WO2022065804A1 - Film de polyimide à faible constante diélectrique et son procédé de fabrication - Google Patents

Film de polyimide à faible constante diélectrique et son procédé de fabrication Download PDF

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WO2022065804A1
WO2022065804A1 PCT/KR2021/012687 KR2021012687W WO2022065804A1 WO 2022065804 A1 WO2022065804 A1 WO 2022065804A1 KR 2021012687 W KR2021012687 W KR 2021012687W WO 2022065804 A1 WO2022065804 A1 WO 2022065804A1
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dianhydride
mol
component
polyimide film
diamine
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PCT/KR2021/012687
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English (en)
Korean (ko)
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조민상
이길남
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피아이첨단소재 주식회사
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Priority to CN202180064230.2A priority Critical patent/CN116194512A/zh
Publication of WO2022065804A1 publication Critical patent/WO2022065804A1/fr

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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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • 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 low-k polyimide film having improved dielectric properties and a method for manufacturing the same.
  • Polyimide (PI) is a polymer material with the highest level of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials based on an imide ring with excellent chemical stability along with a rigid aromatic main chain. am.
  • Such a thin circuit board has a structure in which a circuit including a metal foil is formed on a polyimide film that is easy to bend while having excellent heat resistance, low temperature resistance and insulating properties is widely used.
  • 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 and insulating film for thin circuit boards.
  • the dielectric properties are not excellent enough to maintain sufficient insulation in high-frequency communication.
  • the insulator has a low dielectric characteristic, it is possible to reduce the occurrence of undesirable stray capacitance and noise in the thin circuit board, thereby substantially solving the cause of communication delay.
  • polyimide with low dielectric properties is recognized as the most important factor in the performance of thin circuit boards.
  • Dielectric dissipation factor (Df) refers to the degree of dissipation of electrical energy in a thin circuit board, and is closely related to the signal propagation delay that determines communication speed. It is recognized as an important factor in the performance of the substrate.
  • the polyimide film contains more moisture, the dielectric constant increases and the dielectric loss factor increases.
  • a polyimide film it is suitable as a material for a thin circuit board due to its excellent intrinsic properties, but may be relatively vulnerable to moisture due to polar imide groups, which may deteriorate insulation properties.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-2015-0069318
  • An object of the present invention is to provide a polyimide film having high heat resistance, low dielectric properties, and low moisture absorption properties, and a method for manufacturing the same.
  • a dianhydride component comprising a biphenyltetracarboxylic dianhydride (BPDA) and a pyromellitic dianhydride (PMDA); and
  • the content of m-tolidine is 30 mol% or more and 50 mol% or less
  • the content of paraphenylene diamine is 50 mol% or more and 70 mol% or less
  • polyimide film is provided.
  • the content of the biphenyltetracarboxylic dianhydride is 45 mol% or more and 65 mol% or less, based on 100 mol% of the total content of the dianhydride component, and pyromelliticdian
  • the content of hydride (PMDA) may be 35 mol% or more and 55 mol% or less.
  • the polyimide film may include a block copolymer consisting of two or more blocks.
  • a first block obtained by imidizing a dianhydride component containing biphenyltetracarboxylic dianhydride and a diamine component containing m-tolidine and paraphenylene diamine;
  • the polyimide film may have a glass transition temperature (Tg) of 300° C. or more and a dielectric loss factor (Df) of 0.003 or less.
  • moisture permeability may be 0.02 (g/(m 2 *day))/ ⁇ m) or less, and the thermal expansion coefficient may be 15 to 18 ppm/°C.
  • Another embodiment of the present invention comprises the steps of: (a) polymerizing a first dianhydride component and a first diamine component in an organic solvent to prepare a first polyamic acid;
  • the first dianhydride component and the second dianhydride component each include at least one selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA),
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • the first diamine component and the second diamine component each include at least one selected from the group consisting of m-tolidine and paraphenylene diamine (PPD),
  • the content of m-tolidine is 30 mol% or more and 50 mol% or less
  • the content of paraphenylene diamine is 50 mol% or more It provides a method for producing a polyimide film, which is 70 mol% or less.
  • the present invention provides a multilayer film comprising the above-described polyimide film and a thermoplastic resin layer.
  • the present invention provides a flexible metal clad laminate comprising the above-described polyimide film and an electrically conductive metal foil.
  • the polyimide film according to the embodiment of the present invention can have low dielectric properties and high heat resistance properties by minimizing moisture absorption and air permeability by using a specific dianhydride component and a specific diamine component in a specific molar ratio in combination.
