WO2023013569A1 - Procédé de fabrication de feuille, procédé de fabrication de feuille stratifiée et feuille - Google Patents

Procédé de fabrication de feuille, procédé de fabrication de feuille stratifiée et feuille Download PDF

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Publication number
WO2023013569A1
WO2023013569A1 PCT/JP2022/029434 JP2022029434W WO2023013569A1 WO 2023013569 A1 WO2023013569 A1 WO 2023013569A1 JP 2022029434 W JP2022029434 W JP 2022029434W WO 2023013569 A1 WO2023013569 A1 WO 2023013569A1
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Prior art keywords
particles
mass
inorganic particles
sheet
ptfe
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PCT/JP2022/029434
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English (en)
Japanese (ja)
Inventor
敦美 光永
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Ａｇｃ株式会社
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Priority to CN202280052642.9A priority Critical patent/CN117836356A/zh
Priority to JP2023540324A priority patent/JPWO2023013569A1/ja
Priority to KR1020247000797A priority patent/KR20240041317A/ko
Publication of WO2023013569A1 publication Critical patent/WO2023013569A1/fr

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    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to a method for manufacturing a sheet, and a method for manufacturing a laminated sheet having a plurality of sheets obtained by the manufacturing method. Further, the invention relates to a seat.
  • metal-clad laminates having a metal layer made of metal foil and a resin layer are used, for example, as printed wiring boards.
  • metal-clad laminates for printed wiring boards there has been a demand for improved performance of metal-clad laminates for printed wiring boards, particularly due to the development of high-speed communication technology.
  • Polytetrafluoroethylene has excellent heat resistance, electrical properties, and other physical properties, so it is expected to be used for resin layers in metal-clad laminates of printed wiring boards. At that time, a sheet formed from a coaggregate of polytetrafluoroethylene particles and inorganic particles has been proposed in order to form a resin layer having more excellent physical properties (see Patent Documents 1 and 2).
  • the uniform dispersibility of the inorganic particles in the sheet was not sufficient, and the inorganic particles tended to fall off from the sheet. Therefore, it cannot be said that the resulting sheet is sufficiently functionalized by the inorganic particles.
  • the adhesiveness of the sheet was low, and it was difficult to directly bond the sheet to the substrate at a low temperature.
  • the present inventors prepared a sheet from a mixture obtained by mixing particles containing polytetrafluoroethylene, agglomerates containing inorganic particles, and a specific tetrafluoroethylene-based polymer, thereby uniformly dispersing inorganic particles in the sheet. It has been found that the dispersibility and the low-temperature adhesion to the substrate can be improved, and the falling of the inorganic particles from the sheet can be suppressed.
  • the present invention provides a method for producing a sheet containing particles containing polytetrafluoroethylene, inorganic particles and a specific tetrafluoroethylene-based polymer.
  • the present invention also provides a method for producing a laminated sheet of the sheets obtained by the above production method. Further, the present invention provides a sheet in which powder fall-off is sufficiently suppressed while containing inorganic particles having a particle size and a specific surface area that facilitate powder fall-off.
  • the present invention has the following aspects.
  • the content of the particles containing the polytetrafluoroethylene and the inorganic particles in the aggregate is such that the total weight of the particles containing the polytetrafluoroethylene and the inorganic particles is 100% by mass, and the polytetrafluoroethylene is included.
  • [5] The production method according to any one of [1] to [4], wherein the inorganic particles have an average particle diameter of 1 to 20 ⁇ m and a specific surface area of 1 to 20 m 2 /g.
  • [6] The production method according to any one of [1] to [5], wherein the particles containing the tetrafluoroethylene-based polymer have an average particle size of 0.1 ⁇ m or more and 25 ⁇ m or less.
  • [7] The production method according to any one of [1] to [6], wherein the particles containing the tetrafluoroethylene-based polymer are mixed in the form of powder with the aggregate.
  • the present invention there is provided a method for producing a sheet that has high uniform dispersibility of inorganic particles, suppresses powder falling of inorganic particles, and has excellent low-temperature adhesiveness. Moreover, the laminated sheet and laminate obtained according to the present invention are sufficiently equipped with the inherent properties of polytetrafluoroethylene and inorganic particles.
  • a “tetrafluoroethylene-based polymer” is a polymer containing units (hereinafter also referred to as “TFE units”) based on tetrafluoroethylene (hereinafter also referred to as “TFE”).
  • TFE units polymer containing units (hereinafter also referred to as “TFE units”) based on tetrafluoroethylene (hereinafter also referred to as “TFE”).
  • Tg Polymer glass transition point
  • DMA dynamic viscoelasticity measurement
  • the “melting temperature (melting point) of a polymer” is the temperature corresponding to the maximum melting peak of the polymer measured by differential scanning calorimetry (DSC).
  • D50 is the average particle diameter of particles, which is the volume-based cumulative 50% diameter of particles determined by a laser diffraction/scattering method.
  • a unit based on a monomer means an atomic group based on the monomer formed by polymerization of the monomer. The units may be units directly formed by a polymerization reaction, or may be units in which some of said units have been converted to another structure by treatment of the polymer. Hereinafter, units based on monomer a are also simply referred to as "monomer a units”.
