WO2023032376A1 - 液晶ポリマーフィルムおよび液晶ポリマーフィルムの製造方法 - Google Patents

液晶ポリマーフィルムおよび液晶ポリマーフィルムの製造方法 Download PDF

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WO2023032376A1
WO2023032376A1 PCT/JP2022/022346 JP2022022346W WO2023032376A1 WO 2023032376 A1 WO2023032376 A1 WO 2023032376A1 JP 2022022346 W JP2022022346 W JP 2022022346W WO 2023032376 A1 WO2023032376 A1 WO 2023032376A1
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Prior art keywords
lcp
liquid crystal
crystal polymer
filler
polymer film
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PCT/JP2022/022346
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English (en)
French (fr)
Japanese (ja)
Inventor
裕之 大幡
有彌 井田
成道 牧野
恵大 椿本
大輝 折戸
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to JP2023545644A priority Critical patent/JP7609288B2/ja
Priority to DE112022003224.3T priority patent/DE112022003224T5/de
Priority to CN202280058517.9A priority patent/CN117897435A/zh
Priority to PCT/JP2022/032795 priority patent/WO2023033052A1/ja
Publication of WO2023032376A1 publication Critical patent/WO2023032376A1/ja
Priority to US18/442,218 priority patent/US20240182655A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/08—Screen moulding, e.g. forcing the moulding material through a perforated screen on to a moulding surface
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29K2105/0079—Liquid crystals
    • 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
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • 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
    • B29K2105/16—Fillers
    • 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
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • 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
    • B29K2305/00—Use of metals, their alloys or their compounds, as reinforcement
    • B29K2305/08—Transition metals
    • B29K2305/10—Copper
    • 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
    • B29K2427/00—Use of polyvinylhalogenides or derivatives thereof as filler
    • B29K2427/12—Use of polyvinylhalogenides or derivatives thereof as filler containing fluorine
    • B29K2427/18—PTFE, i.e. polytetrafluoroethylene, e.g. ePTFE, i.e. expanded polytetrafluoroethylene
    • 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
    • C08J2329/00—Characterised by the use 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/10—Homopolymers or copolymers of unsaturated ethers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2427/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08J2429/00—Characterised by the use 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/10—Homopolymers or copolymers of unsaturated ethers
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • 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
    • C08K2003/343—Peroxyhydrates, peroxyacids or salts thereof

Definitions

  • the present invention relates to a liquid crystal polymer film and a method for producing a liquid crystal polymer film.
  • Liquid crystal polymer has a smaller dielectric constant and dielectric loss than polyimide resin, which is a conventional substrate material. , especially for high-frequency FPC boards (flexible circuit boards). However, there is a demand for further improvement in high-frequency characteristics, and for example, the addition of fillers with excellent electrical characteristics is under study.
  • Known methods for producing LCP films from LCP resins include, for example, the melt extrusion method and the solution casting method.
  • the melt extrusion method is a method of forming an LCP film by extruding a molten LCP resin through a slit-shaped die.
  • the solution casting method is a method of forming an LCP film or a flexible copper clad laminate (FCCL) by coating a copper foil with a varnish obtained by dissolving an LCP raw material such as LCP pellets in a solvent and drying the varnish.
  • the LCP film has a linear expansion coefficient (thermal expansion coefficient: CTE) equivalent to that of the copper used as the wiring by orienting the LCP resin molecules strongly in the direction of the main surface of the film.
  • CTE thermal expansion coefficient
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2014-111699 describes a method of mixing a plate-like filler with a liquid crystal polymer powder and producing a filler-mixed liquid crystal polymer film by a melt extrusion method.
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2004-315678
  • a liquid crystal polymer resin composition containing a liquid crystalline polyester and an aprotic solvent is produced, and a liquid crystal polymer film is produced from the resin composition by a melt casting method.
  • a method is described and it is also stated that fillers may be added.
  • JP 2014-111699 A Japanese Patent Application Laid-Open No. 2004-315678
  • the present disclosure provides a liquid crystal polymer film in which the coefficient of linear expansion in the main surface of the liquid crystal polymer film containing a filler is controlled, and a flexible copper-clad laminate having a liquid crystal polymer film in which the coefficient of linear expansion is controlled.
  • the purpose is to provide a board.
  • the liquid crystal polymer film of the present disclosure is A liquid crystal polymer film comprising a liquid crystal polymer powder and a filler,
  • the filler includes a flat filler,
  • the average aspect ratio of the filler is 3 or more,
  • the average inclination of the filler with respect to the main surface direction of the liquid crystal polymer film is within 15°.
  • a liquid crystal polymer film having a controlled coefficient of linear expansion in the main surface of the liquid crystal polymer film containing a filler, and a flexible copper-clad laminate having the liquid crystal polymer film having a controlled coefficient of linear expansion are provided. be able to.
  • FIG. 1 is a photograph of a cross section of a liquid crystal polymer film in Example 1.
  • FIG. 2 is a photograph of a cross section of the liquid crystal polymer film in Example 2.
  • FIG. 3 is a photograph of a cross section of the liquid crystal polymer film in Comparative Example 1.
  • FIG. 4 is a photograph of a cross section of the liquid crystal polymer film in Comparative Example 2.
  • FIG. 5 is a photograph of the flexible copper-clad laminate in Example 1.
  • FIG. 6 is a photograph of the flexible copper-clad laminate in Comparative Example 1.
  • FIG. FIG. 7 is a flow diagram showing the manufacturing process of the liquid crystal polymer film of the embodiment.
  • a liquid crystal polymer film (LCP film) includes a liquid crystal polymer (LCP) and a filler, the filler includes a flattened filler, the average aspect ratio of the filler is 3 or more, and the filler The average inclination with respect to the thickness direction of the LCP film is within 15°.
  • thermotropic liquid crystal polymer is, for example, an aromatic polyester synthesized mainly from monomers such as aromatic diols, aromatic dicarboxylic acids, and aromatic hydroxycarboxylic acids, and exhibits liquid crystallinity when melted.
  • Liquid crystal polymer molecules have a negative coefficient of linear expansion (CTE) in the axial direction of the molecular axis and a positive CTE in the radial direction of the molecular axis.
  • CTE negative coefficient of linear expansion
  • the liquid crystal polymer does not have an amide bond.
