thereby securing high-temperature stability of the polyimide film.
  • the elastic modulus of the polyimide film may be 5 GPa or more, and the strength may be 340 MPa or more.
  • the polyimide film may have a glass transition temperature (Tg) of 360° C. or more and an elongation of 60% or more.
  • Tg glass transition temperature
  • composition and composition ratio containing 4,4'-diaminobenzanilide containing an amide group of the present invention expresses a desirable level of strength At the same time, it can play a major role in suppressing the expression of a decrease in elongation.
  • Some diamine components and some dianhydride components are reacted in an excess amount in a solvent to form a first composition, and some diamine components and some dianhydride components in another solvent are reacted in an excess amount to form a first composition.
  • the method of polymerizing by making it mole, etc. are mentioned.
  • the polymerization method is not limited to the above examples, and any known method may be used for preparing the polyamic acid.
  • a dianhydride component including biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylic dianhydride (BTDA), and oxydianiline ( ODA)
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • BTDA benzophenonetetracarboxylic dianhydride
  • ODA oxydianiline
  • the content of oxydianiline is 23 mol% or more and 43 mol% or less
  • the content of paraphenylene diamine is 50 mol% or more and 60 mol% or less
  • the content of the 4,4'-diaminobenzanilide is 10 mol% or more and 30 mol% or less
  • the biphenyltetracarboxylic dianhydride based on 100 mol% of the total content of the dianhydride component
  • the content of the pyromellitic dianhydride is 50 mol% or more and 65 mol% or less
  • the content of the benzophenone tetracarboxylic dianhydride is 10 mol% or more 35 mol% or less.
  • the polyimide film may have an elastic modulus of 5 GPa or more, strength of 340 MPa or more, a glass transition temperature (Tg) of 360° C. or more, and an elongation of 60% or more.
  • the polymerization method of the polyamic acid as described above can be defined as a random polymerization method, and the polyimide film prepared from the polyamic acid of the present invention manufactured by the above process has improved mechanical properties and heat resistance. It can be preferably applied to the effect of the present invention.
  • the solvent for synthesizing the polyamic acid is not particularly limited, and any solvent can be used as long as it dissolves the polyamic acid, but an amide-based solvent is preferable.
  • the solvent may be an organic polar solvent, and in detail, may be an aprotic polar solvent, for example, N,N-dimethylformamide (DMF), N,N- Dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), p-chlorophenol, o-chlorophenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), Digrim ( Diglyme), but is not limited thereto, and may be used alone or in combination of two or more, if necessary.
  • DMF N,N-dimethylformamide
  • DMAc N,N- Dimethylacetamide
  • NMP N-methyl-pyrrolidone
  • p-chlorophenol o-chlorophenol
  • N-methyl-pyrrolidone NMP
  • GBL gamma butyrolactone
  • Digrim Diglyme
  • N,N-dimethylformamide and N,N-dimethylacetamide may be particularly preferably used as the solvent.
  • fillers other than nano silica may be added for the purpose of improving various properties of the film, such as sliding properties, thermal conductivity, corona resistance, and loop hardness.
  • the filler to be added is not particularly limited, but preferable examples include titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like.
  • the particle size 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. Generally, the average particle size is 0.05 to 100 ⁇ m, preferably 0.1 to 75 ⁇ m, more preferably 0.1 to 50 ⁇ m, particularly preferably 0.1 to 25 ⁇ m.
  • the addition amount of the filler is not particularly limited either, and may be determined according to the properties of the film to be modified, the particle size of the filler, and the like. Generally, the added amount of the filler is 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, and more preferably 0.02 to 80 parts by weight, based on 100 parts by weight of the polyimide.
  • the added amount of the filler is less than this range, the modification effect by the filler is difficult to appear, and if it exceeds this range, the mechanical properties of the film may be significantly damaged.
  • the method of adding the filler is not particularly limited, and any known method may be used.
  • the polyimide film may be prepared by thermal imidation or chemical imidation.
  • it may be prepared by a complex imidation method in which thermal imidation and chemical imidation are combined.
  • the thermal imidization method is a method of inducing an imidization reaction by excluding a chemical catalyst and using a heat source such as hot air or an infrared dryer.
  • the amic acid group present in the gel film may be imidized by heat-treating the gel film at a variable temperature in the range of 100 to 600 ° C, specifically 200 to 500 ° C, more specifically , Heat treatment at 300 to 500 ° C. may imidize the amic acid group present in the gel film.
  • amic acid about 0.1 mol% to 10 mol% may be imidized even in the process of forming the gel film. This may also be included in the scope of the thermal imidization method.
  • a polyimide film may be prepared using a dehydrating agent and an imidizing agent according to a method known in the art.
  • dehydrating agent means a substance that promotes a ring closure reaction through dehydration of polyamic acid, and non-limiting examples thereof include aliphatic acid anhydride, aromatic acid anhydride, N,N' -dialkyl carbodiimide, halogenated lower aliphatic, halogenated lower patty acid anhydride, aryl phosphonic dihalide, and thionyl halide; and the like.
  • aliphatic acid anhydride may be preferred in view of ease of availability and cost, and non-limiting examples thereof include acetic anhydride (or acetic anhydride, AA), propion acid anhydride, and lactic acid anhydride. Acid anhydride etc. are mentioned, These can be used individually or in mixture of 2 or more types.
  • the term "imidizing agent” means a substance having an effect of accelerating a ring closure reaction for polyamic acid, and for example, an imine component such as aliphatic tertiary amine, aromatic tertiary amine, and heterocyclic tertiary amine can Among these, heterocyclic tertiary amines may be preferable from the viewpoint of reactivity as a catalyst.
