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WO2020096363A1 - Film composite de polyimide ayant d'excellentes caractéristiques diélectriques et son procédé de formation - Google Patents

Film composite de polyimide ayant d'excellentes caractéristiques diélectriques et son procédé de formation Download PDF

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Publication number
WO2020096363A1
WO2020096363A1 PCT/KR2019/015044 KR2019015044W WO2020096363A1 WO 2020096363 A1 WO2020096363 A1 WO 2020096363A1 KR 2019015044 W KR2019015044 W KR 2019015044W WO 2020096363 A1 WO2020096363 A1 WO 2020096363A1
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Prior art keywords
bis
aminophenoxy
phenyl
composite film
polyimide
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English (en)
Korean (ko)
Inventor
이길남
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PI Advanced Materials Co Ltd
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SKCKolon PI Co Ltd
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Priority claimed from KR1020190141138A external-priority patent/KR102284431B1/ko
Application filed by SKCKolon PI Co Ltd filed Critical SKCKolon PI Co Ltd
Priority to CN201980073463.1A priority Critical patent/CN112996664B/zh
Publication of WO2020096363A1 publication Critical patent/WO2020096363A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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

Definitions

  • the present invention relates to a polyimide composite film having excellent dielectric properties and a method for manufacturing the same.
  • Polyimide (PI) is a polymer having 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 backbone It is material. Therefore, polyimide has been spotlighted as an insulating material for microelectronic components in which the aforementioned properties are strongly required.
  • FPCB flexible printed circuit board
  • TAB tape automated bonding
  • COF chip on film
  • microelectronic component examples include a thin circuit board having high circuit density and being flexible so as to be able to cope with the weight reduction and miniaturization of electronic products, and the polyimide is widely used as an insulating film for thin circuit boards.
  • an insulator having a high impedance capable of maintaining electrical insulation even at high frequencies is required.
  • Impedance is inversely related to the frequency and dielectric constant (dielectric constant, Dk) formed on the insulator, so the dielectric constant should be as low as possible to maintain insulation even at high frequencies.
  • the dielectric constant is not high enough to maintain sufficient insulation in high-frequency communication with a degree of 3.4 to 3.6, for example, partially or wholly insulation in a thin circuit board in which high-frequency communication of 2 GHz or higher is performed. There is a possibility of loss.
  • the dielectric constant of the insulator the less the occurrence of undesirable stray capacitance and noise in a thin circuit board, and thus, it is known that the cause of communication delay can be substantially eliminated.
  • the dielectric constant of is recognized as the most important factor in the performance of a thin circuit board.
  • the present invention provides a polyimide composite film having excellent dielectric constant, dielectric constant and moisture absorption.
  • the polyimide composite film of the present invention includes a core layer and a skin layer as essential factors, and the skin layer may advantageously act to impart a low moisture absorption rate and dielectric constant of the polyimide composite film.
  • the skin layer includes a second polyimide resin, which may have a coefficient of thermal expansion suitable for adhesion to, for example, a thermoplastic polyimide or metal foil, and based on this, the polyimide composite film is formed from a thermoplastic polyimide or metal foil.
  • the second polyimide resin based on its molecular structure, may advantageously have a skin layer having excellent dielectric properties, such as low dielectric constant.
  • the skin layer also includes a fluorine-based resin capable of inhibiting moisture penetration through its surface and / or diffusion of moisture therein. This can lower the moisture absorption rate, which can adversely affect the dielectric properties, and as a result, the polyimide composite film may have inherent dielectric properties in a desirable form, and in particular, have a low dielectric constant.
  • the polyimide composite film of the present invention further includes a core layer comprising a first polyimide resin having excellent mechanical rigidity. Based on this core layer, the polyimide composite film can be exhibited with excellent mechanical properties, such as tensile strength and modulus, at desired levels.
  • the present invention provides a production method suitable for implementing a novel polyimide composite film having the above advantages.
  • the present invention provides a flexible metal foil-clad laminate comprising a novel polyimide composite film having the above and a few advantages.
  • the present invention has a practical purpose in providing a specific embodiment thereof.
  • the invention in one embodiment, the invention
  • a core layer comprising a first polyimide resin
  • the skin layer contains 60% by weight or less of a fluorine-based resin based on the total weight of the skin layer,
  • a polyimide composite film having a dielectric loss of 0.003 or less, a dielectric constant (Dk) of 3.2 or less, and a moisture absorption rate of 0.6 or less.
  • the polyimide composite film according to the present invention may have an elongation of 30% or more, specifically 40% or more.
  • the present invention provides a method specialized in preparing the polyimide composite film.