  • a thermotropic liquid crystal polymer having no amide bond for example, a copolymer of parahydroxybenzoic acid, terephthalic acid, and dihydroxybiphenyl with a high melting point and a low CTE called a type 1 liquid crystal polymer (parahydroxybenzoic acid and block copolymer with ethylene terephthalate), or parahydroxybenzoic acid and 2,6-hydroxynaphthoate, which have a melting point between type 1 and type 2 liquid crystal polymers, called type 1.5 (or type 3).
  • Copolymers with acids block copolymers
  • liquid crystal polymer powder An LCP film according to an embodiment of the present disclosure can be manufactured by a manufacturing method described below using the liquid crystal polymer powder (LCP powder) made of the liquid crystal polymer described above.
  • the LCP powder contains fibrous particles (liquid crystal polymer fibers: LCP fibers) made of liquid crystal polymer.
  • the LCP fiber contained in the LCP powder is not particularly limited as long as it contains a fibrous portion.
  • the fibrous portion may be linear or branched.
  • the average diameter of the LCP fibers is 2 ⁇ m or less, preferably 1.4 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the average diameter of LCP fibers is, for example, 0.07 ⁇ m or more.
  • the smaller the average diameter of the LCP fibers the less overlap between the LCP fibers during LCP film production. This facilitates the in-plane orientation of the LCP during the production of the LCP film, and reduces the coefficient of linear expansion (CTE) in the main plane of the LCP film and the amount of warpage of the flexible copper-clad laminate (FCCL).
  • the average aspect ratio of the LCP fiber is preferably 10 or more and 500 or less, more preferably 10 or more and 300 or less.
  • the average diameter and average aspect ratio of LCP fibers are measured by the following methods.
  • LCP powder composed of LCP fibers to be measured is dispersed in ethanol to prepare a slurry in which 0.01% by mass of LCP powder is dispersed. At this time, the slurry is prepared so that the water content in the slurry is 1% by mass or less. Then, after dropping 5 to 10 ⁇ L of this slurry onto a slide glass, the slurry on the slide glass is naturally dried. The LCP powder is placed on the glass slide by allowing the slurry to air dry. Next, by observing a predetermined region of the LCP powder placed on the slide glass with a scanning electron microscope (SEM), 100 or more image data of particles (LCP fibers) constituting the LCP powder are collected.
  • SEM scanning electron microscope
  • the area is set according to the size of one particle of the LCP so that the number of image data is 100 or more.
  • the magnification of the SEM is changed to 500 times, 3000 times, or 10000 times as appropriate, and the image data is collected. do.
  • the longitudinal dimension and the width dimension of each of the LCP fibers are measured using the image data collected above. In one LCP fiber photographed in each of the above image data, the longest route among the routes from one end to the end opposite to the one end through the approximate center of the particle defined as the longitudinal direction. Then, the length of the straight line connecting both ends of the longest path is measured as the longitudinal dimension.
  • the dimension of the particle in the direction orthogonal to the longitudinal direction is measured at three different points in the longitudinal direction of one particle of the LCP powder.
  • the average value of the dimensions measured at these three points is taken as the width direction dimension (fiber diameter) per particle of the LCP powder.
  • the ratio of the longitudinal dimension to the fiber diameter [longitudinal dimension/fiber diameter] is calculated as the aspect ratio of the LCP fiber.
  • the average value of the fiber diameters measured for 100 LCP fibers is taken as the average diameter.
  • the average value of the aspect ratios measured for 100 LCP fibers is taken as the average aspect ratio.
  • the fibrous particles may be contained in the LCP powder as aggregates of fibrous particles.
  • the axial direction of the LCP molecules constituting the fibrous particles and the longitudinal direction of the fibrous particles tend to coincide with each other.
  • LCP powder is produced, a plurality of domains formed by bundles of LCP molecules are broken so that the axial direction of the LCP molecules is along the longitudinal direction of the fibrous particles. This is thought to be due to the orientation of the
  • the content (number ratio) of particles other than fibrous particles is 20% or less.
  • particles having a maximum height of 10 ⁇ m or less when the LCP powder is placed on a flat surface are fibrous particles, and particles having a maximum height of more than 10 ⁇ m are aggregate particles.
  • the LCP powder preferably has a D50 (average particle diameter) value of 13 ⁇ m or less as measured by particle size measurement using a particle size distribution measuring device based on a laser diffraction scattering method.
  • the surface of the LCP powder may be further treated with ultraviolet rays (UV treatment) in advance.
  • UV treatment ultraviolet rays
  • the number of oxygen atoms located on the surface of the LCP powder increases.
  • the intermolecular force between the molecules that form the surface of the LCP powder and the molecules that form the surface of the filler in the LCP film increases. This improves the interfacial adhesion between the LCP powder and the filler. As a result, the strength of the LCP film is improved.
  • fillers of the present disclosure include flat fillers, and may include fillers in shapes other than flat.
  • the “flat filler” in the present disclosure is a filler obtained by heating and compressing the filler used as a raw material (hereinafter sometimes referred to as “filler raw material”), a flat filler raw material, a spherical filler raw material, etc. It also includes fillers that have become flat aggregates, and the like.
  • the filler raw material is not particularly limited, and both organic fillers and inorganic fillers can be used.
  • organic fillers include perfluoroalkoxy fluorine (PFA) resin, polytetrafluoroethylene (PTFE), polyphenylene ether (PPE), polyimide, polyamideimide, polyetherimide, polyethersulfone, cyclic polyolefin, syndiotactic polystyrene, polyphenylene sulfide and the like.
  • organic fillers include perfluoroalkoxy fluorine (PFA) resin, polytetrafluoroethylene (PTFE), polyphenylene ether (PPE), polyimide, polyamideimide, polyetherimide, polyethersulfone, cyclic polyolefin, syndiotactic polystyrene, polyphenylene sulfide and the like.
  • inorganic fillers that can be used include powders of inorganic oxides such as talc,
  • the filler raw material is preferably an organic filler.
  • PFA resin, PTFE, and PPE are preferably used as the organic filler. Only one filler raw material may be used alone, or two or more filler raw materials may be used in combination.
  • the shape of the filler raw material is not particularly limited, and amorphous fillers, plate-like fillers, granular fillers, and the like can be used.
