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WO2023002999A1 - Procédé de production d'une feuille composite, et feuille composite - Google Patents

Procédé de production d'une feuille composite, et feuille composite Download PDF

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Publication number
WO2023002999A1
WO2023002999A1 PCT/JP2022/028125 JP2022028125W WO2023002999A1 WO 2023002999 A1 WO2023002999 A1 WO 2023002999A1 JP 2022028125 W JP2022028125 W JP 2022028125W WO 2023002999 A1 WO2023002999 A1 WO 2023002999A1
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WO
WIPO (PCT)
Prior art keywords
polymer
composite sheet
tetrafluoroethylene
liquid crystal
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/028125
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English (en)
Japanese (ja)
Inventor
省吾 小寺
渉 笠井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2023536764A priority Critical patent/JPWO2023002999A1/ja
Priority to KR1020247001559A priority patent/KR20240034188A/ko
Priority to CN202280049993.4A priority patent/CN117715959A/zh
Publication of WO2023002999A1 publication Critical patent/WO2023002999A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/465—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating by melting a solid material, e.g. sheets, powders of fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0872—Prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2267/00—Use of polyesters or derivatives thereof as reinforcement

Definitions

  • the present disclosure relates to a composite sheet manufacturing method and a composite sheet.
  • Patent Literature 1 describes a composite sheet comprising a liquid crystal polymer-containing nonwoven fabric on the facing surfaces of a layer containing a liquid crystal polymer and a layer containing a tetrafluoroethylene-based polymer.
  • a tetrafluoroethylene-based polymer has excellent electrical properties and a high coefficient of linear expansion. Therefore, when the laminate of the composite sheet and the base material described in Patent Document 1 is processed at a high temperature, for example, when subjected to a reflow process in the production of a wiring board, the composite sheet thermally expands and the composite sheet and the base material are separated from each other. It was easy to peel off the material.
  • the present disclosure relates to providing a composite sheet having excellent electrical properties and low linear expansion and a method for manufacturing the composite sheet.
  • Means for solving the above problems include the following aspects.
  • a method for producing a composite sheet comprising impregnating a woven fabric or nonwoven fabric of a liquid crystal polymer with a film containing a heat-melting tetrafluoroethylene-based polymer having oxygen atoms to obtain a composite sheet.
  • ⁇ 3> The production method according to ⁇ 1> or ⁇ 2>, wherein the tetrafluoroethylene-based polymer has a melting temperature of 260°C or higher.
  • ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the tetrafluoroethylene-based polymer has an oxygen-containing polar group, and the oxygen-containing polar group is a hydroxyl group-containing group or a carbonyl group-containing group. Method of manufacture as described.
  • the tetrafluoroethylene-based polymer has an oxygen-containing polar group, and the number of the oxygen-containing polar groups in the tetrafluoroethylene-based polymer is 10 to 5000 per 1 ⁇ 10 6 carbon atoms in the main chain.
  • the tetrafluoroethylene-based polymer contains units based on perfluoro(alkyl vinyl ether), and the content of the units based on perfluoro(alkyl vinyl ether) in all units in the tetrafluoroethylene-based polymer is 2.
  • ⁇ 7> The production method according to any one of ⁇ 1> to ⁇ 6>, wherein the liquid crystal polymer has a deflection temperature under load of 240° C. or higher.
  • ⁇ 8> The production method according to any one of ⁇ 1> to ⁇ 7>, wherein the liquid crystal polymer contains a liquid crystalline aromatic polyester.
  • ⁇ 9> The production method according to ⁇ 8>, wherein the aromatic ring content of the aromatic polyester is 55% by mass or more.
  • ⁇ 10> The manufacturing method according to any one of ⁇ 1> to ⁇ 9>, wherein the composite sheet has a thickness of 200 ⁇ m or less.
  • ⁇ 11> The production method according to any one of ⁇ 1> to ⁇ 10>, wherein the film and the woven fabric or nonwoven fabric are thermocompressed to impregnate the film.
  • ⁇ 12> The manufacturing method according to ⁇ 11>, wherein the pressure bonding temperature in the thermocompression bonding is within ⁇ 30° C. of the melting temperature of the tetrafluoroethylene-based polymer.
  • thermocompression bonding is 1 MPa or more.
  • thermocompression bonding is performed under reduced pressure.
  • thermocompression bonding is performed under reduced pressure.
  • a method for manufacturing a composite sheet and a composite sheet that are excellent in electrical properties and low linear expansion are provided.
  • each component may contain multiple types of applicable substances.
  • the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
  • Plural types of particles corresponding to each component in the present disclosure may be included.
  • the particle size of each component means a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
  • a “composite sheet” is a sheet comprising a polymer and a woven or non-woven fabric of liquid crystal polymer.
  • film and “sheet” are used interchangeably, and their thickness is not particularly limited.
  • the term “layer” includes the case where the layer or film is formed in the entire region when the region where the layer or film is present is formed only in a part of the region. case is also included.
  • the term “laminate” indicates stacking layers, and two or more layers may be bonded, or two or more layers may be detachable.
  • average particle size (D50) is the volume-based cumulative 50% diameter of particles determined by a laser diffraction/scattering method. That is, the particle size distribution is measured by a laser diffraction/scattering method, and the cumulative curve is obtained with the total volume of the group of particles being 100%.
  • the D50 of the particles is obtained by dispersing the particles in water and analyzing them by a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution analyzer (LA-920 measuring instrument manufactured by Horiba, Ltd.).
  • the “specific surface area” is a value calculated by measuring particles by gas adsorption (constant volume method) BET multipoint method, and is determined using NOVA4200e (manufactured by Quantachrome Instruments).