  • the present invention can implement high-speed communication at a high frequency of 10 GHz or more including the polyimide film as described above, and thus can be usefully applied to electronic components such as flexible metal clad laminates.
  • dianhydride is intended to include precursors or derivatives thereof, which may not technically be dianhydride acids, but will nevertheless react with a diamine to form a polyamic acid, which in turn is a polyamic acid can be converted into mids.
  • diamine is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nevertheless react with dianhydrides to form polyamic acids, which in turn are polyamic acids. can be converted into mids.
  • the polyimide film according to the present invention is prepared by imidizing a polyamic acid solution containing a dianhydride component and a diamine component.
  • the dianhydride component may include at least one selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA).
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • the diamine component may include at least one selected from the group consisting of m-tolidine and paraphenylene diamine (PPD).
  • PPD paraphenylene diamine
  • the polyimide film of the present invention includes a dianhydride component including biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA), m-tolidine and It can be obtained by imidating a polyamic acid solution containing a diamine component including paraphenylene diamine (PPD).
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • m-tolidine m-tolidine
  • PPD paraphenylene diamine
  • the present invention can implement the crystallinity of the film through the biphenyltetracarboxylic dianhydride (BPDA) and m-tolidine (m-tolidine).
  • BPDA biphenyltetracarboxylic dianhydride
  • m-tolidine m-tolidine
  • the content of m-tolidine is 0 mol% or more and 50 mol% or less, based on 100 mol% of the total content of the diamine component, and the content of paraphenylene diamine It may be 50 mol% or more and 70 mol% or less.
  • the m-tolidine may be included in an amount of 30 mol% or more and 50 mol% or less.
  • Such m-tolidine has a particularly hydrophobic methyl group, and thus may contribute to the low moisture absorption properties of the polyimide film.
  • m-tolidine and paraphenylene diamine are included in the diamine component in the above content range, low dielectric properties may be obtained and low transmission loss characteristics may be obtained even at high frequencies.
  • the content of the biphenyltetracarboxylic dianhydride (BPDA) is 45 mol% or more and 65 mol% or less, based on 100 mol% of the total content of the dianhydride component, and pyromellitic dianhydride
  • the content of the ride (PMDA) may be 35 mol% or more and 55 mol% or less.
  • the content of the biphenyltetracarboxylic dianhydride (BPDA) is 45 mol% or more and 55 mol% or less
  • the content of the pyromellitic dianhydride (PMDA) is 45 mol% or more and 55 mol% or less
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • the mechanical properties of the polyimide film are improved, and to prepare a flexible metal clad laminate It is possible to secure an appropriate level of heat resistance.
  • 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. It has a regular linear structure positioned close to each other, and the intermolecular interaction is strengthened.
  • CTC charge transfer complex
  • this structure Since this structure has an effect of preventing hydrogen bonding with moisture, it can affect the lowering of the moisture absorption rate of moisture, thereby maximizing the effect of lowering the moisture permeability of the polyimide film.
  • the pyromellitic dianhydride included as the dianhydride component is preferable in that it has a relatively rigid structure and can impart appropriate elasticity to the polyimide film.
  • the content ratio of dianhydride is particularly important. For example, as the content ratio of biphenyltetracarboxylic dianhydride decreases, it becomes difficult to expect a low moisture absorption rate due to the CTC structure.
  • biphenyltetracarboxylic dianhydride contains two benzene rings corresponding to the aromatic moiety
  • pyromellitic dianhydride contains one benzene ring corresponding to the aromatic moiety
  • An 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. It can be understood that the ratio of the imide groups derived from the pyromellitic dianhydride in the polyimide polymer chain is relatively increased compared to the imide groups derived from the biphenyltetracarboxylic dianhydride.
  • the increase in the pyromellitic dianhydride content can be seen as a relative increase in the imide group for the entire polyimide film, and thus it is difficult to expect a low moisture absorption rate.
  • the polyimide film may include a block copolymer consisting of two or more blocks, for example, may include two blocks.
  • Each of the two blocks is a first block obtained by imidating a dianhydride component containing biphenyltetracarboxylic dianhydride and a diamine component containing m-tolidine and paraphenylene diamine. ; and a second block obtained by imidizing a dianhydride component including biphenyltetracarboxylic dianhydride and pyromellitic dianhydride and a diamine component including m-tolidine.
  • the first block and the second block may be formed by imidation of specific monomers, respectively.