  • the filler raw material has a D50 (average particle size) value measured by particle size measurement using a particle size distribution measuring device based on a laser diffraction scattering method, which is 5 ⁇ m or less, preferably 3 ⁇ m or less, and 1 ⁇ m or less. is more preferable.
  • the average particle diameter of the filler raw material is preferably smaller than the average diameter of the LCP fibers.
  • the filler raw material may be surface-treated by plasma treatment.
  • Plasma treatment is, for example, in-liquid plasma treatment.
  • in-liquid plasma treatment first, an ethanol slurry is obtained by mixing a filler raw material and a 50% by mass ethanol aqueous solution. Gas is bubbled in this ethanol slurry. Discharge is performed in the bubbling gas. Plasma gas is generated by this discharge, and the surface of the filler raw material can be treated. As a result, chemical bonds of molecules on the surface of filler atoms are cut, and predetermined functional groups are generated according to the type of filler raw material.
  • the filler raw material is, for example, PFA resin, carboxyl groups are generated on the surface.
  • the intermolecular force due to hydrogen bonding between the molecules forming the surface of the LCP powder and the molecules forming the surface of the filler in the LCP film increases. This improves the interfacial adhesion between the LCP powder and the filler. As a result, the strength of the LCP film is improved.
  • Said gas is, for example, nitrogen.
  • the filler in the present disclosure has an average aspect ratio of 3 or more, and includes flat shapes such as flaky, scale-like, and flake-like.
  • the average aspect ratio of the filler is the average value of aspect ratios calculated by measuring the major diameter and minor diameter of a plurality of fillers by the method described later.
  • the major axis represents the diameter of the filler in the longest direction
  • the minor axis represents the longest length in the direction perpendicular to the major axis.
  • the aspect ratio of each filler is the ratio of the major axis to the minor axis. If the average aspect ratio of the filler is less than 3, the LCP molecules are oriented in the thickness direction of the LCP film, and the CTE within the main plane of the LCP film cannot be reduced.
  • the average aspect ratio of the filler is preferably 4 or more.
  • the average inclination of the filler with respect to the main surface direction of the LCP film is within 15°. If the average inclination of the filler with respect to the principal plane direction of the LCP film exceeds 15°, the LCP molecules are oriented in the thickness direction of the LCP film, and the CTE within the principal plane of the LCP film cannot be reduced.
  • the average inclination of the filler with respect to the main surface direction of the LCP film is preferably within 10°.
  • the average aspect ratio of the filler and the average inclination in the thickness direction of the LCP film are obtained by solidifying the LCP film or FCCL containing the filler to be measured with a resin around an arbitrary cross section, polishing it, and photographing the polished cross section with an SEM. Then, it is obtained by image analysis of the photographed image.
  • the filler and LCP powder can be identified by using image processing software (“ImageJ”) as image analysis software and binarizing the SEM image.
  • the binarization process is a process of converting the density of each pixel into two values of 1 and 0 using a constant reference value (threshold value).
  • the SEM image is subjected to binarization processing for recognizing the filler using image processing software (“ImageJ”) to obtain a binarized image.
  • ImageJ image processing software
  • the binarization process is performed based on the brightness of the pixels, for example. Although there is no definite value for the brightness threshold value in the binarization process, it is preferable to adjust the threshold value so that the ratio of the bright portion to the dark portion matches the actual volume mixing ratio of the filler and the LCP powder.
  • the major diameters and minor diameters of the plurality of fillers in the microscopic image and the inclination with respect to the thickness direction of the LCP film are calculated.
  • the number of fillers to be measured is at least 50, preferably 100 or more.
  • image analysis of 50 or more fillers as described above and the average value thereof may be used as the average aspect ratio and the average inclination with respect to the thickness direction of the LCP film.
  • the values measured for 50 or more fillers are taken as the average aspect ratio and average slope.
  • the field of view may be, for example, 50 ⁇ m long by 100 ⁇ m wide.
  • a filler having an aspect ratio between the major axis and the minor axis of 1.1 or less is regarded as a true sphere, with an aspect ratio of 1 and an inclination of 45°.
  • the area of each filler is measured by the following formula (1).
  • Area ( ⁇ m 2 ) major axis radius ( ⁇ m) ⁇ minor axis radius ( ⁇ m) ⁇ circumference ratio (1)
  • the average of the areas measured for 50 or more fillers is defined as the average area, and the area average ratio of each filler is determined by the following formula (2).
  • Area average ratio Area ( ⁇ m 2 )/Average area ( ⁇ m 2 ) Equation (2)
  • the larger the cross-sectional area of the filler the more the orientation of the LCP fibers is affected, and the greater the effect on the CTE.
  • Corrected aspect ratio measured aspect ratio ⁇ area average ratio (3)
  • the average of the corrected aspect ratios is defined as the average aspect ratio.
  • Corrected tilt (°) Measured tilt (°) x Area average ratio (4)
  • the average of the corrected slopes is defined as the average slope.
  • the method for producing a liquid crystal polymer film according to the present embodiment includes a dispersing step (S1), a matting step (S2), a heat pressing step (S3), and a metal foil removing step (S4). ).
  • the LCP powder can be produced, for example, by performing the following coarse pulverization step, fine pulverization step, coarse particle removal step, and fiberization step in this order.
  • LCP raw material examples include uniaxially oriented pellets, biaxially oriented films, and powdery LCP.
  • the LCP that constitutes the LCP raw material is the same as the LCP that constitutes the LCP fiber described above.
  • the LCP raw material is coarsely pulverized.
  • the LCP raw material is coarsely pulverized with a cutter mill.
  • the size of the coarsely pulverized LCP particles is not particularly limited as long as it can be used as a raw material for the fine pulverization step described below.
  • the maximum particle size of the coarsely ground LCP particles is, for example, 3 mm or less.
  • the LCP raw material can be used as a raw material for the fine grinding process
  • the LCP raw material may be used directly as the raw material for the fine grinding process.
  • the LCP raw material (after the coarsely pulverizing step) is pulverized while being dispersed in liquid nitrogen to obtain granular finely pulverized liquid crystal polymer (finely pulverized LCP).
  • the fine pulverization step it is preferable to use media to pulverize the LCP raw material dispersed in liquid nitrogen.