  • the present invention provides a flexible metal thin laminate plate comprising the polyimide composite film, an electronic component including the flexible metal thin laminate plate as an electrical signal transmission circuit, wherein the electrical signal transmission circuit is at least 2 GHz. It may be an electronic component that transmits a signal at a high frequency.
  • dianhydride dianhydride
  • dianhydride is intended to include its precursors or derivatives, which may not technically be dianhydrides, but nevertheless react with diamines to form polyamic acids. And this polyamic acid can be converted back to polyimide.
  • Diamine as used herein 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 are polyamic The acid can be converted back to polyimide.
  • 1 is a schematic view of a co-extruder.
  • the polyimide composite film according to the present invention may be a multilayer composite film having a thickness of 10 to 100 ⁇ m, specifically 10 to 75 ⁇ m, and more specifically 10 to 50 ⁇ m.
  • a core layer comprising a first polyimide resin
  • It may include a second polyimide resin and a fluorine-based resin, and may include at least one skin layer formed in a state bonded to at least one surface of the core layer.
  • the first polyimide resin and the second polyimide resin may be prepared by polymerization of diamine monomers and dianhydride monomers, respectively.
  • the diamine monomer is the diamine monomer
  • 1,4-diaminobenzene (or paraphenylenediamine, PDA, PPD), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzo Diaminodiphenyl ethers, such as diacid (or DABA), 4,4'-diaminodiphenyl ether (or oxidianiline, ODA), 3,4'-diaminodiphenyl ether, 4,4'-dia Minodiphenylmethane (or 4,4'-methylenediamine, MDA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl , 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamino
  • the dianhydride monomer is pyromellitic dianhydride (or PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (or s-BPDA), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (or a-BPDA), oxydiphthalic dianhydride (or ODPA), diphenylsulfone-3,4,3', 4 ' -Tetracarboxylic dianhydride (or DSDA), bis (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3 , 3,3-hexafluoropropane dianhydride, 2,3,3 ', 4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride
  • the monomers capable of implementing the first polyimide resin and / or the second polyimide resin may be components having a relatively rigid molecular structure, which is excellent in mechanical properties of the first polyimide resin and / or the second polyimide resin.
  • Strength such as good tensile strength and inherent modulus, can be directly related. As a result, the tensile strength and modulus of the core layer including the first polyimide resin and the polyimide composite film including the core layer may lead to being expressed at a desired level.
  • the diamine monomer may include two or more components selected from the group consisting of m-tolidine, O-tolidine, ODA and PPD, and more specifically m-tolidine and O- It may include one of tolidine and one or more components of ODA and PPD.
  • the benzidine structure possessed by m-tolidine and O-tolidine minimizes water penetration into the skin layer, water diffusion, and the like, and can mainly act to improve the moisture absorption rate of the polyimide composite film.
  • the skin layer contains a fluorine-based resin that is classified as relatively hydrophobic, and as the second polyimide resin and the fluorine-based resin having such a benzidine structure exhibit a synergistic effect, moisture absorption through the skin layer is significantly suppressed. Can be.
  • the skin layer including the second polyimide resin and the fluorine-based resin may improve the moisture absorption rate that may adversely affect the dielectric properties and may advantageously be implemented in a desired aspect of the dielectric properties of the polyimide composite film.
  • the dianhydride monomer may have a relatively rigid molecular structure, and specifically include one or more components selected from the group consisting of PMDA, s-BPDA, a-BPDA and BTDA. It may be, and more specifically, may include two or more selected from the group consisting of PMDA, s-BPDA and a-BPDA.
  • the combination of monomers capable of implementing the core layer and / or skin layer of the present invention are components having a relatively rigid molecular structure, and the core layer and / or skin layer have excellent mechanical strength, such as excellent tensile strength and modulus. It can work to your advantage.
  • first polyimide resin and / or the second polyimide resin prepared by the monomer combination has advantages related to low moisture absorption, but has dielectric properties that affect the electrical insulation properties of the polyimide composite film, such as low dielectric constant. Can be advantageously expressed.
  • the fluorine-based resin is at least one selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene propylene (FEP) and ethylenetetrafluoroethylene (ETFE). It may include, in detail, it may be a polytetrafluoroethylene that is excellent in compatibility with the second polyimide resin and does not cause a decrease in adhesion.
  • PTFE polytetrafluoroethylene
  • PFA perfluoroalkoxy
  • FEP fluorinated ethylene propylene
  • ETFE ethylenetetrafluoroethylene
  • the fluorine-based resin may be present in the skin layer in at least one state selected from:
  • the fluorine-based resin present in the first state may be physically entangled in the polymer chain of the second polyimide resin, which may advantageously inhibit water penetration into the skin layer and / or diffusion of water within the skin layer.