  • the polyimide film according to the present invention includes a first block having low dielectric properties and film forming processability through heat resistance and a second block for strengthening low dielectric properties through crystallinity to achieve desired high heat resistance, low dielectric properties and low dielectric properties. It may exhibit hygroscopic properties.
  • the polyimide film of the present invention can secure a glass transition temperature (Tg) of 300° C. or higher and a dielectric loss factor (Df) of 0.003 or less, thereby exhibiting high heat resistance and low dielectric properties.
  • the polyid film controls crystallization through a second block containing biphenyltetracarboxylic dianhydride and m-tolidine to minimize moisture absorption and moisture permeability, thereby improving low dielectric strength. properties can be implemented.
  • the present invention provides interlayer dimensional stability by appropriately controlling the content of biphenyltetracarboxylic dianhydride used in forming the second block as necessary to have a coefficient of thermal expansion of 15 to 18 ppm/°C similar to copper foil. can be obtained
  • the polyimide film according to the present invention may have a glass transition temperature (Tg) of 300° C. or more and a dielectric loss factor (Df) of 0.003 or less.
  • Tg glass transition temperature
  • Df dielectric loss factor
  • moisture permeability it may be 0.02 (g/(m 2 *day))/ ⁇ m) or less
  • thermal expansion coefficient it may be 15 to 18 ppm/°C.
  • the polyimide film satisfying the above-described dielectric loss factor (Df), glass transition temperature, moisture permeability and/or thermal expansion coefficient range can be used as an insulating film for flexible metal clad laminates, and the manufactured flexible metal clad laminate Even if it is used as an electrical signal transmission circuit that transmits a signal at a high frequency of GHz or higher, its insulation stability can be secured and signal transmission delay can be minimized.
  • Df dielectric loss factor
  • glass transition temperature glass transition temperature
  • moisture permeability and/or thermal expansion coefficient range can be used as an insulating film for flexible metal clad laminates, and the manufactured flexible metal clad laminate Even if it is used as an electrical signal transmission circuit that transmits a signal at a high frequency of GHz or higher, its insulation stability can be secured and signal transmission delay can be minimized.
  • the "dielectric loss factor” means a force dissipated by a dielectric (or insulator) when friction of molecules interferes with molecular motion caused by an alternating electric field.
  • the value of the dielectric loss factor is commonly used as an index indicating the ease of dissipation of electric charge (dielectric loss). The higher the dielectric loss factor, the easier it is to dissipate the charge. there is. That is, since the dielectric loss factor is a measure of power loss, the lower the dielectric loss factor, the faster the communication speed can be maintained while signal transmission delay due to power loss is alleviated.
  • the polyimide film which is an insulating film
  • the polyimide film according to the present invention may have a dielectric loss factor of 0.004 or less under a very high frequency of 10 GHz.
  • the moisture permeability which indicates the amount of moisture contained in the material, is generally known to increase the dielectric constant and dielectric loss rate when the moisture permeability is high.
  • the dielectric constant is greater than 100, in a liquid state, about 80, and when water vapor in a gaseous state, it is 1.0059.
  • the dielectric constant and dielectric loss factor of the polyimide film may be dramatically increased.
  • the dielectric constant and dielectric loss factor of the polyimide film may change rapidly with only a small amount of moisture absorption.
  • the polyimide film according to the present invention may have a moisture permeability of 0.02 (g/(m 2 *day))/ ⁇ m) or less, and the achievement of this is due to the structural characteristics of the polyimide film according to the present invention.
  • the polyimide film according to the present invention satisfies all of the above conditions, so it can be used as an insulating film for flexible metal clad laminates, and insulation stability can be secured even at high frequencies, and signal transmission delay is minimized can do.
  • the preparation of the polyamic acid is, for example,
  • the polymerization method is not limited to the above examples, and any known method may be used for the preparation of the first to third polyamic acids.
  • (d) forming a film of the precursor composition including the third polyamic acid on a support, and then imidizing the film may include.
  • the first dianhydride component and the second dianhydride component may each include at least one selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA).
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • first diamine component and the second diamine component include at least one selected from the group consisting of m-tolidine and paraphenylene diamine (PPD).
  • PPD paraphenylene diamine
  • the content of m-tolidine is 30 mol% or more and 50 mol% or less
  • the content of paraphenylene diamine is 50 mol% or more 70 mol% or less.
  • the content of the biphenyltetracarboxylic dianhydride is 45 mol% or more and 65 mol% or less, and pyromellitic
  • the content of dianhydride (PMDA) may be 35 mol% or more and 55 mol% or less.