  • melting temperature is the temperature corresponding to the maximum melting peak of the polymer as measured by differential scanning calorimetry (DSC).
  • melt flow rate means the melt mass flow rate of a polymer as defined in JIS K 7210-1:2014 (ISO1133-1:2011).
  • glass transition point (Tg) is a value measured by analyzing a polymer by dynamic viscoelasticity measurement (DMA).
  • a "polymer” is a compound formed by polymerizing monomers. That is, a “polymer” has multiple monomer-based units.
  • a "unit" in a polymer 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.
  • units based on monomer a are also simply referred to as "monomer a units".
  • a woven or nonwoven fabric of a liquid crystal polymer is impregnated with a film containing a heat-melting tetrafluoroethylene-based polymer having oxygen atoms (hereinafter also referred to as "F polymer"). to obtain a composite sheet.
  • F polymer heat-melting tetrafluoroethylene-based polymer having oxygen atoms
  • tetrafluoroethylene-based polymers have excellent electrical properties such as a low dielectric constant and a low dielectric loss tangent, but also have a large coefficient of linear expansion.
  • Conventional composite sheets using tetrafluoroethylene-based polymers do not have sufficient low linear expansion properties.
  • the tetrafluoroethylene-based polymer is impregnated into the nonwoven fabric of the liquid crystal polymer, and the two are simply entangled and adhered, and the adhesion at the interface is insufficient.
  • the laminate of the composite sheet and the base material has problems such as thermal expansion during processing at high temperature and separation from the base material.
  • the inventors have made intensive studies and found that a composite sheet obtained by impregnating a woven or non-woven fabric of a liquid crystal polymer with a film of a heat-meltable tetrafluoroethylene polymer having oxygen atoms has excellent electrical properties and low linear expansion. It was also found that the peel strength when laminated with the base material is also excellent. The reason for this is not necessarily clear, but is considered as follows. In the impregnation, the oxygen atoms contained in the tetrafluoroethylene-based polymer affect the conformation of the tetrafluoroethylene-based polymer, and the adhesion at the interface between the tetrafluoroethylene-based polymer and the liquid crystal polymer woven or non-woven fabric is improved. .
  • the linear expansion of the tetrafluoroethylene-based polymer is buffered by the woven fabric or non-woven fabric of the liquid crystal polymer, and the physical properties of both polymers are considered to be highly balanced.
  • the oxygen atoms in the tetrafluoroethylene-based polymer are also believed to improve adhesion to substrates, and these properties are believed to provide a material useful as, for example, a low transmission loss material.
  • the method of manufacturing the composite sheet of the present disclosure uses a woven or non-woven fabric of liquid crystal polymer.
  • the liquid crystal polymer a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state is preferable.
  • One type of liquid crystal polymer may be used, or two or more types may be used.
  • the woven fabric or non-woven fabric of liquid crystal polymer may be a woven fabric or non-woven fabric containing liquid crystal polymer, and may contain other materials.
  • the liquid crystal polymer content is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass with respect to the total mass of the liquid crystal polymer woven fabric or nonwoven fabric.
  • Liquid crystalline polyester is preferred as the liquid crystalline polymer.
  • the liquid crystalline polyester may be a liquid crystalline polyester amide, a liquid crystalline polyester ether, a liquid crystalline polyester carbonate, or a liquid crystalline polyester imide.
  • the liquid crystalline polyester is preferably a liquid crystalline aromatic polyester, and specifically, a polycondensate of an aromatic dicarboxylic acid and an aromatic diol or an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol and an aromatic A polycondensate with hydroxycarboxylic acid and the like can be mentioned.
  • aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • Aromatic diols include 4,4'-dihydroxybiphenyl, bisphenol A and the like.
  • Aromatic hydroxycarboxylic acids include parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid and the like.
  • components such as aliphatic dicarboxylic acids, aliphatic diols, and aliphatic hydroxycarboxylic acids may be used in combination as long as liquid crystallinity is exhibited.
  • Aliphatic diols include ethylene glycol.
  • the liquid crystal polymer a liquid crystalline aromatic polyester having an aromatic ring content of 55% by mass or more is preferable from the viewpoint of excellent heat resistance.
  • the aromatic ring content of the liquid crystalline aromatic polyester is more preferably 60% by mass or more.
  • the aromatic ring content is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
  • Such a liquid crystal polymer has a small degree of conformational freedom and excellent heat resistance, but it is difficult to interact with other polymers.
  • the F polymer has an oxygen atom, has a relatively high degree of conformational freedom, and has a high affinity with liquid crystal polymers. It's easy to do.
  • the aromatic ring content is obtained from the following formula.
  • the carbon atoms contained in the substituents bonded to the aromatic ring are not included in the carbon atoms forming the aromatic ring.
  • Aromatic ring content (% by mass) 100 x [mass of carbon atoms forming aromatic rings in polymer skeleton (g)/total mass of polymer (g)]
  • the aromatic ring content in a typical unit contained in a liquid crystalline aromatic polyester is as follows, based on the copolymerization ratio (molar ratio) of each unit, the aromatic ring content of the liquid crystalline aromatic polyester Amount can be calculated.
  • 2-hydroxy-6-naphthoic acid 71% 4,4'-dihydroxybiphenyl: 78%
  • Terephthalic acid 54%
  • the liquid crystalline polyester amide includes an aromatic polyester amide obtained by copolymerizing the liquid crystalline aromatic polyester with aminophenol.
  • Specific examples of liquid crystal polymers include liquid crystal polymers described in paragraphs 0032 to 0039 of JP-A-2017-119378.
  • the deflection temperature under load of the liquid crystal polymer is preferably 240° C. or higher, more preferably 270° C. or higher, and even more preferably 300° C. or higher.