  • the media are beads, for example.
  • a bead mill which has relatively few technical problems, from the viewpoint of handling liquid nitrogen.
  • An apparatus that can be used in the pulverization step includes, for example, "LNM-08", which is a liquid nitrogen bead mill manufactured by Imex.
  • the granular, pulverized LCP obtained by the pulverization step preferably has a D50 of 50 ⁇ m or less as measured by a particle size distribution measuring device using a laser diffraction scattering method. This can prevent nozzles from being clogged with particulate pulverized LCP in the fiberization step described below.
  • coarse particle removal step coarse particles are removed from the granular finely pulverized LCP obtained in the finely pulverizing step. For example, by sieving the granular finely ground LCP with a mesh to obtain the granular finely ground LCP under the sieve, and removing the granular LCP on the sieve to remove the coarse particles contained in the granular finely ground LCP can be removed.
  • the type of mesh may be appropriately selected, and examples of meshes include those with an opening of 53 ⁇ m. Note that it is not always necessary to perform the coarse particle removal step.
  • the granular LCP is pulverized with a wet high-pressure pulverizer to obtain LCP powder.
  • the finely ground LCP is dispersed in the dispersion medium for the fiberization step.
  • the finely ground LCP to be dispersed may not have coarse particles removed, but it is preferred that coarse particles have been removed.
  • Dispersion media for the fiberizing step include, for example, water, ethanol, methanol, isopropyl alcohol, toluene, benzene, xylene, phenol, acetone, methyl ethyl ketone, diethyl ether, dimethyl ether, hexane, or mixtures thereof.
  • the finely pulverized LCP dispersed in the dispersion medium for the fiberization step that is, the paste-like or slurry-like finely pulverized LCP is passed through a nozzle while being pressurized at a high pressure.
  • the shear force or collision energy due to the high-speed flow in the nozzle acts on the LCP, crushing the granular finely pulverized LCP, thereby promoting the fiberization of the LCP and forming fine LCP fibers.
  • an LCP powder consisting of The pressure during pressurization is, for example, 100 MPa or more and 300 MPa or less.
  • the nozzle diameter of the nozzle is preferably as small as possible within the range where clogging of the finely pulverized LCP does not occur in the nozzle. Since the particle size of the finely pulverized LCP is relatively small, it is possible to reduce the nozzle diameter of the wet high-pressure crusher used in the fiberization process.
  • the nozzle diameter is, for example, 0.2 mm or less.
  • the dispersion medium penetrates into the finely pulverized LCP through the fine cracks due to the pressurization by the wet high-pressure crusher. Then, when the paste-like or slurry-like finely ground LCP passes through the nozzle and is placed under normal pressure, the dispersion medium that has entered the inside of the finely ground LCP expands in a short time. Due to the expansion of the dispersion medium that has entered the finely pulverized LCP, the destruction progresses from the inside of the finely pulverized LCP.
  • the granular LCP obtained by the conventional freeze-pulverization method is fibrillated by fibrillating the granular pulverized LCP obtained in the pulverization step of the present embodiment. It is possible to obtain an LCP powder which has a lower content of aggregated particles than the LCP powder obtained by crushing and which is composed of fine LCP fibers.
  • LCP powder may be obtained by crushing the finely pulverized LCP a plurality of times with a wet high pressure crusher.
  • the number of times of crushing by is preferably small, for example, 5 times or less.
  • the number of times of crushing by wet high-pressure crushing is preferably large, for example, 6 times or more and 90 times or less.
  • the method for producing LCP powder according to this embodiment may further include a UV treatment step.
  • the UV treatment step the LCP powder obtained in the fiberization step is surface-treated with ultraviolet rays.
  • the LCP powder obtained in the fiberization step is subjected to wet UV treatment.
  • the ultraviolet treatment time is, for example, 1 hour or more and 5 hours or less.
  • Dispersing step which is the first step of the LCP film manufacturing method
  • the LCP powder and filler material are dispersed in a dispersion medium to form a paste or slurry.
  • the LCP powder and the filler raw material can be dispersed in a highly viscous dispersion medium. A homogeneous LCP film can then be produced.
  • Dispersion media used in the dispersion process include butanediol, water, ethanol, terpineol, and a mixture of water and ethanol.
  • a paste-like mixture of LCP powder and filler is obtained.
  • a mixture of water and ethanol is used as the dispersion medium, a slurry-like mixture of LCP powder and filler is obtained.
  • the LCP powder and the filler raw material may be mixed at a volume ratio of 5:5 to 8:2. If the volume ratio of the filler raw material is larger than that of the LCP powder, the filler becomes the main component in the mixture, making it difficult to form the mixture into a film. Moreover, it is more preferable to mix the LCP powder and the filler material at a volume ratio of 5:5 to 7:3.
  • the ratio of the filler content to the total content of the liquid crystal polymer and filler is more preferably 30 vol % or more and 50 vol % or less. When the content ratio of the filler is 30 vol % or more and 50 vol % or less, it becomes easy to achieve both the desired effect of improving the electrical characteristics of the filler and the molding of the LCP film.
  • the paste or slurry mixture of LCP powder and filler is dried to form a liquid crystal polymer fiber mat (LCP fiber mat).
  • the matting step includes, for example, a coating step and a drying step.
  • a mixture of paste-like LCP powder and filler is coated on a metal foil such as copper foil.
  • a mixture of a paste-like LCP powder and a filler is applied onto a metal foil such as a copper foil as described above.
  • a composite sheet or the like made of a reinforcing material and a heat-resistant resin that is difficult to adhere to the LCP may be used. This facilitates industrial production of the LCP film.
  • the mixture of the paste-like LCP powder and the filler applied to the copper foil is heated and dried to evaporate the dispersion medium.
  • An LCP fiber mat is formed on a metal foil such as a copper foil by the heat drying described above.
  • the dispersion medium is gradually removed from the mixture of the paste-like LCP powder and the filler, so the overall thickness of the mixture of the paste-like LCP powder and the filler gradually decreases during drying. Become.
  • the thickness of the LCP fiber mat is reduced compared to the total thickness of the pasty LCP powder and filler mixture formed on the copper foil.