  • the first polyamic acid includes a dianhydride component including biphenyltetracarboxylic dianhydride and a diamine component including m-tolidine and paraphenylene diamine
  • the second polyamic acid may include a dianhydride component including biphenyltetracarboxylic dianhydride and pyromellitic dianhydride and a diamine component including m-tolidine.
  • 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 prepared by the above process has a dielectric loss factor (Df) and It can be preferably applied in terms of maximizing the effect of the present invention for lowering moisture absorption and air permeability.
  • Df dielectric loss factor
  • the polymerization method of the polyamic acid may be a block polymerization method.
  • combining a polyamic acid is not specifically limited, Any solvent can be used as long as it is a solvent in which a polyamic acid is dissolved, It is preferable that it is an amide type solvent.
  • the solvent may be an organic polar solvent, specifically an aprotic polar solvent, for example, N,N-dimethylformamide (DMF), N,N- It may be at least one selected from the group consisting of dimethylacetamide, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), and Diglyme, but is not limited thereto. It can be used in combination of 2 or more types.
  • DMF N,N-dimethylformamide
  • NMP N-methyl-pyrrolidone
  • GBL gamma butyrolactone
  • Diglyme Diglyme
  • N,N-dimethylformamide and N,N-dimethylacetamide may be particularly preferably used.
  • a filler 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 preferred examples thereof include silica, 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 characteristics of the film to be modified and the type of filler to be added. Generally, the average particle diameter 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 modifying effect becomes difficult to appear, and when the particle size exceeds this range, the surface properties may be greatly impaired or the mechanical properties may be greatly reduced.
  • the added amount of a 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 polyimide.
  • the method of adding a filler is not specifically limited, Any well-known method can also be used.
  • the polyimide film may be prepared by thermal imidization and chemical imidization.
  • it may be prepared by a complex imidization method in which thermal imidization and chemical imidization are combined.
  • the thermal imidization method is a method in which a chemical catalyst is excluded and the imidization reaction is induced by a heat source such as hot air or an infrared dryer.
  • the thermal imidization method can imidize the amic acid group present in the gel film 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, The amic acid group present in the gel film can be imidized by heat treatment at 300 to 500 °C.
  • the polyamic acid composition is dried at a variable temperature in the range of 50 °C to 200 °C. and may also be included in the scope of the thermal imidization method.
  • a polyimide film may be prepared by using a dehydrating agent and an imidizing agent according to a method known in the art.
  • a polyimide film can be manufactured.
  • the polyimide film of the present invention manufactured according to the above manufacturing method may have a glass transition temperature (Tg) of 320° C. or higher, a moisture absorption rate of 0.4% or lower, and a dielectric loss factor (Df) of 0.004 or lower.
  • Tg glass transition temperature
  • Df dielectric loss factor
  • the present invention provides a multilayer film including the above-described polyimide film and a thermoplastic resin layer, and a flexible metal clad laminate including the above-described polyimide film and an electrically conductive metal foil.
  • thermoplastic resin layer for example, a thermoplastic polyimide resin layer or the like may be applied.
  • the metal foil to be used is not particularly limited, but when the flexible metal foil laminate of the present invention is used 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 comprising aluminum or an aluminum alloy.
  • copper foils such as rolled copper foils and electrolytic copper foils are often used, and they can be preferably used in the present invention as well.
  • the antirust layer, the heat-resistant layer, or the adhesive layer may be apply
  • the thickness of the metal foil is not particularly limited, and may have a thickness capable of exhibiting a sufficient function according to its use.
  • a metal foil is laminated on one surface of the polyimide film, or an adhesive layer containing a thermoplastic polyimide is added to one surface of the polyimide film, and the metal foil is attached to the adhesive layer. It may have a laminated structure.
  • the present invention also provides an electronic component including the flexible metal clad laminate as an electrical signal transmission circuit.
  • the electrical signal transmission circuit may be an electronic component that transmits a signal at a high frequency of at least 2 GHz, specifically, a high frequency of at least 5 GHz, and more specifically, a high frequency of at least 10 GHz.
  • the electronic component may be, for example, a communication circuit for a portable terminal, a communication circuit for a computer, or a communication circuit for aerospace, but is not limited thereto.
  • DMF was introduced while nitrogen was injected into a 500 ml reactor equipped with a stirrer and nitrogen injection and discharge tube, and the temperature of the reactor was set to 30 ° C.
  • a diamine component m-tolidine and paraphenylene diamine; Biphenyltetracarboxylic dianhydride is added as a dianhydride component to confirm that it is completely dissolved.