  • the heterocyclic tertiary amine include quinoline, isoquinoline, ⁇ -picoline (BP), pyridine, and the like, and these may be used alone or in combination of two or more.
  • the addition amount of the dehydrating agent is preferably in the range of 0.5 to 5 moles, particularly preferably in the range of 1.0 to 4 moles, based on 1 mole of amic acid groups in the polyamic acid.
  • the amount of the imidizing agent added is preferably within the range of 0.05 mol to 2 mol, and may be particularly preferably within the range of 0.2 mol to 1 mol, based on 1 mol of the amic acid group in the polyamic acid.
  • a dehydrating agent and an imidizing agent are added to a polyamic acid solution, and then heated at 80 to 200 ° C, preferably 100 to 180 ° C, partially cured and dried, and then 5 to 400 ° C at 200 to 400 ° C.
  • a polyimide film can be manufactured by heating for a second.
  • the present invention provides a multilayer film comprising the above-described polyimide film and a thermoplastic resin layer, and a flexible metal-clad laminate comprising the above-described polyimide film and electrically conductive metal foil.
  • thermoplastic resin layer for example, a thermoplastic polyimide resin layer may be applied.
  • the metal foil used is not particularly limited, but in the case of using the flexible metal clad laminate of the present invention for electronic devices or electrical devices, for example, copper or copper alloy, stainless steel or its alloy, nickel or nickel alloy (42 alloy) Also included), it may be a metal foil containing aluminum or aluminum alloy.
  • copper foils such as rolled copper foil and electrolytic copper foil are often used, and they can be preferably used in the present invention as well.
  • a rust prevention layer, a heat resistance layer, or an adhesive layer may be applied to the surface of these metal foils.
  • the thickness of the metal foil is not particularly limited, and may be any thickness capable of exhibiting sufficient functions depending on its use.
  • a metal foil is laminated on one surface of the polyimide film, or an adhesive layer containing thermoplastic polyimide is added to one surface of the polyimide film, and the metal foil is attached to the adhesive layer. It may be a laminated structure.
  • the present invention also provides an electronic component including the flexible metal clad laminate as an electrical signal transmission circuit.
  • Inject DMF while injecting nitrogen into a 500 ml reactor equipped with a stirrer and nitrogen inlet/discharge pipe, set the temperature of the reactor to 30 ° C, and then oxydianiline (ODA), paraphenylene diamine (PPD) and 4 as diamine components ,4'-diaminobenzanilide (DABA) and biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylic dianhydride as dianhydride components (BTDA) was added to confirm complete dissolution.
  • ODA oxydianiline
  • PPD paraphenylene diamine
  • DABA paraphenylene diamine
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • BTDA benzophenonetetracarboxylic dianhydride
  • a catalyst and a dehydrating agent were added to the polyamic acid thus prepared, and air bubbles were removed through high-speed rotation of 1,500 rpm or more, and then applied to a glass substrate using a spin coater.
  • a gel film was prepared by drying at a temperature of 120 ° C. for 30 minutes under a nitrogen atmosphere, and the temperature was raised to 450 ° C. at a rate of 2 ° C./min, followed by heat treatment at 450 ° C. for 60 minutes, followed by 2 to 30 ° C. By cooling again at a rate of °C/min, a final polyimide film was obtained and peeled off from the glass substrate by dipping in distilled water.
  • the thickness of the prepared polyimide film was 15 ⁇ m.
  • the thickness of the prepared polyimide film was measured using Anritsu's Electric Film thickness tester.
  • Modulus of elasticity, strength and elongation were measured using Instron 3365SER equipment according to the ASTM D 882 measurement method.
  • T g glass transition temperature
  • the polyimide film prepared according to the embodiment of the present invention has an elastic modulus of 5 GPa or more, strength of 340 MPa or more, excellent mechanical strength, and a glass transition temperature (Tg) of 360 ° C or more. Correspondingly, the thermal stability was excellent.
  • the elongation corresponds to 60% or more, so that excellent mechanical strength and excellent elongation could be achieved together.
  • the elastic modulus of the polyimide films of Comparative Examples 1 to 3 was higher than that of the polyimide films of Examples 1 to 4.
  • the strength and elongation of the polyimide films of Comparative Examples 1 to 3 were lower than those of the polyimide films of Examples 1 to 4, and in particular, the polyimide films of Comparative Examples 2 and 3 were superior to the polyimide films of Examples 1 to 4. In comparison, the glass transition temperature was also found to be low.
  • the polyimide film according to the embodiment of the present invention may simultaneously have excellent high heat resistance properties and mechanical properties by using a combination of a specific dianhydride component and a specific diamine component in a specific molar ratio. In addition, adhesion can be improved.
  • the present invention can be usefully applied to electronic parts such as flexible metal clad laminates including the polyimide film as described above.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

La présente invention concerne un film de polyimide et son procédé de fabrication, le film de polyimide étant fabriqué par imidisation d'une solution d'acide polyamique comprenant : un composant d'acide dianhydride comprenant un dianhydride biphényltétracarboxylique (BPDA), un dianhydride pyromellitique (PMDA) et un dianhydride benzophénonetétracarboxylique (BTDA) ; ainsi qu'un composant diamine comprenant de l'oxydianiline (ODA), de la paraphénylène diamine (PPD) et du 4,4 '-diaminobenzanilide (DABA).
PCT/KR2022/014670 2021-09-30 2022-09-29 Film de polyimide présentant une résistance mécanique et une résistance à la chaleur améliorées et son procédé de fabrication Ceased WO2023055133A1 (fr)

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