  • the deflection temperature under load is preferably 400° C. or less.
  • the composite sheet is preferable because it tends to be excellent in heat resistance.
  • the F polymer since the F polymer has oxygen atoms and has a relatively high degree of conformational freedom, it is also compatible with liquid crystal polymers that have a high deflection temperature under load, that is, have a small degree of conformational freedom and are difficult to interact with other polymers. Easy to adhere to.
  • the deflection temperature under load of the liquid crystal polymer is preferably above the melting temperature of the F polymer.
  • the deflection temperature under load is a value measured according to ASTM D648 with a load of 0.46 MPa.
  • the average fiber diameter of the liquid crystal polymer nonwoven fabric is preferably 0.01 to 20 ⁇ m, more preferably 0.05 to 10 ⁇ m, and most preferably 0.1 to 4 ⁇ m.
  • the average fiber diameter is obtained by measuring the fiber diameters of 200 fibers by electron microscope observation, and excluding the data of the 10 thinnest and 10 thickest fibers, and obtaining the average value.
  • the volume basis weight of the liquid crystal polymer nonwoven fabric is preferably 3 to 100 cm 3 /m 2 , more preferably 5 to 60 cm 3 /m 2 , still more preferably 10 to 40 cm 3 /m 2 .
  • the volume basis weight of the liquid crystal polymer nonwoven fabric is obtained by dividing the basis weight of the liquid crystal polymer nonwoven fabric by the specific gravity of the liquid crystal polymer nonwoven fabric.
  • the nonwoven fabric of the liquid crystal polymer may be a manufactured one or a ready-made one. Either a dry method or a wet method may be employed for molding the nonwoven fabric of the liquid crystal polymer.
  • the liquid crystal structure In the dry method, especially when forming into a non-woven fabric by melting, the liquid crystal structure generally collapses and randomly aligns in a region higher than the glass transition temperature and on the higher temperature side than the temperature region in which the liquid crystal structure exists in a non-flowing state. It can be molded in the temperature range.
  • melt molding is possible at a molding temperature of 200 to 400° C., for example.
  • Melt-molding methods for non-woven fabrics of liquid crystal polymers include spunbonding and melt-blowing, for example, the molding method described in International Publication No. 2010/098400.
  • a wet method a pre-spun liquid crystal polymer fiber is used as a raw material, and short fibers obtained by cutting it to a certain length are formed into a sheet by a papermaking method as exemplified in JP-A-2012-36538. can also form nonwovens.
  • the non-woven fabric of liquid crystal polymer may be formed by electrospinning a solution containing liquid crystal polymer, and the method exemplified in Japanese Patent Application Laid-Open No. 2010-196228, that is, the method of stretching liquid crystal polymer filaments while heating with a laser. may be formed by In such a case, a nonwoven fabric containing liquid crystal polymer fibers having a small average fiber diameter can be obtained.
  • the woven fabric of liquid crystal polymer can also be regarded as a woven fabric of liquid crystal polymer fibers, and specifically includes a plain weave fabric.
  • the warp density of the liquid crystal polymer plain weave is preferably 2 to 80/cm, more preferably 4 to 60/cm.
  • the weft density of the liquid crystal polymer plain weave is preferably 2 to 80 wefts/cm, more preferably 4 to 60 wefts/cm.
  • the liquid crystal polymer fiber is preferably a fiber obtained by melt-spinning a liquid crystal polymer.
  • the liquid crystal polymer fibers obtained by melt spinning may be further heat-treated in order to improve the strength.
  • the liquid crystal polymer fibers may consist of one kind of liquid crystal polymer or two or more kinds of liquid crystal polymers.
  • the fiber of the liquid crystal polymer may be a core-sheath composite fiber having a core-sheath structure.
  • the liquid crystal polymer may be contained as a core component, may be contained as a sheath component, or may be contained as both a core component and a sheath component.
  • the liquid crystal polymer woven or non-woven fabric is preferably surface-treated.
  • the affinity between the liquid crystal polymer woven fabric or non-woven fabric and the F polymer is improved, and the adhesiveness between the liquid crystal polymer woven fabric or non-woven fabric and the F polymer is likely to be improved.
  • the fine voids in the liquid crystal polymer woven fabric or nonwoven fabric are easily impregnated with the F polymer, and the mechanical properties of the obtained composite sheet are easily improved.
  • Surface treatments include corona treatments and plasma treatments.
  • Plasma treatment includes vacuum plasma treatment and atmospheric pressure plasma treatment, with vacuum plasma treatment being preferred.
  • the vacuum plasma treatment is preferably performed in an atmosphere containing argon gas, an atmosphere containing oxygen gas, or an atmosphere containing hydrogen gas and nitrogen gas.
  • a film containing F polymer (hereinafter also referred to as F film) is used.
  • F film a film containing F polymer
  • One type of F polymer may be used, or two or more types may be used.
  • 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").
  • the content of TFE units in the tetrafluoroethylene-based polymer is preferably 50 mol% or more, preferably 90 mol% or more, based on the total units in the tetrafluoroethylene-based polymer, from the viewpoint of suitably expressing the properties of the TFE units. is more preferred.
  • the above content may be 99 mol % or less, or 98 mol % or less.
  • the F polymer has oxygen atoms. According to the manufacturing method of the present disclosure using the F polymer, a composite sheet having excellent electrical properties and low linear expansion is obtained. In addition, composite sheets produced using F-polymer tend to have excellent adhesiveness to substrates.
  • a polymer "having oxygen atoms” means a polymer having oxygen atoms which are intended as constituent atoms of the polymer, and even if oxygen atoms are unavoidably mixed in the manufacturing process, such oxygen atoms may be mixed. Polymers with oxygen atoms are not included in polymers "having oxygen atoms".