  • the fluorine-based resin present in the second state is hydrogen bonded to a polar group in the polymer chain of the second polyimide resin, such as an imide group, and may provide advantages similar to the second state.
  • the fluorine-based resin present in a predetermined amount while present in the first state and the second state, respectively, acts positively as described above, but when included in an excessive amount, deterioration of mechanical properties of the skin layer, in particular, tensile It can cause a significant decrease in strength and modulus, and can significantly decrease the surface properties of the produced film.
  • the surface properties include, for example, thermal wrinkles.
  • the skin layer containing too little fluorine-based resin is difficult to embed the above-mentioned advantages for moisture.
  • the content of the fluorine-based resin should be determined in a range in which there is no deterioration in the physical properties of the skin layer and further the polyimide composite film. Accordingly, in the present invention, the fluorine-based resin is added to the total weight of one skin layer. With respect to 10 to 60% by weight, specifically 20 to 50% by weight may be included.
  • the first skin layer is 10 to 60% by weight relative to the total weight thereof, Specifically, 30 to 60% by weight, in particular 40 to 60% by weight of a fluorine-based resin
  • the second skin layer is 10 to 60% by weight relative to its total weight, specifically 30 to 60% by weight , In particular, it may include 40 to 60% by weight of a fluorine-based resin.
  • the polyimide composite film according to the present invention is a multi-layered composite film composed of a skin layer and a core layer
  • the polyimide resins constituting each layer may each have a specific composition, and accordingly, the skin layer and the core layer may have any Desired physical properties can be inherent.
  • the skin layer of the present invention may be directly related to the polyimide composite film having a low moisture absorption rate and a dielectric constant based on the second polyimide resin and fluorine resin constituting the same, and the core layer of the polyimide composite film While supporting the shape, it may be advantageous to meet various mechanical properties required for the insulating film.
  • a conventional polyimide monolayer film that does not include a skin layer and a core layer may include, for example, a fluorine-based resin.
  • the polyimide monolayer film contains a fluorine-based resin for the purpose of suppressing moisture permeation
  • a large amount of fluorine-based resin may be present inside the polyimide film, for example, in the center of the film, and the concentration of the fluorine-based resin in the surface direction of the film from the center of the film A gradually decreasing concentration gradient may appear. Therefore, a conventional polyimide monolayer film has a limit to suppress the penetration of moisture through the surface even if it contains a fluorine-based resin.
  • the polyimide monolayer film has been required to contain a relatively high content of a fluorine-based resin so that a large number of fluorine-based resins may be present on the surface of the film and adjacent portions thereof.
  • the fluorine-based resin can significantly degrade the mechanical properties of the polyimide film, the polyimide film can be expected to improve the moisture absorption rate at the expense of the mechanical properties.
  • the single-layer polyimide film is composed of a single polyimide resin produced by any one monomer combination, not only the desired level of mechanical properties, but also the correlation with each other to the desired level of moisture absorption, dielectric constant, and thermal expansion coefficient Is difficult.
  • the polyimide composite film according to the present invention can be compatible with a variety of properties that are less related to each other based on its special structure, which is a specific effect in that it cannot be expressed in a conventional single-layer polyimide film. It can be recognized as.
  • the polyimide composite film may include a first skin layer having a skin layer formed on one surface of the core layer and a second skin layer formed on the other surface of the core layer,
  • the first skin layer contains 10 to 60% by weight of fluorine-based resin based on the total weight thereof, and the second skin layer contains 10 to 60% by weight of fluorine-based resin based on its total weight,
  • the ratio of the thickness of the core layer to the sum of the thicknesses of the first skin layer and the second skin layer is 1 to 5, specifically 1.5 to 4, more specifically, may be 2.0 to 3.0.
  • Each of the first skin layer and the second skin layer may be a single layer composed of one layer, and in some cases, may be formed in the form of a composite layer laminated with a plurality of unit layers bonded together.
  • the sum of the thicknesses of the first skin layer and the second skin layer and the thickness ratio of the core layer are particularly important when the mechanical properties of the polyimide composite film are maintained at a predetermined level, while the desired level of moisture absorption and dielectric properties are expressed. Can be.
  • the polymer chains of the second polyimide resin constituting the skin layer are excessively reduced to exclude the fluorine resin, thereby substantially reducing the It is difficult to form, and the structure can break even if layered.
  • the thickness of the first skin layer and the second skin layer may be the same or different from each other, and when different, 7: 3 to 3: 7 (first skin layer: second skin layer) except 5: 5 It can have a thickness ratio.