  • the method for producing a sheet of the present invention is a method for producing particles containing polytetrafluoroethylene (hereinafter also referred to as “PTFE”), aggregates containing inorganic particles, and oxygen-containing polar groups. and particles (hereinafter also referred to as “F particles”) containing a tetrafluoroethylene polymer (hereinafter also referred to as “F polymer”) having a melting temperature of 320 ° C. or less, and the resulting mixture is sheeted molded into
  • PTFE polytetrafluoroethylene
  • F polymer tetrafluoroethylene polymer having a melting temperature of 320 ° C. or less
  • PTFE is a polymer with low surface tension and extremely low affinity with other components. Therefore, even if PTFE and inorganic particles are mixed, the dispersibility of the inorganic particles in PTFE is low.
  • the F polymer acts as a binder or an adhesive component between the PTFE and the inorganic particles, and the inorganic particles in the resulting sheet It is considered that the particles improve the uniform dispersibility, suppress powder falling of the inorganic particles, and develop the low-temperature adhesiveness.
  • the PTFE in the present invention may be a homopolymer of TFE, and a very small amount of perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE"), hexafluoropropylene (hereinafter also referred to as "HFP"), fluoro So-called modified PTFE, which is a copolymer of comonomers such as alkylethylene and TFE, may also be used.
  • PAVE perfluoro(alkyl vinyl ether)
  • HFP hexafluoropropylene
  • modified PTFE which is a copolymer of comonomers such as alkylethylene and TFE
  • PTFE is preferably PTFE having a number average molecular weight, Mn, calculated based on the following formula (1) of 200,000 or more.
  • Mn 2.1 ⁇ 10 10 ⁇ ⁇ Hc -5.16 (1)
  • Mn represents the number average molecular weight of PTFE
  • ⁇ Hc represents the heat of crystallization (cal/g) of PTFE measured by differential scanning calorimetry.
  • D50 of the particles containing PTFE is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more. D50 is preferably 3 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the shape of the inorganic particles in the present invention is preferably spherical, scale-like, layer-like, needle-like or plate-like, more preferably spherical, scale-like or layer-like, and still more preferably spherical or scale-like.
  • the spherical inorganic particles are preferably substantially spherical.
  • the substantially spherical shape means that the ratio of the minor axis to the major axis is 0.7 or more when the inorganic particles are observed with a scanning electron microscope (SEM). It is preferable that the ratio of inorganic particles having a substantially spherical shape is 95% or more.
  • the aspect ratio of non-spherical inorganic particles is preferably 2 or more, more preferably 5 or more. The aspect ratio is preferably 10000 or less.
  • the inorganic particles may be hollow.
  • the sheet obtained by this method (hereinafter also referred to as “this sheet") tends to have excellent electrical properties.
  • the inorganic particles are particles containing at least one inorganic substance, preferably particles containing at least one selected from the group consisting of metal oxides, silicon oxides and nitrides.
  • Specific examples of inorganic substances include carbon, boron nitride, aluminum nitride, beryllia, silica, wollastonite, talc, cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, barium titanate, lead zirconate titanate, and lead titanate. , zirconium oxide and titanium oxide.
  • the inorganic particles are preferably particles containing silica or boron nitride from the viewpoint of reducing the dielectric constant and dielectric loss tangent of the present sheet and improving the low linear expansion property.
  • the silica is preferably amorphous silica.
  • the boron nitride is hexagonal boron nitride.
  • the inorganic particles are preferably particles containing titanium dioxide or barium titanate from the viewpoint of improving the dielectric constant.
  • the inorganic particles When the inorganic particles contain silicon oxide, the inorganic particles are preferably hollow silica from the viewpoint of electrical properties.
  • the inorganic particles When the inorganic particles contain nitrides, the inorganic particles preferably contain boron nitride or aluminum nitride from the viewpoint of the electrical properties and low linear expansion of the present sheet, and are scaly boron nitride or columnar aluminum nitride. is more preferred.
  • the scaly boron nitride may aggregate to form secondary particles.
  • D50 of the inorganic particles is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. D50 is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, still more preferably 1 ⁇ m or more, and particularly preferably 2 ⁇ m or more.
  • the specific surface area of the inorganic particles is preferably 1 to 20 m 2 /g. Inorganic particles having a D50 of 1 to 20 ⁇ m and a specific surface area of 1 to 20 m 2 /g form paths between particles in the sheet, and improve sheet physical properties such as thermal conductivity, low linear expansion, and electrical properties. However, the interaction with the PTFE-containing particles is low and tends to be easily removed from the sheet. In the present invention, this can be greatly suppressed by the action of the F polymer.
  • the surfaces of the inorganic particles may be surface-treated with a silane coupling agent.
  • a silane coupling agent include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanate. Silane coupling agents with functional groups such as propyltriethoxysilane are preferred.
  • particles containing silica include the "ADMAFINE” series (manufactured by Admatechs), the “SFP” series (manufactured by Denka), the “E-SPHERES” series (manufactured by Taiheiyo Cement), and the “Silinax” series. (manufactured by Nittetsu Mining Co., Ltd.), “Ecoco Spray” series (manufactured by Emerson & Cumming), “Hydrophobic AEROSIL” series (“RX200” etc.) (manufactured by Nippon Aerosil Co., Ltd.).
  • particles containing zinc oxide include the "FINEX” series (manufactured by Sakai Chemical Industry Co., Ltd.).