  • F polymers include heat-meltable tetrafluoroethylene-based polymers having oxygen-containing polar groups.
  • the oxygen-containing polar group in the F polymer interacts with the liquid crystal polymer and the substrate, and the composite sheet tends to be excellent in low linear expansion and adhesiveness to the substrate, which is preferable.
  • the oxygen-containing polar group includes a hydroxyl group-containing group, a carbonyl group-containing group, an epoxy group-containing group, a phosphono group-containing group and the like, preferably a hydroxyl group-containing group or a carbonyl group-containing group, more preferably a carbonyl group-containing group.
  • the F polymer may have one or more oxygen-containing polar groups.
  • 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 carboxy 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, and acid anhydride residues are more preferred.
  • the number of oxygen-containing polar groups in F polymer is preferably 10 to 5,000, more preferably 100 to 3,000 per 1 ⁇ 10 6 carbon atoms in the main chain.
  • the number of oxygen-containing polar groups 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.
  • a tetrafluoroethylene polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., a polymer obtained by plasma treatment or ionizing radiation treatment of a tetrafluoroethylene polymer, etc. is mentioned.
  • the F polymer or its film may not be subjected to surface treatment such as plasma treatment or ionizing radiation treatment.
  • NAH 5-norbornene-2,3-dicarboxylic anhydride
  • F polymer having an oxygen-containing polar group examples include polytetrafluoroethylene (PTFE) having an oxygen-containing polar group, a polymer containing TFE units and ethylene-based units (ETFE), and TFE units and propylene-based units.
  • PTFE polytetrafluoroethylene
  • ETFE ethylene-based units
  • FFE units and propylene-based units examples include polytetrafluoroethylene (PTFE) having an oxygen-containing polar group, a polymer containing TFE units and ethylene-based units (ETFE), and TFE units and propylene-based units.
  • polymers containing TFE units and units based on perfluoro(alkyl vinyl ether) (PAVE) (PAVE units) (PFA) or polymers containing TFE units and units based on hexafluoropropylene (HFP units) (FEP) is preferred, PFA and FEP having an oxygen-containing polar group are more preferred, and PFA having an oxygen-containing polar
  • the F polymer is preferably a polymer having carbonyl group-containing groups comprising TFE units and PAVE units, more preferably comprising units based on monomers having TFE units, PAVE units and carbonyl group-containing groups, TFE units , PAVE units and units based on monomers having a carbonyl group-containing group, with respect to all units, these units in this order 90 to 99 mol%, 0.99 to 9.97 mol%, 0.01 to More preferably, the polymer contains 3 mol %, or the polymer contains 87-96 mol %, 0.99-9.97 mol %, 3-6 mol %.
  • the former case is preferable because it facilitates obtaining a composite sheet having excellent heat resistance. In the latter case, the composite sheet having excellent adhesiveness between the F polymer and the liquid crystal polymer woven fabric or non-woven fabric is easily obtained, which is preferable.
  • Specific examples of such F polymers include the polymers described in WO2018/016644.
  • F polymers include hot melt tetrafluoroethylene-based polymers containing PAVE units.
  • PAVE units by having PAVE units, the degree of conformational freedom of the F polymer can be improved while maintaining the excellent electrical properties of the tetrafluoroethylene-based polymer, and the composite sheet has electrical properties, low linear expansion, and a base material. It is easy to be excellent in adhesiveness with.
  • the heat-melting tetrafluoroethylene-based polymer containing PAVE units may be one that does not have a carbonyl group-containing group, or one that does not contain a unit based on a monomer having a carbonyl group-containing group.
  • the content of the PAVE units in the total units in the F polymer is preferably 1.0 mol% or more, more preferably 2.0 mol% or more, and further preferably 2.3 mol% or more. preferable.
  • the PAVE unit content is at least the above lower limit, it is believed that the melt flowability of the F polymer is increased, and that microspherulites are easily formed, thereby improving adhesive strength.
  • the content of PAVE units in the total units in the F polymer is preferably 10.0 mol % or less, more preferably 5.0 mol % or less.
  • the content of PAVE units in the total units in the F polymer is 2.0 mol % or more of the F polymer is preferably terminally fluorinated, and the number of oxygen-containing polar groups in the F polymer is preferably 500 or less per 1 ⁇ 10 6 carbon atoms in the main chain, and 100 The following are more preferable, and 0 is even more preferable.
  • This polymer consists of TFE units and PPVE units, and preferably has a TFE unit content of 95.0 to 98.0 mol % and a PPVE unit content of 2.0 to 5.0 mol %.
  • a hot-melt polymer means a polymer for which there exists a temperature at which the melt flow rate is between 1 and 1000 g/10 minutes under the condition of a load of 49N.
  • the melt flow rate of the F polymer is preferably 1 to 30 g/min, more preferably 5 to 30 g/min under a load of 49 N from the viewpoint of impregnating the woven or nonwoven fabric of the liquid crystal polymer with the F polymer satisfactorily.
  • the melting temperature of the F polymer is preferably 200°C or higher, more preferably 260°C or higher.
  • the melting temperature of the F polymer is preferably 325° C. or lower, more preferably 320° C. or lower, from the viewpoint of satisfactorily impregnating the liquid crystal polymer woven fabric or non-woven fabric with the F polymer.
  • the glass transition point of the 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, from the viewpoint of good impregnation into the liquid crystal polymer woven fabric or non-woven fabric.
  • the fluorine content of the F polymer is preferably 70% by mass or more, more preferably 72 to 76% by mass, from the viewpoint of improving the electrical properties and heat resistance of the composite sheet.