  • the polyimide composite film according to the present invention may have a dielectric loss (Df) of 0.003 or less, a dielectric constant (Dk) of 3.2 or less, and a moisture absorption of 0.6% by weight or less.
  • the permittivity is an important characteristic value indicating the electrical properties of a dielectric (or insulator), that is, a nonconductor.
  • the dielectric constant is not directly related to the electrical properties of DC current, but is directly related to the properties of AC current, especially AC electromagnetic waves. It is said to be.
  • + and-moment components which are normally scattered in random directions, are aligned with changes in the electromagnetic field applied from the outside. That is, by changing the moment components in accordance with the changing direction of the electromagnetic field, it is possible to enable the propagation of electromagnetic waves inside the non-conductor yet on the other side.
  • a high dielectric constant means that electrical energy is well transmitted
  • an insulator such as a polyimide film is preferable as the dielectric constant is lower.
  • the conventional polyimide film is not at a level sufficient to maintain sufficient insulation in high-frequency communication. This becomes evident when compared with the dielectric constant of liquid crystal polymers.
  • the dielectric constant is known to be approximately 2.9 to 3.3, and most of them are superior to insulators compared to conventional polyimides having higher dielectric constants. can see.
  • the polyimide composite film according to the present invention is close to the dielectric constant of the liquid crystal polymer, or a lower dielectric constant, specifically, the dielectric constant may be 3.2 or less, in particular, 3.0 or less, and the lower limit may be 2.0 have. It can be seen that polyimide is an ideal form as an insulator when recalling that the engineering properties are at the highest level.
  • a capacitor has a property that an impedance decreases as a frequency of a current or a voltage across the capacitor increases, and the value can be expressed by the following equation.
  • -C e * S / d; Where e is the dielectric constant, S is the area of the conductor, and d is the distance.
  • the polyimide film according to the present invention has a relatively low dielectric constant as described above, and thus it is easy to maintain insulation even in communication equipment operating at a frequency of giga (GIGA) unit, for example, ultra-high frequency of 2 GHz or more. There is this.
  • GIGA giga
  • the moisture absorption rate is a rate indicating the amount of moisture the material is absorbing, and is generally known to increase the dielectric constant and dielectric loss rate when the moisture absorption rate is high.
  • the dielectric constant is 100 or more, when it is in the liquid state, it is about 80, and when it is in the gaseous state, it is known as 1.0059.
  • water existing in a water vapor state other than the polyimide film does not substantially affect the dielectric constant and dielectric loss rate of the polyimide film.
  • water exists in a liquid state and in this case, the dielectric constant and dielectric loss rate of the polyimide film may increase dramatically. In other words, the dielectric constant and dielectric loss rate of the polyimide film may change rapidly even with a small amount of moisture absorption.
  • the polyimide composite film according to the present invention may have a moisture absorption rate of 1.0% by weight or less, specifically 0.7% by weight or less, and more specifically 0.6% by weight or less, and the achievement of the polyimide composite film of the present invention It is due to the constitutional characteristics.
  • the polyimide composite film according to the present invention includes a fluorine-based resin in which the skin layer can inhibit the penetration of moisture, and includes benzidine, which is not water-friendly due to the polymer structure of the second polyimide resin. It is presumed to be due to the manifestation of a synergistic effect.
  • the thermal expansion coefficient of the polyimide film at 300 to 350 ° C is the same as the thermal expansion coefficient of the metal foil.
  • the difference between the thermal expansion coefficient of the polyimide film and the thermal expansion coefficient of the metal foil is within ⁇ 10 ppm, detailed It is preferable to be within ⁇ 5 ppm.
  • thermoplastic polyimide when used as the adhesive layer, the dimensional change can be minimized when the thermal expansion coefficient at 340 ° C of the polyimide film is 7 ppm / ° C or higher, and less, the dimensional change in the relationship with the metal foil and the adhesive layer Can appear excessively and cause bad appearance.
  • the thermal expansion coefficient is preferably 15 ppm / ° C. or less, and when it exceeds this, the degree of expansion in the MD and TD directions is excessive, which may also cause poor appearance.
  • a more preferable range for this may be a thermal expansion coefficient of 8 ppm / ° C or more to 15 ppm / ° C or less, particularly preferably 8 ppm / ° C or more to 3 ppm / ° C or less, and the polyimide composite film according to the present invention has a thermal expansion coefficient Is within the above preferred range, it can be expected that there is an advantage in the implementation of the flexible metal foil laminate.
  • the polyimide composite film may include a core layer derived from the first composition and a skin layer derived from the second composition.
  • Each of the first polyamic acid solution and the second polyamic acid solution may include an organic solvent in which polyamic acid is soluble.