  • the longitudinal orientation of the fibrous particles in the LCP powder changes. Specifically, among the fibrous particles, the fibrous particles having a longitudinal direction in the entire thickness direction of the mixture of the paste-like LCP powder and the filler are oriented in the direction of the main surface of the copper foil. Like, tilt. Therefore, there is anisotropy in the longitudinal direction of the fibrous particles in the formed LCP fiber mat.
  • a paste-like mixture of LCP powder and filler is further applied on the LCP fiber mat formed on the metal foil by the drying step, and then dried to vaporize the dispersion medium.
  • the coating process and the drying process may be repeated in this order.
  • an LCP fiber mat having a desired basis weight can be obtained.
  • a mixture in which the mixing ratio of the LCP powder and the filler is changed for each coating process may be used.
  • an LCP fiber mat capable of forming an LCP film having desired properties can be obtained.
  • a mixture of slurry LCP powder and filler may be formed into an LCP fiber mat by a papermaking method.
  • a papermaking method there is no need to use a special dispersion medium (eg, expensive terpineol) used in the coating step.
  • the dispersion medium used in the dispersion step can be easily recovered and reused.
  • LCP films can be produced at low cost by the above papermaking method.
  • slurry-like LCP powder and filler are made on a mesh, a non-woven microporous sheet, or a woven fabric. Then, the LCP fiber mat is obtained by heating and drying the mixture of the slurry-like LCP powder and the filler arranged on the mesh.
  • the LCP fiber mat is heat-pressed to obtain an LCP film. Further, by hot-pressing the LCP fiber mat, the filler raw material or the aggregate of the filler raw material becomes flattened, and the filler is oriented at an angle of 15° or less with respect to the main surface direction of the LCP film. Specifically, in the hot press step, the LCP fiber mat is hot pressed together with the copper foil. As a result, the heat pressing step also serves as the step of joining the LCP film and the copper foil together, so the LCP film with the copper foil joined can be obtained at a low cost. In the heat press step, when heating for a long time, it is preferable to subject the LCP fiber mat to vacuum heat press.
  • the heating in the heat press process is performed to bond the LCP fibers together.
  • the average particle size of the filler raw material exceeds 1 ⁇ m, it is preferable to heat-press in the range of ⁇ 10° C. of the melting point of the filler raw material. .
  • the heating temperature is not limited.
  • the heating in the heat press process Preferably the temperature is below the melting point of the LCP fiber.
  • the pressure in the heat pressing step is preferably 3 MPa or more, and 5 MPa or more, so that the filler raw material becomes flat and the filler is oriented so that the inclination is within 15° with respect to the main surface direction of the LCP film. It is more preferable to have If the pressure is too high, the LCP resin melts and flows, so the pressure is preferably 10 MPa or less.
  • the holding time in the heat press process is not particularly limited, and may be, for example, 5 seconds or longer, or 10 seconds or longer. Further, since the filler raw material becomes more flattened by holding it for a long time, the holding time may be, for example, 3 minutes or longer, or 5 minutes or longer.
  • LCP in the heat press process, it is difficult to bond LCP to a reinforcing material such as a polyimide film, PTFE film, or glass fiber fabric as a release film between the press used in the heat press process and the LCP fiber mat.
  • a reinforcing material such as a polyimide film, PTFE film, or glass fiber fabric
  • a composite sheet or the like made of a heat-resistant resin may be sandwiched.
  • an additional copper foil may be sandwiched between the press and the LCP fiber mat.
  • an LCP film with copper foil bonded on both sides can be obtained.
  • An LCP film with copper foil bonded on both sides can be used as a double-sided copper foil FCCL.
  • the external dimensions of the LCP film formed by the heat pressing process as seen from the thickness direction are approximately the same as the LCP fiber mat before heat pressing. Then, by the heat press, among the fibrous particles of the LCP powder in the LCP fiber mat, the fibrous particles having a longitudinal direction along the thickness direction of the LCP fiber mat are pushed down in the main surface direction of the copper foil. It is heated while Since the LCP constituting the LCP powder has the molecular axis direction in the longitudinal direction of the fibrous particles, the molecular axis direction of the LCP is also pushed down in the direction of the main surface of the copper foil.
  • the axial direction of each molecule constituting the LCP is oriented along the main in-plane direction of the LCP film over the thickness direction of the LCP film, except for the molecules constituting the aggregated particles. Therefore, in the molded LCP film, the main orientation direction of the LCP molecules tends to follow the main in-plane direction of the copper foil, that is, the main in-plane direction of the LCP film.
  • the filler is heated while being pushed down in the in-plane direction of the copper foil by the heating press. Therefore, the major axis of the filler is oriented along the main in-plane direction of the LCP film over the thickness direction of the LCP film.
  • the LCP film of the present embodiment has a reduced CTE in the main surface due to these factors.
  • Metal foil removal step S24
  • the metal foil bonded to the LCP film may be removed by etching or the like. This yields a single LCP film to which no metal foil is bonded.
  • Example 1 Manufacture of liquid crystal polymer powder
  • LCP pellets cylindrical pellets with a diameter of 3 to 4 mm, melting point: 315° C.
  • the LCP material is a block copolymer of parahydroxybenzoic acid and 4,6-hydroxynaphthoic acid.
  • This LCP raw material was coarsely pulverized with a cutter mill (manufactured by IKA, MF10).
  • Coarsely pulverized LCP was obtained by passing the coarsely pulverized LCP through a mesh with a diameter of 3 mm provided at the outlet of the cutter mill.
  • the coarsely pulverized LCP was finely pulverized with a liquid nitrogen bead mill (LNM-08 manufactured by Imex, vessel capacity: 0.8 L). Specifically, 500 mL of media and 30 g of coarsely pulverized LCP were put into a vessel and pulverized for 120 minutes at a rotation speed of 2000 rpm. As media, zirconia (ZrO 2 ) beads with a diameter of 5 mm were used. In the liquid nitrogen bead mill, wet pulverization is performed in a state in which the coarsely pulverized LCP is dispersed in liquid nitrogen. Thus, by pulverizing the coarsely pulverized LCP with a liquid nitrogen bead mill, granular finely pulverized LCP was obtained.
  • a liquid nitrogen bead mill liquid nitrogen bead mill
  • the particle size of this finely ground LCP was measured.