  • fluorine content is calculated
  • the surface tension of the F polymer is preferably 16-26 mN/m.
  • the surface tension can be measured by placing a droplet of a wetting index reagent (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) on a flat plate made of F polymer. Even if the F polymer has a low surface tension, it tends to have excellent adhesiveness to the woven fabric or non-woven fabric of the liquid crystal polymer because the F polymer has oxygen atoms.
  • the spherulite radius of the F polymer in the composite sheet is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m, from the viewpoint of adhesion of the liquid crystal polymer to the woven fabric or nonwoven fabric and substrate.
  • the F film may consist of only the F polymer, or may further contain components other than the F polymer.
  • the content of the F polymer in the F film is preferably 50% by mass or more, more preferably 80% by mass or more.
  • the content of the F polymer is preferably 100% by mass or less.
  • the F film may contain a polymer different from the F polymer (hereinafter also referred to as "different polymer").
  • different polymers include tetrafluoroethylene-based polymers that do not have oxygen atoms, non-heat-melting tetrafluoroethylene-based polymers, epoxy resins, polyimide resins, polyamic acids that are polyimide precursors, polyamideimide resins, and precursors of polyamideimide resins.
  • the different polymers non-thermally fusible tetrafluoroethylene-based polymers and aromatic polymers are preferred.
  • One type of different polymer may be used, or two or more types may be used.
  • Tetrafluoroethylene-based polymers having no oxygen atoms include PTFE, ETFE, polymers containing TFE units and propylene-based units, and FEP. These polymers may or may not contain further units based on other comonomers. However, the polymers exemplified above do not have oxygen atoms.
  • Non-heat-melting tetrafluoroethylene-based polymers include non-heat-melting PTFE.
  • aromatic polymers are aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, and aromatic polyamideimide precursors.
  • aromatic polymers include "Upia-AT” series (manufactured by Ube Industries, Ltd.), “Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria (registered trademark)” series (manufactured by 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 polymers is preferably 0.1 to 60% by mass, more preferably 1 to 40% by mass, relative to the total mass of the F film.
  • the different polymer is a non-thermally fusible tetrafluoroethylene-based polymer
  • the content of the non-thermally fusible tetrafluoroethylene-based polymer relative to the total mass of the F film is preferably 10 to 60 mass%, preferably 20 to 50. % by mass is more preferred.
  • the different polymer is an aromatic polymer
  • the content of the aromatic polymer is preferably 0.1-30% by weight, more preferably 1-10% by weight, relative to the total weight of the F film.
  • the F film may contain an inorganic filler.
  • inorganic fillers carbon fillers, inorganic nitride fillers or inorganic oxide fillers are preferable, and carbon fiber fillers, glass fiber fillers, boron nitride fillers, aluminum nitride fillers, beryllia fillers, silica fillers, wollastonite fillers, talc fillers.
  • cerium oxide filler, aluminum oxide filler, magnesium oxide filler, zinc oxide filler or titanium oxide filler are more preferable, and boron nitride filler or silica filler is more preferable.
  • One type of inorganic filler may be used, or two or more types may be used.
  • D50 of the inorganic filler 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.
  • the specific surface area of the inorganic filler is preferably 1-20 m 2 /g.
  • the surface of the inorganic filler may be surface-treated with a silane coupling agent.
  • Silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Silane coupling agents with functional groups are preferred, such as isocyanatopropyltriethoxysilane.
  • the shape of the inorganic filler is preferably spherical, needle-like, fibrous or plate-like, preferably spherical, scale-like or layer-like, more preferably spherical or scale-like.
  • the spherical inorganic filler is preferably substantially spherical.
  • substantially spherical means that the proportion of inorganic fillers having a minor axis to major axis ratio of 0.7 or more is 95% by number or more when the inorganic filler is observed with a scanning electron microscope (SEM). do.
  • the aspect ratio of the non-spherical inorganic filler is preferably 2 or more, more preferably 5 or more. The aspect ratio is preferably 10,000 or less.
  • silica fillers include the “ADMAFINE” series (manufactured by Admatechs), the “SFP” series (manufactured by Denka), the “E-SPHERES” series (manufactured by Taiheiyo Cement), and the “Q” series (Ginet company).
  • zinc oxide fillers include the “FINEX” series (manufactured by Sakai Chemical Industry Co., Ltd.).
  • titanium oxide fillers include the “Tipake (registered trademark)” series (manufactured by Ishihara Sangyo Co., Ltd.) and the “JMT” series (manufactured by Tayca Corporation).
  • talc filler examples include "SG” series (manufactured by Nippon Talc Co., Ltd.).
  • a specific example of the steatite filler is the “BST” series (manufactured by Nippon Talc Co., Ltd.).
  • Specific examples of the boron nitride filler include the "UHP” series (manufactured by Showa Denko KK) and the "GP" and “HGP” grades of the "Denka Boron Nitride” series (manufactured by Denka).
  • the content of the inorganic filler with respect to the total mass of the F film is preferably 1 to 50% by mass, more preferably 5 to 20% by mass.
  • the F film contains an organic filler, a thixotropic agent, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, Other ingredients such as whitening agents, coloring agents, conductive agents, release agents, surface treatment agents, viscosity modifiers, and flame retardants may also be contained.
  • the content of components excluding the F polymer, polymers different from the F polymer, and inorganic filler in the total mass of the F film is preferably 0 to 10% by mass.
  • the thickness of the F film is preferably 1-200 ⁇ m.
  • the F film may be surface-treated with a silane coupling agent.
  • the silane coupling agent include those similar to the silane coupling agent that may be used for the surface treatment of the inorganic filler described above.