  • a first polyamic acid having a viscosity of 200,000 cP at 23°C was prepared after stirring was continued for 120 minutes while heating and raising the temperature to 40°C in a nitrogen atmosphere.
  • NMP was introduced while nitrogen was injected into a 500 ml reactor equipped with a stirrer and nitrogen injection/discharge tube, and the temperature of the reactor was set to 30° C., m-tolidine as a diamine component, and biphenyltetracarboxylic dian Confirm that the hydride and pyromellitic dianhydride are completely dissolved.
  • a second polyamic acid having a viscosity of 200,000 cP at 23°C was prepared after stirring was continued for 120 minutes while heating and raising the temperature to 40°C in a nitrogen atmosphere.
  • the temperature of the first polyamic acid and the second polyamic acid was raised to 40° C. under a nitrogen atmosphere and stirring was continued for 120 minutes while heating, the final viscosity at 23° C. was 200,000 cP, and the diamine component and dianhydride acid
  • a third polyamic acid including the components as shown in Table 1 was prepared.
  • the third polyamic acid prepared above was bubbled through a high-speed rotation of 1,500 rpm or more. Thereafter, the polyamic acid and the catalyst are mixed and mixed, followed by film casting, and dried under a nitrogen atmosphere and at a temperature of 90-200° C. for 30 minutes to prepare a gel film, and the gel film is heated to 450° C. at a rate of 2° C./min. The temperature was raised, heat treatment was performed at 450° C. for 60 minutes, and cooling was performed to 30° C. at a rate of 2° C./min to obtain a polyimide film.
  • the polyimide film was peeled off 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 an Anritsu film thickness tester (Electric Film thickness tester).
  • Example 1 a polyimide film was prepared in the same manner as in Example 1, except that the components and their contents were respectively changed as shown in Table 1 below.
  • Dianhydride component (mol%) Diamine component (mol%) Polyamic acid polymerization method BPDA (mol%) PMDA (mol%) m-Tolidine (mol%) PPD (mol%)
  • Example 1 55 45 40 60 block polymerization Example 2 60 40 46 54 block polymerization Example 3 60 40 34 66 block polymerization Example 4 48 52 46 54 block polymerization Comparative Example 1 40 60 90 10 block polymerization Comparative Example 2 50 50 60 40 block polymerization Comparative Example 3 40 60 100 - block polymerization Comparative Example 4 60 40 100 - block polymerization Comparative Example 5 50 50 50 50 block polymerization
  • Moisture permeability was measured using a Permatran-W 3/33 MA instrument at 38 ⁇ 2°C, 100% R.H. (Measurement standards are in accordance with ASTM F1249).
  • the dielectric loss factor (Df) was measured by leaving the flexible metal clad laminate for 72 hours using an Agilent 4294A ohmmeter.
  • CTE coefficient of thermal expansion
  • the glass transition temperature (T g ) was obtained by obtaining the loss modulus and storage modulus of each film using DMA, and the inflection point was measured as the glass transition temperature in their tangent graph.
  • the polyimide film prepared according to the embodiment of the present invention exhibits a remarkably low dielectric loss factor of 0.003 or less, and the glass transition temperature is at a desired level.
  • the moisture permeability also showed excellent results, and it was found that the filmization was well implemented because it had excellent flatness because wrinkles did not occur.
  • Comparative Examples 2 and 4 it can be seen that the filmization is not realized because the flatness of the film is not constant due to the inflow of wrinkles. From this, it can be expected that the comparative examples are difficult to be used in electronic components in which signals are transmitted at high frequencies in the unit of gigabytes.
  • the polyimide film according to the embodiment of the present invention can have low dielectric properties and high heat resistance properties by minimizing moisture absorption and air permeability by using a specific dianhydride component and a specific diamine component in a specific molar ratio in combination.
  • the present invention can implement high-speed communication at a high frequency of 10 GHz or more, including the polyimide film as described above, and thus can be usefully applied to electronic components such as flexible metal clad laminates.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

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 dianhydride d'acide comprenant un dianhydride biphényltétracarboxylique (BPDA) et un dianhydride pyromellitique (PMDA) ; et un composant diamine comprenant une m-tolidine et une p-phénylènediamine (PPD). Selon l'invention, sur la base de 100 % en moles de la quantité totale du composant diamine, la quantité de m-tolidine est de 30 à 50 % en moles et la quantité de PPD est de 50 à 70 % en moles.
PCT/KR2021/012687 2020-09-23 2021-09-16 Film de polyimide à faible constante diélectrique et son procédé de fabrication WO2022065804A1 (fr)

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