  • the finely pulverized LCP dispersed in the dispersion medium was subjected to ultrasonic treatment for 10 seconds, and then set in a particle size distribution measuring device (manufactured by Horiba, LA-950) using a laser diffraction scattering method. , particle size measurements were performed.
  • Ekinen registered trademark, Nippon Alcohol Sales Co., Ltd.
  • the measured D50 of the micronized LCP was 23 ⁇ m.
  • the dispersion obtained by dispersing the finely ground LCP in Ekinene was sieved through a mesh with an opening of 100 ⁇ m to remove coarse particles contained in the finely ground LCP, and the finely ground LCP that passed through the mesh was recovered.
  • the yield of finely pulverized LCP by removing coarse particles was 85% by mass.
  • the finely pulverized LCP from which coarse particles were removed was dispersed in a 20% by mass ethanol aqueous solution.
  • the ethanol slurry in which the finely pulverized LCP was dispersed was crushed five times using a wet high-pressure crusher under conditions of a nozzle diameter of 0.2 mm and a pressure of 200 MPa to form fibers.
  • a high-pressure disperser (Nanoveita manufactured by Yoshida Kikai Kogyo Co., Ltd.) was used as the wet high-pressure crusher.
  • LCP powder was obtained by drying the ethanol slurry in which finely ground LCP was dispersed with a spray dryer.
  • the average fiber diameter measured for 100 LCP fibers contained in the LCP powder was 0.8 ⁇ m.
  • a perfluoroalkoxy fluororesin (PFA resin) (irregular shape, average particle size: 2 ⁇ m, melting point: 300° C.) was prepared as a filler raw material.
  • the PFA resin and the LCP powder obtained above were dispersed in butanediol as a dispersion medium to form a paste.
  • the mixing ratio of the PFA resin and the LCP powder was 3:7 by volume.
  • the paste mixture is applied to a 180 mm square, 12 ⁇ m thick electrolytic copper foil (Furukawa Electric Co., Ltd., FWJ-WS-12) on the roughened surface. applied. Then, the electrolytic copper foil coated with the paste-like mixture was heated on a hot plate to 180° C. to vaporize the butanediol as the dispersion medium, and the paste-like mixture on the electrolytic copper foil was dried. . Thus, a thin LCP fiber mat was formed on the electrolytic copper foil.
  • the pasty mixture was further applied onto this thin LCP fiber mat.
  • the applied pasty mixture was dried in the same manner as the previously applied pasty mixture was dried. In this way, by repeating the above-described application and drying a plurality of times, an LCP fiber mat adjusted to have a basis weight of 35 g/m 2 was formed on the electrolytic copper foil.
  • the LCP fiber mat formed on the electrolytic copper foil was heat-pressed together with the electrolytic copper foil using a high-temperature press machine. Specifically, first, a release film was laminated on the side opposite to the electrodeposited copper foil side of the LCP fiber mat formed on the electrodeposited copper foil. As the release film, a polyimide film (Kapton (registered trademark) 100H manufactured by Toray DuPont) was used. Then, the LCP fiber mat laminated with the release film was set in a high-temperature press. The set LCP fiber mat was pressed together with the release film and the electrolytic copper foil at a temperature of 295° C. and a press pressure of 6 MPa for 10 seconds. The size of the pressing member used for pressing was 170 mm square. After the hot press was completed, the release film was removed to obtain FCCL.
  • a release film was laminated on the side opposite to the electrodeposited copper foil side of the LCP fiber mat formed on the electrodeposited copper foil.
  • a polyimide film Kerpton (registered trademark
  • the electrolytic copper foil bonded to the LCP film was removed by etching using an aqueous solution of ferric chloride. An LCP film was thus obtained.
  • the thickness of the LCP film was 25 ⁇ m.
  • Example 2 PFA resin, which is a filler raw material similar to that in Example 1, was used.
  • the PFA resin was pulverized by repeatedly crushing 20 times.
  • the same LCP powder as in Example 1 and the pulverized PFA resin obtained above were pressed using the same vacuum high-temperature press as in Example 1 at a temperature of 310 ° C. and a press pressure of 6 MPa.
  • FCCL and LCP films were manufactured in the same manufacturing process as in Example 1, except that they were pressed for a minute.
  • Example 3 PTFE micropowder (irregular shape, average particle diameter: 0.2 ⁇ m, melting point: 327° C.) was used as a filler raw material, and an LCP fiber mat was formed by a papermaking method.
  • the PTFE micropowder and the same LCP powder as in Example 1 were dispersed in a 50% by mass ethanol aqueous solution as a dispersion medium to form a slurry.
  • the mixing ratio of PTFE micropowder and LCP powder was 3:7 by volume.
  • the slurry mixture was placed on a wire mesh of 80 mesh, and the polyester microfiber nonwoven fabric (weight per unit area: 14 g/m 2 ) was placed on the paper using a rectangular sheet machine (manufactured by Kumagai Riki Kogyo Co., Ltd.). Raised to obtain an LCP fiber mat.
  • the weight of the LCP fiber mat was 2.55 g so that the thickness of the LCP film was 25 ⁇ m.
  • the LCP fiber mat was dried with a hot air dryer and transferred onto the same electrolytic copper foil as in Example 1 to form an LCP fiber mat.
  • FCCL and LCP films were manufactured in the same manufacturing process as in Example 1, except that the LCP fiber mat was formed by a papermaking method.
  • Example 4 In Example 4, uniaxially oriented LCP pellets (cylindrical pellets with a diameter of 3 to 4 mm, melting point: 340° C.) were prepared as the LCP raw material.
  • the LCP material is a block copolymer of parahydroxybenzoic acid and 4,6-hydroxynaphthoic acid.
  • LCP powder was prepared in the same manner as in Example 1, except that the LCP raw material was changed as described above. The average fiber diameter measured for 100 LCP fibers contained in the LCP powder was 1.4 ⁇ m.
  • Example 3 The same PTFE micropowder as in Example 3 and the LCP powder obtained above were pressed for 10 seconds at a temperature of 310° C. and a press pressure of 6 MPa using the same vacuum high-temperature press apparatus as in Example 1.
  • FCCL and LCP films were manufactured in the same manufacturing process as in Example 1, except for the following.