  • the adhesiveness at the interface between the F polymer and the woven or nonwoven fabric of the liquid crystal polymer and the adhesiveness of the composite sheet to the base material are likely to increase, which is preferable.
  • the F film may be formed by melt extruding the F polymer.
  • a sheet further containing different polymers, inorganic fillers and other components can be formed by melt-kneading the F polymer with different polymers, inorganic fillers and other components, followed by extrusion molding.
  • the F film may be formed from a dispersion containing particles of F polymer and a liquid dispersion medium.
  • the F film is produced by applying a dispersion containing particles of the F polymer to the surface of a temporary substrate, heating the temporary substrate to which the dispersion has been applied, and heating the temporary substrate and the F polymer.
  • a layer containing and a layer may be obtained and formed by removing the temporary base material from the layered product.
  • the temporary base material to which the dispersion has been applied in two stages: heating for removing the liquid dispersion medium and heating for baking the F polymer.
  • the temporary base material include metal foils and resin films, and methods for removing the temporary base material include peeling, etching, and the like.
  • sheets further containing different polymers, inorganic fillers and other ingredients can be formed by using particles of F polymer and a liquid dispersion medium, and dispersions containing different polymers, inorganic fillers and other ingredients.
  • the ratio of the volume concentration of the F polymer to the volume concentration of the liquid crystal polymer woven fabric or non-woven fabric in the composite sheet is preferably 0.6 or more, more preferably 1 or more, where the volume concentration of the liquid crystal polymer woven fabric or non-woven fabric is 1. .
  • Such a ratio is preferably 4 or less, more preferably 3 or less.
  • the dielectric constant of the composite sheet is preferably 3.0 or less, more preferably 2.5 or less. A dielectric constant of 1.5 or more is preferable.
  • the dielectric loss tangent of the composite sheet is preferably 0.0100 or less, more preferably 0.0010 or less. The dielectric loss tangent is preferably 0.0001 or more. Relative permittivity and dielectric loss tangent are measured at a frequency of 10 GHz by the SPDR (split post dielectric resonance) method.
  • the thickness of the composite sheet is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the thickness of the composite sheet is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and may be less than 50 ⁇ m.
  • the composite sheet may be roll-shaped or sheet-shaped.
  • the composite sheet may be surface-treated.
  • Surface treatment includes corona discharge treatment, discharge treatment such as plasma treatment, plasma graft polymerization treatment, electron beam irradiation, light irradiation treatment such as excimer UV light irradiation, Itro treatment using flame, and wet etching treatment using sodium metal. is mentioned. These surface treatments can introduce polar functional groups such as hydroxyl groups, carbonyl groups, and carboxy groups onto the surface of the composite sheet.
  • the linear expansion coefficient of the composite sheet is preferably 80 ppm/°C or less, more preferably 50 ppm/°C or less, even more preferably 30 ppm/°C or less, and particularly preferably 20 ppm/°C or less.
  • the lower limit of the coefficient of linear expansion is, for example, 5 ppm/°C.
  • the coefficient of linear expansion is measured by the method specified in JIS C 6471:1995. Specifically, it is measured by the method described in Examples.
  • a woven or non-woven liquid crystal polymer fabric is impregnated with a film containing the F polymer.
  • the impregnation may be performed by impregnating one surface of the liquid crystal polymer woven fabric or nonwoven fabric with the F film, or by impregnating both surfaces of the liquid crystal polymer woven fabric or nonwoven fabric with the F film.
  • the impregnation is preferably carried out by thermally compressing the film containing the F polymer and the woven or non-woven fabric of the liquid crystal polymer.
  • the F polymer is likely to be impregnated between the fibers of the liquid crystal polymer woven fabric or non-woven fabric.
  • the adhesion between the woven fabric or non-woven fabric of the liquid crystal polymer and the F polymer tends to increase, which is preferable.
  • Thermocompression bonding is, for example, a method in which the film is superimposed on a liquid crystal polymer woven or nonwoven fabric and passed between a pair of heated rolls, a method in which pressure is applied between a pair of opposing hot plates, or a hot plate and It can be performed by a method of pinching with rolls and applying pressure.
  • the temperature for thermocompression bonding is preferably the melting temperature of the F polymer -30° C. or higher, more preferably the melting temperature of the F polymer or higher, from the viewpoint of facilitating impregnation of the liquid crystal polymer into the woven fabric or nonwoven fabric.
  • the crimping temperature is preferably the melting temperature of F polymer +30° C. or lower.
  • the thermocompression bonding temperature is preferably 280 to 380°C, more preferably 300 to 330°C.
  • the compression pressure in thermocompression bonding is preferably 0.2 MPa or more, more preferably 1 MPa or more, and more preferably 10 MPa or more.
  • the crimping pressure is preferably 1000 MPa or less, more preferably 300 MPa or less.
  • the thermocompression bonding is preferably performed under reduced pressure.
  • the atmospheric pressure is preferably 10 KPa or less, more preferably 1 KPa or less.
  • the composite sheet may be laminated with a substrate to form a laminate.
  • the composite sheet of the present disclosure tends to have excellent adhesion to the substrate.
  • the composite sheet of the present disclosure is excellent in low linear expansion properties, even if the laminate is subjected to high-temperature processing, it is difficult to separate from the substrate.
  • metal substrates copper, nickel, aluminum, titanium, metal foils of their alloys, etc.
  • heat-resistant resin films polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, Liquid crystalline polyester, heat-resistant resin film such as tetrafluoroethylene polymer), prepreg substrate (precursor of fiber reinforced resin substrate), ceramic substrate (ceramic substrate such as silicon carbide, aluminum nitride, silicon nitride), and glass substrate mentioned.
  • the shape of the substrate examples include planar, curved, and uneven shapes.