  • the organic solvent is not particularly limited as long as it is a solvent in which the polyamic acid can be dissolved, but as an example, the organic solvent may be an aprotic polar solvent.
  • amide solvents such as N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), p-chlorophenol, o-chloro And phenol-based solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma brotirolactone (GBL) and digrime, and these may be used alone or in combination of two or more.
  • the solubility of the polyamic acid may be controlled by using auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • organic solvents that can be particularly preferably used in the preparation of the first polyamic acid solution and the second polyamic acid solution of the present invention are amide solvents N, N'-dimethylformamide and N, N'-dimethyl Acetamide.
  • the method of polymerizing the first polyamic acid solution and the second polyamic acid solution may be respectively prepared through the following methods:
  • Some diamine monomer components and some dianhydride monomer components are reacted so as to be in excess in one of the organic solvents to form a first polymer, and some diamine monomer components and some dianhydride monomer components are formed in another organic solvent.
  • a method for reacting such that one is in excess to form a second polymer mixing the first and second polymers, and completing the polymerization, wherein the diamine monomer component is excessive when forming the first polymer.
  • Each of the polyamic acid contained in the first polyamic acid solution and the second polyamic acid solution may have a weight average molecular weight of 150,000 g / mole or more to 1,000,000 g / mole or less, and more specifically, 260,000 g / mole or more to 700,000 g / mole It may be the following, and more specifically, may be 280,000 g / mole or more to 500,000 g / mole or less.
  • Polyamic acid having such a weight average molecular weight may be preferable for the production of a polyimide composite film having better heat resistance and mechanical properties.
  • the weight average molecular weight of the polyamic acid can be proportional to the viscosity of the polyamic acid solution containing the polyamic acid and the organic solvent, and the weight average molecular weight of the polyamic acid can be controlled within the above range by adjusting the viscosity.
  • the viscosity of the polyamic acid solution is proportional to the content of the polyamic acid solid content, in particular, the total amount of the dianhydride monomer and the diamine monomer used in the polymerization reaction.
  • the weight average molecular weight does not represent a linear linear relationship with respect to viscosity, but is proportional to the logarithmic function.
  • the range in which the weight average molecular weight can be increased is limited while increasing the viscosity in order to obtain a higher weight average molecular weight polyamic acid, when the viscosity is too high, polya through a multi-layer die in the film forming process for coextrusion When discharging the mixed acid solution, it may cause a processability problem due to an increase in pressure inside the die.
  • each of the first polyamic acid solution and the second polyamic acid solution of the present invention may include 15% to 20% by weight of a polyamic acid solid content and 80% to 85% by weight of an organic solvent, in which case the viscosity is 90,000 It may be cP or more to 300,000 cP or less, specifically 100,000 cP or more to 250,000 cP. Within this viscosity range, the weight average molecular weight of the polyamic acid may fall within the above range, and the polyamic acid solution may not cause problems in the film forming process described above.
  • fillers may be added during the production of the first composition and the second composition for the purpose of improving various properties of the film such as sliding property, thermal conductivity, conductivity, corona resistance, and loop hardness of the polyimide composite film.
  • the filler to be added is not particularly limited, and preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
  • the average particle diameter of the filler is not particularly limited, and can be determined according to the characteristics of the polyimide composite film to be modified and the type of filler to be added.
  • the average particle diameter of the filler may be 0.05 ⁇ m to 100 ⁇ m, specifically 0.1 ⁇ m to 75 ⁇ m, more preferably 0.1 ⁇ m to 50 ⁇ m, and particularly specifically 0.1 ⁇ m to 25 ⁇ m.
  • the filler may significantly impair the surface properties of the polyimide composite film or cause mechanical properties of the composite film to deteriorate.
  • the addition amount of the filler is not particularly limited, and can be determined by the characteristics of the polyimide film to be modified, the particle size of the filler, and the like.
  • the amount of the filler added 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 polyamic acid solution.
  • the method for adding the filler is not particularly limited, and any known method can be used.
  • the step of forming the film is co-extruded on a support so as to be laminated in the order of the second composition, the first composition and the second composition, and the coextruded first composition and the second composition are 50 ° C to It may include the step of heat treatment in a temperature range of 200 °C.
  • the step of forming the film is co-extruded on a support so as to be laminated in the order of the first composition and the second composition, and the temperature of the co-extruded first composition and the second composition is 50 ° C to 200 ° C. It may include a step of heat treatment in the range.
  • the precursor composition When the precursor composition is heat-treated as described above, the precursor composition may be converted into a form having self-support in an intermediate step with respect to conversion from polyamic acid to polyimide.