  • particles containing titanium oxide include the “Tipaque” series (manufactured by Ishihara Sangyo Co., Ltd.) and the “JMT” series (manufactured by Tayca Corporation).
  • particles containing talc include the "SG” series (manufactured by Nippon Talc Co., Ltd.).
  • steatite-containing particles include the "BST” series (manufactured by Nippon Talc Co., Ltd.).
  • particles containing boron nitride include "UHP” series (manufactured by Showa Denko KK) and "GP” and “HGP” grades of the “Denka Boron Nitride” series (manufactured by Denka KK).
  • inorganic particles may be used, or two or more types may be used.
  • silica particles, boron nitride particles and titanium dioxide particles may be used in combination.
  • the content of silica particles, boron nitride particles and titanium dioxide particles in the total amount of inorganic particles is 10 to 60% by mass, 10 to 60% by mass and 5 to 40% by mass in this order. preferable.
  • An aggregate containing PTFE-containing particles and inorganic particles can be obtained, for example, by the following method.
  • inorganic particles are added to a dispersion liquid of particles containing PTFE, or particles containing PTFE and inorganic particles are mixed in advance, and the mixture is dispersed in a dispersion medium to obtain particles containing PTFE, inorganic particles, and a dispersion medium.
  • the dispersion medium to be used is preferably water.
  • the dispersion of PTFE-containing particles a commercially available aqueous dispersion of PTFE-containing particles may be used, or one obtained by further diluting it with water may be used.
  • the mixture may contain a surfactant.
  • the solid content concentration in the resulting mixture is, for example, 3 to 50% by weight.
  • the content of the PTFE-containing particles is, for example, 0.5 to 20% by mass
  • the content of the inorganic particles is, for example, 10 to 30% by mass.
  • Mixing devices used for mixing include stirring devices equipped with blades, such as Henschel mixers, pressure kneaders, Banbury mixers and planetary mixers, ball mills, attritors, basket mills, sand mills, sand grinders, Dyno mills, Dispermat, and SC mills. , Spike mill or agitator mill equipped with media, microfluidizer, nanomizer, agitzer, ultrasonic homogenizer, desolver, disper, high speed impeller, rotation or revolution stirrer or thin film swirling high speed mixer, etc. Dispersing device with
  • the mixture may contain only particles containing PTFE and inorganic particles, or may contain fluorine resins other than PTFE.
  • fluororesins include, for example, a polymer containing TFE units and ethylene-based units (ETTE), a polymer containing TFE units and propylene-based units (TFEP), TFE units and perfluoro ( Alkyl vinyl ether) (PAVE)-based units (PFA), polymers containing TFE units and hexafluoropropylene-based units (FEP), and other fluororesins, which are miscible with PTFE. It is preferable to use a good fluororesin.
  • the content of PTFE is preferably 5% by weight or more, more preferably 10% by weight or more, based on the total fluororesin component.
  • aggregates containing particles containing PTFE and inorganic particles are obtained.
  • Methods for obtaining aggregates include, for example, a freeze-drying method, a spray-drying method, a method of stirring and shearing the mixture to coalesce particles containing PTFE and inorganic particles to remove the dispersion medium.
  • Examples include a method of aggregating particles containing PTFE and inorganic particles and removing the dispersion medium.
  • a method of coaggregating particles containing PTFE and inorganic particles in a mixture containing particles containing PTFE, inorganic particles, and water is preferred.
  • the aggregates are preferably aggregates obtained by co-aggregating a mixture containing PTFE-containing particles, inorganic particles, and water.
  • a method of co-aggregation includes a method of adding a flocculant to the mixture.
  • a flocculant for example, a solvent such as alcohol or a material having a large specific surface area such as activated carbon can be used.
  • a method of increasing the temperature of the mixture to deactivate the surfactant and promote coaggregation can be used.
  • a co-aggregate can be obtained by separating the aggregate obtained by co-aggregation from the dispersion medium.
  • the resulting coagglomerate may be further dried.
  • a known method such as filtration can be used to separate the aggregate from the dispersion medium.
  • the drying method is also not particularly limited.
  • the content of the inorganic particles in the aggregate is appropriately set according to the physical properties required for the present sheet.
  • the content of inorganic particles is preferably 40% to 95% by mass, the content of particles containing PTFE is 20% to 50% by mass, and the content of inorganic particles is more preferably 60% by mass or more and 80% by mass or less.
  • the mixture is prepared, the PTFE-containing particles and the inorganic particles are aggregated, the obtained aggregates are separated from the dispersion medium to obtain aggregates, and the obtained aggregates are mixed with the dispersion medium.
  • the mixture may be mixed again and aggregated again to form an aggregate.
  • the melting temperature of the F polymer is 320° C. or lower, preferably 200° C. or higher, more preferably 260° C. or higher.
  • the glass transition point of F polymer is preferably 50° C. or higher, more preferably 75° C. or higher.
  • the glass transition point of the F polymer is preferably 150° C. or lower, more preferably 125° C. or lower.
  • the fluorine content of the F polymer is preferably 70% by mass or more, more preferably 72 to 76% by mass.
  • the surface tension of the F polymer is preferably 16 to 26 mN/m.