  • the shape of the substrate may be any of foil, plate, film, and fibrous.
  • the ten-point average roughness of the substrate surface is preferably 0.01 to 0.05 ⁇ m.
  • the surface of the substrate may be surface-treated with a silane coupling agent or plasma-treated.
  • a method of laminating the composite sheet and the substrate a method of thermocompression bonding can be mentioned.
  • a method of thermocompression bonding the same method as the thermocompression bonding in the production of the above-described composite sheet can be used.
  • a composite sheet is formed by impregnating a liquid crystal polymer woven or nonwoven fabric with an F film and simultaneously laminating it with a substrate to obtain a laminate of the composite sheet and the substrate.
  • a woven or non-woven fabric of liquid crystal polymer, an F film, and a base material are laminated in this order and then thermocompressed to obtain a laminate of the composite sheet and the base material.
  • thermocompression bonding the same method as the thermocompression bonding in the production of the above-described composite sheet can be used.
  • the composite sheet is formed by impregnating a liquid crystal polymer woven or nonwoven fabric with an F film, simultaneously laminating it with a copper foil, and bonding the composite sheet and the copper foil together.
  • a laminate may be obtained.
  • a woven or non-woven fabric of liquid crystal polymer, an F film and a copper foil are laminated in this order and then thermocompression bonded to obtain a copper-clad laminate in which the composite sheet and the copper foil are bonded together.
  • thermocompression bonding the same method as the thermocompression bonding in the production of the above-described composite sheet can be used.
  • a single composite sheet may be obtained by removing the substrate from the laminate.
  • the peel strength between the composite sheet and the substrate in the laminate is preferably 10 to 100 N/cm, more preferably 12 to 100 N/cm.
  • Composite sheets are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sporting goods, food industrial goods, heat dissipation parts, and the like.
  • electric wire coating materials wires for aircraft, etc.
  • enameled wire coating materials used for motors such as electric vehicles, electrical insulating tapes, insulating tapes for oil drilling, oil transportation hoses, hydrogen tanks, printed circuit boards materials, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrode binders (for lithium secondary batteries, fuel cells, etc.), copy rolls, Furniture, automobile dashboards, home appliance covers, sliding parts (load bearings, yaw bearings, slide shafts, valves, bearings, bushes, seals, thrust washers, wear rings, pistons, slide switches, gears, cams, belt conveyors , food conveyor belts, etc.), tension ropes, wear pads, wear strips, tube ramp
  • Spatter and various other materials It is useful as a heat-dissipating component in a processing unit such as a dry etching apparatus, an electromagnetic wave shield, a process film for semiconductor sintering processes, a release film for high-temperature sealing for power semiconductors, and the like.
  • Composite sheets are excellent in electrical properties and low linear expansion, so they are suitable for applications where such properties are desired.
  • the composite sheet is suitably used as a material such as a copper-clad laminate for printed wiring boards.
  • a composite sheet in one aspect of the present disclosure is a composite sheet containing a liquid crystal polymer woven or nonwoven fabric and an F polymer impregnated in the liquid crystal polymer woven or nonwoven fabric.
  • the characteristics of the composite sheet the above-mentioned items can be applied.
  • the composite sheet is preferably manufactured by the aforementioned manufacturing method of the present disclosure.
  • Nonwoven fabric of liquid crystal polymer Nonwoven fabric 1: Film-like nonwoven fabric of liquid crystalline aromatic polyester having an aromatic ring content of 60% by mass or more (deflection temperature under load: 300°C, specific gravity: 1.42 g/cm 3 , fiber diameter: 7 ⁇ m, volume basis weight: 9.9 cm 3 /m 2 )
  • Nonwoven fabric 2 Film-like nonwoven fabric of liquid crystalline aromatic polyester having an aromatic ring content of 60% by mass or more (deflection temperature under load: 300°C, specific gravity: 1.42 g/cm 3 , fiber diameter: 7 ⁇ m, volume basis weight: 28.2 cm 3 /m 2 )
  • Nonwoven fabric 3 Film-like nonwoven fabric of liquid crystalline aromatic polyester having an aromatic ring content of 60% by mass or more (deflection temperature under load: 300°C, specific gravity: 1.42 g/cm 3 , fiber diameter: 3 ⁇ m, volume basis weight: 4.2 cm 3 /m 2 )
  • Nonwoven fabric 4 Film-like nonwoven fabric of liquid
  • Woven fabric 1 A liquid crystalline aromatic polyester plain fabric having an aromatic ring content of 60% by mass or more (load deflection temperature: 300°C, specific gravity: 1.42 g/cm 3 , fiber diameter: 7 ⁇ m, thickness: 123 ⁇ m , volume basis weight: 32 cm 3 /m 2 , warp density: 20/cm, weft density: 20/cm)
  • Fabric 2 Plain fabric of liquid crystalline aromatic polyester (deflection temperature under load: 350°C, basis weight: 45 g/m 2 , “Vectran (registered trademark)” manufactured by Kuraray Co., Ltd.)
  • Copper foil 1 copper foil (thickness: 18 ⁇ m, surface ten-point average roughness: 0.8 ⁇ m)
  • Example 1 Two films 1 are superimposed on both sides of the nonwoven fabric 1, and copper foils 1 are further superimposed on both sides of the nonwoven fabric 1 to form copper foil 1/film 1/film 1/nonwoven fabric 1/film 1/film 1/copper foil 1.
  • a laminate 1 having in order is obtained.
  • Laminate 1 is thermocompression bonded under reduced pressure under thermocompression conditions of 320° C., 10 MPa, and 10 minutes for 10 minutes, impregnating film 1 from both surfaces of nonwoven fabric 1, nonwoven fabric 1, and nonwoven fabric 1.