  • a process of stretching the heat-treated precursor composition may be performed, and the stretching may be performed in a machine conveying direction (MD) and It may be performed in at least one of the transverse direction (TD) with respect to the machine transport direction.
  • MD machine conveying direction
  • TD transverse direction
  • the imidization step may include heat-treating the first composition and the second composition in a heat-treated state to a temperature of 200 ° C to 700 ° C again.
  • imidization refers to a phenomenon, process, or method in which the amic acid group is converted to an imide group by inducing a ring-closure and dehydration reaction of an amic acid group forming a polyamic acid through heat and / or a catalyst.
  • the imidization method may be performed through a thermal imidization method, a chemical imidization method, or a complex imidization method using a combination of the thermal imidization method and a chemical imidization method.
  • the thermal imidization method may be a method of excluding chemical catalysts and performing heat treatment at a temperature of 200 ° C to 700 ° C using a heat source such as hot air or an infrared dryer.
  • the polyimide composite film obtained as described above may be heated to a temperature of 400 ° C to 700 ° C for 5 seconds to 400 seconds to further harden the polyimide composite film, and may remain in the obtained polyimide composite film. This may be done under a given tension to relieve any internal stresses that may be present.
  • the chemical imidization method is a method of promoting imidization of an amic acid group in the imidization process by adding a dehydrating agent and / or an imidizing agent to each of the first composition and the second composition.
  • the term “dehydrating agent” refers to a substance that promotes a cyclization reaction through dehydration of a polyamic acid, and includes, without limitation, aliphatic acid anhydrides, aromatic acid anhydrides, N, N'- Dialkyl carbodiimide, halogenated lower aliphatic, halogenated lower patty acid anhydride, aryl phosphonic dihalide, thionyl halide, and the like.
  • aliphatic acid anhydrides may be preferred from the viewpoint of ease of availability and cost, and non-limiting examples include acetic anhydride (AA), propionic acid anhydride, and lactic acid anhydride. Etc. are mentioned, These can be used individually or in mixture of 2 or more types.
  • imide agent means a substance having an effect of promoting a ring-closure reaction to polyamic acid, and may be, for example, imine-based components such as aliphatic tertiary amine, aromatic tertiary amine, and heterocyclic tertiary amine. .
  • imine-based components such as aliphatic tertiary amine, aromatic tertiary amine, and heterocyclic tertiary amine.
  • heterocyclic tertiary amines may be preferable from the viewpoint of reactivity as a catalyst.
  • Non-limiting examples of heterocyclic tertiary amines include quinoline, isoquinoline, ⁇ -picoline (BP), pyridine and the like, and these may be used alone or in combination of two or more.
  • the amount of the dehydrating agent added is preferably in the range of 0.5 to 5 moles, and particularly preferably in the range of 1.0 to 4 moles, per 1 mole of the amic acid group in the polyamic acid contained in the composition.
  • the amount of the imidizing agent added is preferably in the range of 0.05 mol to 2 mol with respect to 1 mol of the amic acid group in the polyamic acid contained in the composition, and in the range of 0.2 mol to 1 mol It may be particularly desirable to be scented.
  • the composite imidization method may be to perform a thermal imidization method in addition to the above chemical imidization method.
  • the present invention provides a flexible metal foil-clad laminate comprising the polyimide composite film described in the previous embodiment.
  • a metal foil is laminated to the skin layer of the polyimide composite film, or an adhesive layer containing a thermoplastic polyimide is added to the skin layer of the polyimide composite film, and the metal foil is attached to the adhesive layer. It may be a laminated structure in the state.
  • the metal foil is not particularly limited, and may be, for example, copper, copper alloy, stainless steel, stainless steel alloy, nickel, nickel alloy, aluminum or aluminum alloy.
  • an anti-rust layer, a heat-resistant layer, or an adhesive layer may be coated on the surface of the metal foil.
  • the thickness of the metal foil may be a thickness capable of exerting a sufficient function depending on its use, and as a non-limiting example to aid implementation, the thickness of the metal foil may be 0.1 ⁇ m to 1000 ⁇ m.
  • the adhesive may be a thermoplastic polyimide-based material such as a thermoplastic polyimide thermoplastic polyamideimide, a thermoplastic polyetherimide, and a thermoplastic polyesterimide, which may be preferred in terms of dimensional stability with a polyimide composite film. This is an example to aid implementation, and is not limited thereto.
  • the flexible metal foil-clad laminate according to the present invention can be produced by a thermal lamination method of bonding a metal foil to a polyimide composite film as a base film.
  • the method allows, for example, to continuously pass a base film and a metal foil ('coated body') to a roll laminate device including two or more metal heating rolls, and the heat and pressure applied in the process may It may include a process of thermal lamination of the laminate.