  • Example 5 In Example 5, PPE powder (irregular shape, average particle size: 4.5 ⁇ m, melting point: 290° C.) was used as a filler raw material. This was obtained by coarsely pulverizing and finely pulverizing PPE pellets under the same conditions using the same cutter mill and liquid nitrogen bead mill as used in the production of the LCP powder of Example 1. FCCL and LCP films were manufactured in the same manufacturing process as in Example 1, except that the PPE powder was used as the filler raw material.
  • Example 6 FCCL and LCP films were manufactured in the same manufacturing process as in Example 1, except that pulverized talc (platy, average particle size: 2.7 ⁇ m) was used as the filler raw material.
  • Example 7 An ethanol slurry in which finely pulverized LCP was dispersed was repeatedly crushed 30 times under conditions of a nozzle diameter of 0.18 mm and a pressure of 200 MPa using a wet high-pressure crusher (Starburst Lab, manufactured by Sugino Machine Co., Ltd.). By doing so, an LCP powder was manufactured by the same manufacturing process as in Example 1, except that it was made into fibers. The average fiber diameter measured for 100 LCP fibers contained in the LCP powder was 0.6 ⁇ m. As a filler raw material, the same PFA resin as in Example 1 was prepared.
  • Example 8 the ethanol slurry in which finely pulverized LCP is dispersed is crushed once under the conditions of a nozzle diameter of 0.18 mm and a pressure of 200 MPa using a wet high-pressure crusher (Starburst Lab manufactured by Sugino Machine Co., Ltd.). Therefore, the LCP powder was manufactured by the same manufacturing process as in Example 1, except that it was made into fibers. The average fiber diameter measured for 100 LCP fibers contained in the LCP powder was 1.7 ⁇ m. FCCL and LCP films were manufactured by the same manufacturing method as in Example 7, except that this LCP powder was used.
  • Example 9 An ethanol slurry in which finely pulverized LCP was dispersed was repeatedly crushed 90 times under the conditions of a nozzle diameter of 0.18 mm and a pressure of 200 MPa using a wet high-pressure crusher (Starburst Lab manufactured by Sugino Machine Co., Ltd.). By doing so, an LCP powder was manufactured by the same manufacturing process as in Example 1, except that it was made into fibers. The average fiber diameter measured for 100 LCP fibers contained in the LCP powder was 0.07 ⁇ m. FCCL and LCP films were manufactured by the same manufacturing method as in Example 7, except that this LCP powder was used.
  • Example 10 FCCL and LCP films were manufactured in the same manner as in Example 7, except that the mixing ratio of PFA resin and LCP powder was 4:6 by volume.
  • Example 11 FCCL and LCP films were manufactured in the same manner as in Example 7, except that the mixing ratio of PFA resin and LCP powder was 5:5 by volume.
  • Example 12 the LCP powder produced by the same production process as in Example 1 was subjected to wet ultraviolet treatment using a low-pressure mercury UV lamp under the conditions of a wavelength of 253.7 nm and a treatment time of 2 hours. .
  • the LCP powder before treatment and the LCP powder after treatment were each subjected to X-ray Photoelectron Spectroscopy (XPS) measurement.
  • the measurement was performed in an energy range of 0 eV or more and 1200 eV or less under the conditions of a measurement range of 1000 ⁇ m ⁇ 200 ⁇ m and two integration times using “Quantes I” manufactured by ULVAC-Phi as an XPS measurement device.
  • Example 13 An ethanol slurry was obtained by mixing the same PFA resin as in Example 1 and a 50 mass wt % ethanol aqueous solution. This ethanol slurry was subjected to submerged nitrogen plasma discharge treatment 30 times under the conditions that the electrode material was SUS, the voltage was ⁇ 4 kV, and the amount of nitrogen bubbling was 3 L/min. A plasma-treated PFA resin was thus obtained. The XPS measurement was performed for each of the PFA resin before treatment and the PFA resin after treatment. The measurement was carried out under the same conditions as those used for measuring the LCP powder in Example 12.
  • Example 14 the PFA resin pulverized in the same manner as in Example 2 was mixed with a 50% by mass ethanol aqueous solution to obtain an ethanol slurry. This ethanol slurry was subjected to submerged nitrogen plasma treatment 30 times under the conditions that the electrode material was SUS, the voltage was ⁇ 4 kV, and the amount of nitrogen bubbling was 3 L/min. A plasma-treated PFA resin was thus obtained. XPS measurement was performed under the same conditions as in Example 13 for each of the PFA resin before treatment and the PFA resin after treatment. As a result of this measurement, it was confirmed that the carboxyl group content on the surface of the PFA resin after treatment was higher than that of the PFA resin before treatment.
  • Example 15 LCP powder subjected to wet UV treatment in the same manner as in Example 12 and PFA resin treated in the same manner as in Example 14 were used, and the LCP fiber mat was used as a release film and an electrolytic copper foil.
  • FCCL and LCP films were manufactured by the same manufacturing method as in Example 3, except that the temperature was set to 310° C. and the pressing pressure was set to 6 MPa for 300 seconds.
  • Comparative Example 1 FCCL and LCP films were produced in the same manufacturing process as in Example 1, except that inorganic hollow filler alumina silica (spherical, average particle size: 4 ⁇ m) was used as the filler raw material.
  • Comparative Example 2 In Comparative Example 2, the same LCP powder and filler raw material as in Example 1 were used, and the same high temperature press apparatus as in Example 1 was used, except that the temperature was 310 ° C. and the press pressure was 2 MPa for 10 seconds. FCCL and LCP films were manufactured in the same manufacturing process as in Example 1.
  • FIGS. 1 to 4 are photographs (SEM images) of cross sections of LCP films in Examples 1, 2, Comparative Examples 1 and 2.
  • fillers with a smaller area than a perfect circle with a diameter of 1/100 or less of the thickness of the LCP film are excluded from measurement, and fillers with an aspect ratio of the major axis and the minor axis of 1.1 or less are regarded as perfect spheres. Assume that the aspect ratio is 1 and the inclination is 45°.
  • the CTE in the main surface was measured.
  • the CTE in the main plane was measured by the TMA (thermo-mechanical analysis) method according to JIS K 7197.