  • a copper-clad laminate 1 (thickness: 94 ⁇ m) containing a polymer 1 and copper foils 1 laminated on both outer sides thereof is obtained.
  • Example 2 A laminate having a film 1 laminated on both sides of a nonwoven fabric 2 and copper foil 1 laminated on both sides of the nonwoven fabric 2 in order of copper foil 1/film 1/nonwoven fabric 2/film 1/copper foil 1. get 2.
  • the laminate 2 is thermocompression bonded under reduced pressure under thermocompression conditions of a temperature of 320° C., a pressure of 10 MPa, and a time of 10 minutes, impregnating the nonwoven fabric 2 with the film 1 from both surfaces, and A copper-clad laminate 2 (thickness: 88 ⁇ m) containing polymer 1 and copper foil laminated on both outer sides is obtained.
  • Example 3 A copper-clad laminate 3 (thickness: 89 ⁇ m) is obtained in the same manner as in Example 1, except that the nonwoven fabric 1 is changed to the nonwoven fabric 3.
  • Example 4 A copper-clad laminate 4 (thickness: 77 ⁇ m) is obtained in the same manner as in Example 2 except that the nonwoven fabric 1 is changed to the nonwoven fabric 4 .
  • Example 5 A copper-clad laminate 5 (thickness: 94 ⁇ m) is obtained in the same manner as in Example 1 except that the film 1 is changed to the film 2 and the thermocompression bonding temperature is set to 290°C.
  • Example 6 A copper-clad laminate 6 (thickness: 94 ⁇ m) is obtained in the same manner as in Example 1 except that the film 1 is changed to the film 3.
  • Example 7 A copper clad laminate 7 (thickness: 94 ⁇ m) is obtained in the same manner as in Example 1 except that the film 1 is changed to the film 4.
  • Example 8 A copper clad laminate 8 (thickness: 130 ⁇ m) is obtained in the same manner as in Example 1 except that the film 1 is changed to the film 5 and the nonwoven fabric 1 is changed to the woven fabric 1.
  • Example 9 A copper-clad laminate 9 (thickness: 130 ⁇ m) is obtained in the same manner as in Example 1 except that the film 1 is changed to the film 5 and the nonwoven fabric 1 is changed to the woven fabric 2 .
  • Composite Sheet The copper foil of the copper-clad laminate 1 is removed by etching with an aqueous solution of ferric chloride, followed by drying by heating in an oven at 100° C. for 1 hour to obtain a composite sheet 1 .
  • Composite sheets 2-9 are obtained in the same manner as composite sheet 1, except that copper-clad laminate 1 is changed to copper-clad laminates 2-9.
  • A relative permittivity is 2.2 or less, and dielectric loss tangent is 0.0010 or more and less than 0.0020, It has a dielectric constant of more than 2.2 and 2.4 or less and a dielectric loss tangent of less than 0.0010.
  • B Relative permittivity is more than 2.2 and 2.4 or less, and dielectric loss tangent is 0.0010 or more and less than 0.0020.
  • Table 1 summarizes the materials used to manufacture each copper-clad laminate and composite sheet, the thickness of the copper-clad laminate, and the evaluation results.
  • composite sheets 1 to 6, 8 and 9 are excellent in electrical properties and low linear expansion properties, and composite sheet 9 is particularly excellent in low linear expansion properties.
  • Composite sheets 1 to 6, 8 and 9 are also excellent in peel strength from the copper foil.

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Abstract

L'invention concerne : un procédé de production d'une feuille composite, qui produit une feuille composite par imprégnation d'un tissu tissé ou non tissé d'un polymère à cristaux liquides avec un film comprenant un polymère de tétrafluoroéthylène thermofusible qui contient l'atome d'oxygène ; et ladite feuille composite.
PCT/JP2022/028125 2021-07-20 2022-07-19 Procédé de production d'une feuille composite, et feuille composite Ceased WO2023002999A1 (fr)

Priority Applications (3)

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JP2023536764A JPWO2023002999A1 (fr) 2021-07-20 2022-07-19
KR1020247001559A KR20240034188A (ko) 2021-07-20 2022-07-19 복합 시트의 제조 방법 및 복합 시트
CN202280049993.4A CN117715959A (zh) 2021-07-20 2022-07-19 复合片的制造方法及复合片

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JP2021119740 2021-07-20
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JP2006182886A (ja) * 2004-12-27 2006-07-13 Du Pont Mitsui Fluorochem Co Ltd 含フッ素樹脂積層体
JP2006190627A (ja) * 2005-01-07 2006-07-20 Asahi Kasei Chemicals Corp 補強材を有する高分子固体電解質膜
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JP2003200534A (ja) * 2001-10-24 2003-07-15 Du Pont Mitsui Fluorochem Co Ltd フッ素樹脂積層体及びその製造方法
JP2006182886A (ja) * 2004-12-27 2006-07-13 Du Pont Mitsui Fluorochem Co Ltd 含フッ素樹脂積層体
JP2006190627A (ja) * 2005-01-07 2006-07-20 Asahi Kasei Chemicals Corp 補強材を有する高分子固体電解質膜
JP2007118528A (ja) * 2005-10-31 2007-05-17 Nippon Pillar Packing Co Ltd 基板材料及びプリント基板
JP2017119378A (ja) * 2015-12-28 2017-07-06 住友電工ファインポリマー株式会社 積層体、プリント配線板用基材及び積層体の製造方法

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Publication number Priority date Publication date Assignee Title
WO2024203950A1 (fr) * 2023-03-30 2024-10-03 パナソニックＩｐマネジメント株式会社 Préimprégné, stratifié à revêtement métallique et carte de câblage

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