  • a protective material may be disposed between the heating roll and the object to be laminated, in particular between the heating roll and the metal foil, in order to improve the appearance of the obtained flexible metal foil-clad laminate.
  • the protective material is not particularly limited as long as it is a material that can withstand the heating temperature of the thermal laminate, but may be a heat-resistant plastic such as non-thermoplastic polyimide, or a metal foil such as copper foil, aluminum foil, stainless steel foil. Among them, a non-thermoplastic polyimide having excellent heat resistance and reusability may be preferable.
  • the thickness of the protective material When the thickness of the protective material is excessively thin, when heat-laminating, the role of cushioning and protection may be insufficient, and the thickness of the protective material may be at least 70 ⁇ m, in particular, 75 ⁇ m or more.
  • the protective material may be one layer, but in some cases, it may be used in a multi-layered form of two or more layers.
  • the heating method of the layered object in the thermal laminate is not particularly limited, and for example, a heating means capable of heating to a predetermined temperature, such as a thermal circulation method, a hot air heating method, or an induction heating method, may be used.
  • a heating means capable of heating to a predetermined temperature such as a thermal circulation method, a hot air heating method, or an induction heating method
  • the method of pressing the layered object in the thermal laminate is not particularly limited, and for example, a method capable of applying a predetermined pressure, such as a hydraulic method, an air pressure method, and a gap-to-gap pressure method, may be selected and used.
  • the heating temperature that is, the laminate temperature may be + 50 ° C or higher of the polyimide film glass transition temperature (T g ) of the base film, and more specifically, to increase the lamination rate, the polyimide film glass transition It may be more than +100 °C of the temperature (T g ).
  • the first composition prepared in Preparation Example 1 is introduced into the first storage tank 101 of the coextrusion die 100 having the structure shown in FIG. 1, and the second prepared storage tank 102 is manufactured in Preparation Example 2 2 The composition was added.
  • the second composition, the first composition, and the second composition were coextruded on the endless belt 105 to form a precursor composition with a thickness of about 25 micrometers.
  • a mixture of isoquinoline, dimethylformamide and acetic anhydride was mixed from the catalyst storage tank 103.
  • the contents of the second polyamic acid solid content and the PTFE solid content in the second composition are changed as described in Table 1 below, and / or the polyimide composite film
  • a polyimide composite film was prepared in the same manner as in Example 1, except that the extrusion amount of the coextruder was controlled to have the ratio of the thickness and the thickness of the core layer and the skin layer as shown in Table 1 below.
  • a precursor composition obtained by mixing isoquinoline and acetic anhydride as a catalyst was applied to the first composition prepared in Preparation Example 1 on a SUS plate. Thereafter, heat treatment was performed in a temperature range of 100 ° C to 200 ° C, heating was performed from 200 ° C to 600 ° C in a high-temperature tenter, and then cooled at 25 ° C to obtain a polyimide film.
  • the contents of the second polyamic acid solid content and the PTFE solid content in the second composition are changed as described in Table 1 below, and / or the polyimide composite film
  • a polyimide composite film was prepared in the same manner as in Example 1, except that the extrusion amount of the coextruder was controlled to have the ratio of the thickness and the thickness of the core layer and the skin layer as shown in Table 1 below.
  • a precursor composition obtained by mixing isoquinoline, dimethylformamide and acetic anhydride as a catalyst was applied to the second composition prepared in Preparation Example 2 on a SUS plate. Then, heat treatment was performed in a temperature range of about 150 ° C, and this was heated again from 150 ° C to 600 ° C in a high-temperature tenter, and then cooled at 25 ° C to obtain a polyimide film.
  • the dielectric constant and dielectric loss were measured by connecting the E5063A to SPDR (10GHz).
  • Example 1 3.04 0.0028 0.5 Good 44
  • Example 2 3.01 0.0027 0.5 Good 42
  • Example 3 3.08 0.0029 0.4 Good 45
  • Example 4 2.98 0.0025 0.6 Good 40
  • Comparative Example 2 which included an excess of PTFE outside the scope of the present invention, a gel film having a self-supporting property was not well formed, and the appearance of wrinkles or cracks was very poor, which was not applicable to a thin circuit board. was confirmed.
  • the polyimide composite film of the present invention is excellent in dielectric constant, dielectric constant and moisture absorption.
  • the polyimide composite film of the present invention includes a core layer and a skin layer as essential factors, and the skin layer can advantageously act to impart a low moisture absorption and dielectric constant of the polyimide composite film.