  • the surface tension of the F polymer can be measured by placing a droplet of a wetting index reagent (manufactured by Wako Pure Chemical Industries, Ltd.) on a flat plate made of the F polymer.
  • F polymer with a high fluorine content is excellent in physical properties such as electrical properties, but on the other hand, it has low surface tension and tends to have low adhesiveness. Easy to act as an adhesive component.
  • the F polymer is preferably ETTE, TFEP, PFA, FEP, more preferably PFA and FEP, still more preferably PFA. These polymers may also contain units based on other comonomers.
  • the oxygen-containing polar group possessed by the F polymer includes a hydroxyl group-containing group and a carbonyl group-containing group, and from the viewpoint of improving adhesiveness, the oxygen-containing polar group is preferably a carbonyl group-containing group.
  • the hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF 2 CH 2 OH and -C(CF 3 ) 2 OH.
  • a carbonyl group-containing group includes a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH 2 ), an acid anhydride residue (-C(O)OC(O)-), an imide Residues (--C(O)NHC(O)--, etc.) and carbonate groups (--OC(O)O--) are preferred, with anhydride residues being more preferred.
  • the number of oxygen-containing polar groups in F polymer is preferably 10 to 5000, more preferably 100 to 3000, per 1 ⁇ 10 6 carbon atoms in the main chain.
  • the number of oxygen-containing polar groups in the F polymer can be quantified by the composition of the polymer or the method described in WO2020/145133.
  • the oxygen-containing polar group may be contained in a unit based on a monomer in the F polymer, or may be contained in a terminal group of the main chain of the F polymer, the former being preferred.
  • Examples of the latter embodiment include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer obtained by subjecting the F polymer to plasma treatment or ionizing radiation treatment.
  • the monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH”), more preferably NAH.
  • the F polymer is preferably a polymer having carbonyl-containing groups containing TFE units and PAVE units, comprising units based on monomers containing TFE units, PAVE units and carbonyl-containing groups, for all units: More preferred are polymers containing 90 to 99 mol %, 0.99 to 9.97 mol % and 0.01 to 3 mol % of these units in this order. Specific examples of such F polymers include the polymers described in WO2018/16644.
  • D50 of the F particles is preferably 0.1 ⁇ m or more, more preferably more than 0.3 ⁇ m, and still more preferably 1 ⁇ m or more.
  • D50 of the F particles is preferably 25 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less.
  • the specific surface area of the F particles is preferably 1 to 25 m 2 /g.
  • One type of F particles may be used, or two or more types may be used.
  • the F particles are particles containing an F polymer, preferably consisting of an F polymer.
  • the F particles may contain a resin or an inorganic compound other than the F polymer, and may form a core-shell structure in which the F polymer is the core and the shell is a resin or inorganic compound other than the F polymer, and the F polymer may be may form a core-shell structure in which a resin or an inorganic compound other than the F polymer is used as a core.
  • Resins other than the F polymer include aromatic polyesters, polyamideimides, polyimides, and maleimides.
  • examples of the inorganic compound include the same inorganic substances as those that may be contained in the inorganic particles, and among these, silica and boron nitride are preferred.
  • the method of mixing the aggregates and the F particles includes a method of mixing the aggregates and the F particles, a dispersion liquid in which the F particles are dispersed in a dispersion medium such as water or an organic solvent, and the dispersion liquid and the aggregates are mixed.
  • a method of mixing aggregates and F particles, and a method of forming a dispersion by dispersing F particles in a dispersion medium such as water or an organic solvent and mixing the dispersion and aggregates are the present invention. It is preferable from the viewpoint of uniform dispersibility of the inorganic particles in the sheet.
  • the agglomerate and the F particles are mixed, it is preferable to mix them in a powder state which is an aggregate of the F particles in a dry state.
  • the dispersion medium is preferably a compound selected from the group consisting of water, amides, ketones and esters, more preferably water, from the viewpoint of improving the dispersion stability of the dispersion.
  • alkanes such as decane, dodecane, etc., which serve as molding aids for molding into a sheet to be described later, are also preferred.
  • Amides include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N ,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone.
  • Ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone and cycloheptanone.
  • Esters include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, ⁇ -butyrolactone, ⁇ -valero Lactones are mentioned.
  • the content of the dispersion medium in the dispersion of F particles is preferably 40% by mass or more, more preferably 60% by mass or more.
  • the content of the liquid dispersion medium is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the content of the F particles in the dispersion liquid of the F particles is preferably 10% by mass or more, more preferably 20% by mass or more.
  • the content of F particles is preferably 60% by mass or less, more preferably 40% by mass or less.
  • the pH of the F particle dispersion is preferably 5 to 10, more preferably 8 to 10.
  • a pH adjuster or pH buffer may be further included to adjust the pH of the dispersion.
  • pH adjusters include amines, ammonia, and citric acid.
  • pH buffers include tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium bicarbonate, ammonium carbonate and ammonium acetate.
  • the dispersion of F particles may contain a nonionic surfactant.
  • the nonionic surfactant is preferably a glycol-based surfactant, an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
  • One type of nonionic surfactant may be used, or two or more types may be used.
  • the nonionic surfactants are preferably a silicone-based surfactant and a glycol-based surfactant.
  • nonionic surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafac” series (manufactured by DIC), “Unidyne” series (manufactured by DIC).