  • TMA thermo-mechanical analysis
  • a thermal analysis apparatus TMA4030SA, manufactured by Bruker
  • TMA4030SA thermal analysis apparatus
  • the shape was a strip (5 mm ⁇ 10 mm), and the CTE between 80° C. and 40° C. during the cooling process was determined.
  • the measurement results of the CTE of the LCP film are shown in the column of "CTE (ppm/°C)" in Table 1.
  • FCCL The amount of warpage was measured for the FCCLs according to Examples 1-15 and Comparative Examples 1-2. Specifically, a 150 mm square FCCL was placed on a glass plate with the copper foil side down, the distance from the glass plate was measured for each square of the FCCL, and the average value was taken as the amount of warpage. The measurement results of the amount of warpage of FCCL are shown in the column of "amount of warpage (mm)" in Table 1. It should be noted that the FCCL becomes cylindrical as the warp increases, and the distance from the glass plate cannot be measured for a square. When a cylinder with a circumference of 150 mm is formed, the distance of the square from the glass plate becomes the maximum value (approximately 48 mm).
  • the MIT folding endurance test was performed on the LCP films according to each of Examples 1-3 and 12-15. Specifically, first, a part of the LCP film was cut to obtain a strip-shaped test piece having a width of 1 cm and a length of 10 cm. Using an MIT folding endurance tester, the test piece was subjected to a load of 500 g, a curvature radius of the bending clamp of 0.2 mm, a bending angle of 135 degrees, and a bending speed of 175 cpm. number of folds) was measured. Table 2 shows the measurement results of the MIT folding endurance.
  • the LCP films according to Examples 1 to 15, in which the average aspect ratio of the filler is 3 or more and the inclination of the filler with respect to the thickness direction of the LCP film is within 15° are the same as in Comparative Examples 1 and 2. It can be seen that the CTE is lower than that of Also, it can be seen that the amount of warpage of the FCCL is reduced in proportion to the value of CTE. This can also be confirmed from the FCCL photographs of Example 1 in FIG. 5 and Comparative Example 1 in FIG. In addition, Example 6 uses an inorganic filler as a filler raw material, and the CTE and the amount of warpage are the lowest compared to the other examples, but the flexibility is inferior to the other examples. Therefore, it can be said that the LCP films of Examples 1 to 5 using an organic filler having high flexibility are suitable for the FPC substrate (flexible circuit board).
  • Example 7 in which the average diameter of the fibrous LCP particles was 0.07 ⁇ m or more and 1.4 ⁇ m or less, the average diameter was 1.4 ⁇ m or less. It can be seen that the amount of CTE and FCCL warpage in the plane of the LCP film is reduced compared to Example 8, which is 7 ⁇ m. If the average fiber diameter of the fibrous LCP powder is 0.07 ⁇ m or more and 1.4 ⁇ m or less, the average fiber diameter of the LCP powder is relatively small, so that the mutual interaction between the fibrous LCP powders is reduced. It is believed that this facilitates in-plane orientation of the LCP during production of the LCP film, and reduces the amount of warping of the CTE and FCCL in the plane of the LCP film.
  • the LCP film according to Example 12 obtained using the LCP powder whose surface has been treated with UV light is MIT compared to the LCP films according to Examples 1 and 3. It can be seen that the number of folding endurance increased and the strength improved. It can be seen that the LCP film according to Example 13 obtained using the filler whose surface is plasma-treated has an increased MIT folding endurance and improved strength compared to Examples 1 and 3. . It can be seen that the LCP film according to Example 14 obtained using the filler whose surface is plasma-treated has an increased MIT folding endurance number and improved strength compared to Example 2.
  • the LCP film according to Example 15 obtained by using the LCP powder whose surface is UV-treated and the filler whose surface is plasma-treated has a higher MIT folding endurance number than those of Examples 12 to 14. It can be seen that the strength is further increased and the strength is further improved. It is believed that pretreatment of the surface of the LCP powder or filler in this manner improves the interfacial adhesion between the LCP powder and filler, thereby improving the film strength. Furthermore, it is believed that pretreatment of the surfaces of both the LCP powder and the filler improves the affinity between these materials and further improves the film strength.

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PCT/JP2022/022346 2021-08-31 2022-06-01 液晶ポリマーフィルムおよび液晶ポリマーフィルムの製造方法 Ceased WO2023032376A1 (ja)

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DE112022003224.3T DE112022003224T5 (de) 2021-08-31 2022-08-31 Flüssigkristallpolymer-folie und verfahren zur herstellung einer flüssigkristallpolymer-folie
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JP2014111699A (ja) * 2012-12-05 2014-06-19 Primatec Inc 液晶ポリマーフィルムの製造方法および液晶ポリマーフィルム
JP2018029187A (ja) * 2017-09-04 2018-02-22 住友化学株式会社 積層板及び金属ベース回路基板
JP2019065061A (ja) * 2017-09-28 2019-04-25 Ａｇｃ株式会社 プリント基板用樹脂組成物および製造方法
WO2021025056A1 (ja) * 2019-08-06 2021-02-11 株式会社村田製作所 樹脂シート及び樹脂多層基板
WO2021039181A1 (ja) * 2019-08-27 2021-03-04 東レ株式会社 液晶ポリエステル樹脂組成物、積層体、液晶ポリエステル樹脂フィルムおよびその製造方法
JP2021095520A (ja) * 2019-12-18 2021-06-24 共同技研化学株式会社 液状組成物，液晶ポリエステルフィルム及び該液晶ポリエステルフィルムの製造方法，並びに，積層フィルム及び該積層フィルムの製造方法

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JP2014111699A (ja) * 2012-12-05 2014-06-19 Primatec Inc 液晶ポリマーフィルムの製造方法および液晶ポリマーフィルム
JP2018029187A (ja) * 2017-09-04 2018-02-22 住友化学株式会社 積層板及び金属ベース回路基板
JP2019065061A (ja) * 2017-09-28 2019-04-25 Ａｇｃ株式会社 プリント基板用樹脂組成物および製造方法
WO2021025056A1 (ja) * 2019-08-06 2021-02-11 株式会社村田製作所 樹脂シート及び樹脂多層基板
WO2021039181A1 (ja) * 2019-08-27 2021-03-04 東レ株式会社 液晶ポリエステル樹脂組成物、積層体、液晶ポリエステル樹脂フィルムおよびその製造方法
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