  • the skin layer includes a second polyimide resin, which may have a coefficient of thermal expansion suitable for adhesion to, for example, a thermoplastic polyimide or metal foil, and based on this, the polyimide composite film is formed from a thermoplastic polyimide or metal foil.
  • the second polyimide resin based on its molecular structure, may advantageously have a skin layer having excellent dielectric properties, such as low dielectric constant.
  • the skin layer also includes a fluorine-based resin capable of inhibiting moisture penetration through its surface and / or diffusion of moisture therein. This can lower the moisture absorption rate, which can adversely affect the dielectric properties, and as a result, the polyimide composite film may have inherent dielectric properties in a desirable form, and in particular, have a low dielectric constant.
  • the polyimide composite film of the present invention further includes a core layer comprising a first polyimide resin having excellent mechanical rigidity. Based on this core layer, the polyimide composite film can be exhibited with excellent mechanical properties, such as tensile strength and modulus, at desired levels.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un film composite de polyimide comprenant : une couche centrale contenant une première résine de polyimide ; et au moins une couche de peau contenant une seconde résine de polyimide et une résine fluorée, et fixée à au moins un côté de la couche centrale.
PCT/KR2019/015044 2018-11-07 2019-11-07 Film composite de polyimide ayant d'excellentes caractéristiques diélectriques et son procédé de formation Ceased WO2020096363A1 (fr)

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CN201980073463.1A CN112996664B (zh) 2018-11-07 2019-11-07 介电特性优秀的聚酰亚胺复合膜及其制备方法

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KR20180135963 2018-11-07
KR10-2019-0141138 2019-11-06
KR1020190141138A KR102284431B1 (ko) 2018-11-07 2019-11-06 유전특성이 우수한 폴리이미드 복합 필름 및 이를 제조하는 방법

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CN112409621A (zh) * 2020-11-27 2021-02-26 桂林电器科学研究院有限公司 高强度低介电性聚酰亚胺多层膜及其制备方法
CN114919253A (zh) * 2022-05-31 2022-08-19 中山新高电子材料股份有限公司 一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法
CN115558144A (zh) * 2022-10-19 2023-01-03 嘉兴瑞华泰薄膜技术有限公司 一种聚酰亚胺氟树脂复合薄膜及其制备方法
CN115926159A (zh) * 2022-06-09 2023-04-07 常州工学院 一种电机用低介电损耗聚酰亚胺及其制备方法和应用
CN116162275A (zh) * 2023-03-14 2023-05-26 东华大学 一种聚酰亚胺复合膜及其制备方法和应用
CN117887124A (zh) * 2024-01-11 2024-04-16 无锡顺铉新材料有限公司 一种具有高温结合性能的ptfe/改性聚酰亚胺复合膜及其制备方法和应用
CN118596671A (zh) * 2024-06-24 2024-09-06 太湖聚智新材料科技有限公司 耐电晕聚酰亚胺薄膜及其制备方法

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CN112409621A (zh) * 2020-11-27 2021-02-26 桂林电器科学研究院有限公司 高强度低介电性聚酰亚胺多层膜及其制备方法
CN112409621B (zh) * 2020-11-27 2022-09-09 桂林电器科学研究院有限公司 高强度低介电性聚酰亚胺多层膜及其制备方法
CN114919253A (zh) * 2022-05-31 2022-08-19 中山新高电子材料股份有限公司 一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法
CN114919253B (zh) * 2022-05-31 2024-05-17 中山新高电子材料股份有限公司 一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法
CN115926159A (zh) * 2022-06-09 2023-04-07 常州工学院 一种电机用低介电损耗聚酰亚胺及其制备方法和应用
CN115926159B (zh) * 2022-06-09 2024-01-23 常州工学院 一种电机用低介电损耗聚酰亚胺及其制备方法和应用
CN115558144A (zh) * 2022-10-19 2023-01-03 嘉兴瑞华泰薄膜技术有限公司 一种聚酰亚胺氟树脂复合薄膜及其制备方法
CN115558144B (zh) * 2022-10-19 2023-05-23 嘉兴瑞华泰薄膜技术有限公司 一种聚酰亚胺氟树脂复合薄膜及其制备方法
CN116162275A (zh) * 2023-03-14 2023-05-26 东华大学 一种聚酰亚胺复合膜及其制备方法和应用
CN117887124A (zh) * 2024-01-11 2024-04-16 无锡顺铉新材料有限公司 一种具有高温结合性能的ptfe/改性聚酰亚胺复合膜及其制备方法和应用
CN118596671A (zh) * 2024-06-24 2024-09-06 太湖聚智新材料科技有限公司 耐电晕聚酰亚胺薄膜及其制备方法

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