  • the dispersion contains a nonionic surfactant
  • the content of the nonionic surfactant in the dispersion is preferably 1 to 15% by mass.
  • the mixture of the aggregates and the F particles preferably contains 100 parts by mass of PTFE contained in the aggregates and 5 parts by mass or more and 30 parts by mass or less of the F polymer, and 10 parts by mass. 30 mass parts or less is more preferable, and 15 mass parts or more and 25 mass parts or less is more preferable.
  • the mixture contains a resin different from the PTFE and the F polymer (hereinafter referred to as “different resin”) or inorganic particles different from the inorganic particles contained in the aggregate (hereinafter referred to as “different inorganic particles”). It's okay.
  • the different resins may be thermosetting or thermoplastic, preferably thermoplastic. Examples of different resins include liquid crystalline aromatic polyesters, polyester resins such as polyarylate resins, amide resins, imide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, polyphenylene sulfide resins, polyolefin resins, Examples include polycarbonate resins and polyacetal resins.
  • aromatic polymers are more preferred, and at least one aromatic imide polymer selected from the group consisting of aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, and aromatic polyamideimide precursors is even more preferred.
  • the present polymer layer tends to be excellent in adhesiveness, low linear expansion property and UV workability.
  • aromatic imide polymers include "Upia-AT” series (manufactured by Ube Industries, Ltd.), “Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria (registered trademark)” series (Somar ), “Q-PILON (registered trademark)” series (manufactured by PI Technical Research Institute), “WINGO” series (manufactured by Wingo Technology), “Tomide (registered trademark)” series (manufactured by T&K TOKA), “KPI -MX” series (manufactured by Kawamura Sangyo Co., Ltd.), “HPC-1000” and “HPC-2100D” (both manufactured by Showa Denko Materials).
  • the content of the different resins in the mixture is preferably 0.1 to 40% by weight, more preferably 1 to 10% by weight.
  • Different inorganic particles include the same inorganic particles that may be used to obtain the agglomerate.
  • the content of the inorganic particles in the mixture is preferably 1 to 50% by mass, more preferably 3 to 30% by mass.
  • the mixture may contain particles comprising PTFE apart from the PTFE contained in the agglomerates.
  • the mixture may optionally contain a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a brightener, a colorant, a conductive agent, a release agent, a surface Additives such as treating agents, flame retardants, and various fillers may be further contained.
  • the molding method includes a method of casting a mixture.
  • the PTFE is easily fibrillated, and the present sheet from which the inorganic particles are difficult to peel off can be easily obtained.
  • Methods of casting the mixture include press molding, extrusion molding and calendar molding.
  • calendering means a method of rolling a mixture by passing it between a plurality of rolls.
  • the mixture containing the dispersion medium may be molded after removing the dispersion medium. From the mixture containing the dispersion medium, an aggregate containing particles containing PTFE and inorganic particles may be further aggregated with F particles to obtain an aggregate, which may be used for molding.
  • the method for obtaining the aggregate includes the same method as the method for obtaining the aggregate containing particles containing PTFE and inorganic particles.
  • a pasty mixture may be prepared and cast by mixing the mixture and a molding aid before molding.
  • the mixing with the molding aid is desirably carried out under conditions that minimize fiberization of PTFE. Specifically, it is desirable to mix without kneading by reducing the rotation speed and shortening the mixing time so as not to apply a shearing force to the PTFE. If fiberization of PTFE occurs in the stage of mixing materials, the PTFE fibers formed during casting may be cut and the network structure of PTFE may be destroyed, and the sheet shape cannot be maintained. It can be difficult. Therefore, by mixing so as to suppress fibrillation of PTFE, it becomes easy to process the present sheet having PTFE as a matrix in a later step. Alkanes such as dodecane and decane can be used as molding aids.
  • the molding aid may be added in an amount of 20 to 55% by mass with respect to the total mass.
  • Casting of the mixture may be performed using one type of molding method, or two or more types of molding methods may be used in combination. Also, casting may be performed by repeating one molding method a plurality of times. For example, a mother sheet obtained by extruding the mixture may be further calendered and cast, or a mother sheet obtained by calendering the mixture may be further calendered and cast. In this case, it is easy to obtain a sheet of any thickness that is excellent in toughness and uniformity.
  • a plurality of rolls may be used in calendering, and it is preferable to use a combination of four rolls. The arrangement of the four rolls includes I-type, S-type, inverted L-type, Z-type, and oblique Z-type.
  • the casting of the mixture may be performed while heating at a temperature below the melting temperature of PTFE, or may be performed without heating.
  • the sheet may be heated after casting in order to remove the molding aid.
  • the present sheet is obtained as described above.
  • the thickness of this sheet is, for example, 0.5 to 5 mm.
  • the sheet may be fired by heating at a temperature higher than the melting temperature of PTFE.
  • the inorganic particles having a D50 of 1 to 20 ⁇ m and a specific surface area of 1 to 20 m 2 /g form inter-particle paths in the sheet, have thermal conductivity, low linear expansion, While it is easy to improve sheet physical properties such as electrical properties, it has low interaction with particles containing PTFE, and tends to be more easily removed from the sheet.
  • the F polymer to coexist with the inorganic particles, it is possible to highly suppress the powder fall-off even in the case of such particles that are more prone to powder fall-off.
  • the present invention contains PTFE, F polymer, and inorganic particles having an average particle size of 1 to 20 ⁇ m and a specific surface area of 1 to 20 m 2 /g, and the content of the PTFE and the inorganic particles is Taking the total mass of the PTFE and the inorganic particles as 100% by mass, a sheet containing 5% by mass or more and 60% by mass or less and 40% by mass or more and 95% by mass or less (hereinafter also referred to as "other main sheet"). Offer more.
  • the PTFE and F polymer are as described above, and the preferred forms are also the same as described above.
  • the content of PTFE is preferably 20% by mass or more and 50% by mass or less when the total mass of the PTFE and the inorganic particles is 100% by mass. Further, the content of the inorganic particles in the other present sheet is more preferably 60% by mass or more and 80% by mass or less when the total mass of the PTFE and the inorganic particles is 100% by mass.
  • the other main sheet preferably contains 5 parts by mass or more and 30 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less, and 15 parts by mass or more and 25 parts by mass of the F polymer with respect to 100 parts by mass of the PTFE. Part or less is more preferable.
  • the inorganic particles preferably contain at least one selected from the group consisting of metal oxides, silicon oxides and nitrides, as described above.
  • a laminated sheet is obtained by laminating two or more of the above-obtained main sheets or other main sheets.
  • a laminated sheet is obtained by laminating and rolling two or more sheets.
  • the number of laminated sheets is, for example, about 2 to 10 layers. From the viewpoint of strength between laminations, it is preferable to stack the sheets one by one and roll them.
  • the main sheet or other main sheets may be folded and laminated.
  • the sheet strength can be improved and the inorganic particles can be firmly fixed to the PTFE matrix.
  • a plurality of the laminated sheets may be laminated to form a laminated sheet having a larger number of laminated sheets.
  • the rolling direction When making laminated sheets, it is desirable to change the rolling direction. For example, when rolling the second main sheet on the first main sheet and laminating the third main sheet, it is preferable to change the rolling direction by 90 degrees from the rolling direction of the second main sheet. .
  • the PTFE network By rolling while changing the direction in this way, the PTFE network extends lengthwise and breadthwise, making it possible to improve the strength of the present sheet and firmly fix the inorganic particles to the PTFE matrix.
  • the obtained laminated sheet may be pressure-molded. Pressure molding can reduce porosity in the laminated sheet.
  • thermocompression bonding By thermocompression bonding the laminated sheet obtained above to a substrate, a laminate having a substrate layer and a polymer layer containing PTFE, inorganic particles, and F polymer is obtained.
  • Substrates include metal substrates such as metal foils of copper, nickel, aluminum, titanium and alloys thereof, polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester and tetrafluoro
  • metal substrates such as metal foils of copper, nickel, aluminum, titanium and alloys thereof, polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester and tetrafluoro
  • heat-resistant resin films of heat-resistant resin films such as ethylene-based polymers, prepreg substrates that are precursors of fiber-reinforced resin substrates, ceramic substrates such as silicon carbide, aluminum nitride or silicon nitride, and glass substrates.
  • the shape of the base material include planar, curved, and uneven shapes.
  • the shape of the substrate may be any of foil, plate, film, and fiber.
  • the surface of the substrate may be surface-treated with a silane coupling agent or plasma-treated.
  • Silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanate.
  • Silane coupling agents with functional groups such as propyltriethoxysilane are preferred.
  • thermocompression bonding a method of sandwiching the base material and the main sheet between a pair of opposing hot plates and applying pressure, a method of passing the base material and the main sheet between a pair of facing rolls, a method of passing the base material and the main sheet between a pair of opposing rolls, There is a method of applying pressure to the material and the main sheet.
  • the temperature for thermocompression bonding is preferably 200° C. or higher, more preferably the melting temperature of PTFE or higher, and still more preferably 350° C. or higher.
  • the temperature for thermocompression bonding is preferably 400° C. or less. It is preferable to bake PTFE by heating during thermocompression bonding.
  • Thermocompression bonding may be performed under reduced pressure.
  • the degree of vacuum is preferably 20 kPa or less from the viewpoint of suppressing deterioration due to oxidation of the substrate and the main sheet.
  • the thermocompression bonding is preferably performed by a vacuum press.
  • a release film is placed between the surface of the sheet and the hot plate or roll, or is preferably surface-treated with a release agent.
  • the thickness of the release film is preferably 50 to 150 ⁇ m.
  • release films include polyimide films, and specific examples thereof include “Apical NPI” (manufactured by Kaneka), “Kapton EN” (DuPont-Toray), and “Upilex S (Ube Industries, Ltd.)".
  • the laminate sheet may be thermocompression-bonded to only one surface of the substrate, or may be thermocompression-bonded to both surfaces of the substrate.
  • a laminate having a base layer and a polymer layer on one surface of the base layer is obtained, and in the latter case, a base layer and a polymer layer are obtained on both surfaces of the base layer.
  • a laminate is obtained.
  • Preferred specific examples of the laminate include a metal foil and a metal-clad laminate having a polymer layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having a polymer layer on both surfaces of the polyimide film. is mentioned.
  • the peel strength between the polymer layer and the substrate layer is preferably 10 to 100 N/cm.
  • the substrate layer may be removed from the laminate to obtain a sheet containing PTFE, inorganic particles and F polymer.
  • the present sheet, the present laminated sheet, and the laminate having the present laminated sheet are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sporting goods, food products, heat dissipation parts, paints, cosmetics, and the like.
  • wire coating materials for aircraft wires enameled wire coating materials used for motors such as electric vehicles, electrical insulating tapes, insulating tapes for oil drilling, oil transport hoses, hydrogen tanks, and printed circuit boards.
  • separation membranes such as microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes and gas separation membranes, electrode binders for lithium secondary batteries and fuel cells, copy rolls, furniture, automobiles Covers for dashboards, home appliances, etc., sliding members, tension ropes, wear pads, wear strips, tube ramps, test sockets, wafer guides, wear parts for centrifugal pumps, chemical and water supply pumps, shovels, files, drills, and Tools such as saws, boilers, hoppers, pipes, ovens, baking molds, chutes, racket guts, dies, toilet bowls, container covering materials, power devices, transistors, thyristors, rectifiers, transformers, power MOS FETs, CPUs, heat radiation fins, Seals for metal heat sinks, blades for wind turbines, wind power generation facilities, aircraft, etc., housings for personal computers and displays, electronic device materials, interior and exterior of automobiles, processing machines and vacuum ovens that perform heat treatment
  • Sliding members include load bearings, yaw bearings, slide shafts, valves, bearings, bushes, seals, thrust washers, wear rings, pistons, slide switches, gears, cams, belt conveyors and food transport belts.
  • the present sheet, the method for manufacturing the laminated sheet, and other present sheets have been described above, the present invention is not limited to the configurations of the above-described embodiments.
  • the manufacturing method of the present sheet and the laminated sheet may additionally have other arbitrary steps in the configuration of the above-described embodiments, or may be replaced with arbitrary steps that produce similar actions.
  • the other seat may be added with any other configuration, or may be replaced with any configuration that exhibits the same function.
  • PTFE particles PTFE particles (D50: 0.3 ⁇ m)
  • F particle 1 containing 97.9 mol%, 0.1 mol% and 2.0 mol% of TFE units, NAH units and PPVE units in this order, and 1000 carbonyl groups per 1 ⁇ 10 6 main chain carbon atoms
  • Particles D50: 1.7 ⁇ m
  • F polymer 1 melting temperature: 300 ° C.
  • F Particles 2 Particles (D50: 2 .1 ⁇ m)
  • Dispersion 1 Aqueous dispersion containing 60% by mass of PTFE particles
  • Inorganic particles 1 Scale-like boron nitride particles (D50: 7.0 ⁇ m, specific surface area: 2 m 2 /g)
  • Inorganic particles 2 Spherical silica particles (D50: 2.0 ⁇ m, specific surface area: 5 m 2 /g)
  • Example 2 Production of Sheets, Laminated Sheets and Laminates (Example 1) Dispersion 1 was diluted 20 times with water, and inorganic particles 1 were added to the obtained diluted dispersion so that the mass ratio of inorganic particles 1 and PTFE particles was 80:20. As a result, a mixture containing PTFE particles 1 and inorganic particles 1 was obtained. Isopropyl alcohol was added to this mixture to coaggregate the PTFE particles and inorganic particles 1 in the mixture. The resulting aggregates were filtered to separate from the liquid component and dried at 150° C. for 24 hours to obtain aggregates containing PTFE particles and inorganic particles 1 .
  • This aggregate 10 parts by mass of F particles 1 per 100 parts by mass of the PTFE particles, and "Isopar M" (manufactured by ExxonMobil) as a molding aid, are combined with the PTFE particles, the inorganic particles 1, and the F particles.
  • the mixture was mixed so that the ratio of the total mass of 1 and the mass of the molding aid was 5:2, and mixed in a rotary mill for 10 minutes under conditions that minimized fiberization of PTFE.
  • the resulting mixture was preformed and pelletized.
  • the pellets were extruded using an extruder to obtain a mother sheet having a width of 45 mm and a thickness of 2 mm.
  • the mother sheet was rolled in the MD direction (longitudinal direction) with a pair of rolling rolls to obtain a sheet 1 having a thickness of 1 mm.
  • Two sheets 1 were laminated by a roll to roll process with the MD and TD directions aligned, and rolled in the TD direction to obtain a laminated sheet 1 with a thickness of 0.25 mm.
  • Laminated sheet 1 is superimposed on a non-roughened copper foil (surface ten-point average roughness: 0.05 ⁇ m or less, thickness: 18 ⁇ m) and bonded together by thermocompression at 380 ° C. to form a polymer layer composed of a laminated sheet. and a copper foil.
  • a non-roughened copper foil surface ten-point average roughness: 0.05 ⁇ m or less, thickness: 18 ⁇ m
  • Example 2 Laminated sheet 2 and laminate 2 were obtained in the same manner as in Example 1, except that F particles 1 were not added. It should be noted that when the laminated sheet 2 was produced, streaks in the sheet due to falling powder and contamination of the apparatus were observed. Moreover, the peel strength between the copper foil and the laminated sheet in each laminate was measured.
  • Example 3 Dispersion 1 was diluted 20 times with water, and inorganic particles 2 were added to the obtained diluted dispersion so that the mass ratio of inorganic particles 2 and PTFE particles was 60:40. As a result, a mixture containing PTFE particles and inorganic particles 2 was obtained. Isopropyl alcohol was added to this mixture to coaggregate the PTFE particles and the inorganic particles 2 in the mixture. The resulting aggregates were filtered to separate from the liquid component and dried at 150° C. for 24 hours to obtain aggregates containing PTFE particles and inorganic particles 2 .
  • This aggregate 8 parts by mass of F particles 1 per 100 parts by mass of PTFE particles, and "Isopar M" (manufactured by ExxonMobil) as a molding aid, are combined with PTFE particles, inorganic particles 2, and F particles. 2 and the molding aid in a ratio of 5:2, and mixed in a rotating mill for 10 minutes under conditions that minimize fiberization of PTFE.
  • the resulting mixture was preformed and pelletized.
  • the pellets were extruded using an extruder to obtain a mother sheet having a width of 45 mm and a thickness of 2 mm.
  • the mother sheet was rolled in the MD direction (longitudinal direction) with a pair of rolling rolls to obtain a sheet 3 having a thickness of 1 mm.
  • Two sheets 3 were laminated by a roll to roll process with the MD and TD directions aligned, and rolled in the TD direction to obtain a laminated sheet 3 with a thickness of 0.25 mm.
  • Laminated sheet 3 was an adhesive sheet having a low relative permittivity, a low dielectric loss tangent, a low linear expansion property, and excellent surface smoothness in which powder fall-off during use was suppressed.
  • Example 4 An attempt was made to form mother sheet 4 and laminated sheet 4 in the same manner as in Example 3, except that F polymer 1 was changed to F polymer 2. However, the sheets had excellent surface smoothness due to powder falling off during sheet preparation. It was a sheet that not only could not be formed, but also powdered off during use.
  • the sheet and the laminated sheet obtained by this method have inorganic particles uniformly dispersed therein, suppressing dusting of the inorganic particles, and are excellent in low-temperature adhesiveness. Also, the sheets, laminate sheets and laminates obtained by this method are sufficiently equipped with the inherent properties of polytetrafluoroethylene and inorganic particles.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

À cet effet, l'invention concerne un procédé de fabrication d'une feuille qui contient des particules contenant du polytétrafluoroéthylène, des particules inorganiques et un polymère à base de tétrafluoroéthylène spécifique. En outre, l'invention concerne un procédé de fabrication d'une feuille stratifiée qui comprend de multiples feuilles obtenues avec le procédé de fabrication susmentionné, et un procédé de fabrication d'un corps stratifié qui comprend la feuille stratifiée obtenue et un substrat. La solution selon l'invention porte sur un procédé de fabrication de feuille qui consiste à : mélanger un agglomérat qui contient des particules contenant du polytétrafluoroéthylène et des particules inorganiques, et des particules qui contiennent un polymère à base de tétrafluoroéthylène qui possède un groupe polaire contenant de l'oxygène et une température de fusion ne dépassant pas 320 °C ; et former le mélange obtenu.
PCT/JP2022/029434 2021-08-04 2022-08-01 Procédé de fabrication de feuille, procédé de fabrication de feuille stratifiée et feuille WO2023013569A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015044288A (ja) * 2013-08-27 2015-03-12 日東電工株式会社 熱伝導シートの製造方法及び熱伝導シート
JP2015164801A (ja) * 2014-02-04 2015-09-17 日東電工株式会社 熱伝導性シートの製造方法及び熱伝導性シート
JP2015209529A (ja) * 2014-04-30 2015-11-24 日東電工株式会社 熱伝導性ポリマー組成物及び熱伝導性成形体
WO2018016644A1 (fr) * 2016-07-22 2018-01-25 旭硝子株式会社 Composition liquide, procédé de fabrication de film et corps stratifié utilisant ladite composition liquide
WO2020145133A1 (fr) * 2019-01-11 2020-07-16 ダイキン工業株式会社 Composition de résine fluorée, feuille de résine fluorée, stratifié, et substrat pour circuit
WO2022149551A1 (fr) * 2021-01-06 2022-07-14 Ａｇｃ株式会社 Procédé de production d'une composition de polymère à base de tétrafluoroéthylène, composition, stratifié à revêtement métallique et feuille étirée

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015044288A (ja) * 2013-08-27 2015-03-12 日東電工株式会社 熱伝導シートの製造方法及び熱伝導シート
JP2015164801A (ja) * 2014-02-04 2015-09-17 日東電工株式会社 熱伝導性シートの製造方法及び熱伝導性シート
JP2015209529A (ja) * 2014-04-30 2015-11-24 日東電工株式会社 熱伝導性ポリマー組成物及び熱伝導性成形体
WO2018016644A1 (fr) * 2016-07-22 2018-01-25 旭硝子株式会社 Composition liquide, procédé de fabrication de film et corps stratifié utilisant ladite composition liquide
WO2020145133A1 (fr) * 2019-01-11 2020-07-16 ダイキン工業株式会社 Composition de résine fluorée, feuille de résine fluorée, stratifié, et substrat pour circuit
WO2022149551A1 (fr) * 2021-01-06 2022-07-14 Ａｇｃ株式会社 Procédé de production d'une composition de polymère à base de tétrafluoroéthylène, composition, stratifié à revêtement métallique et feuille étirée

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