WO2021177402A1 - 液晶ポリマーフィルムおよびその製造方法 - Google Patents

液晶ポリマーフィルムおよびその製造方法 Download PDF

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Publication number
WO2021177402A1
WO2021177402A1 PCT/JP2021/008426 JP2021008426W WO2021177402A1 WO 2021177402 A1 WO2021177402 A1 WO 2021177402A1 JP 2021008426 W JP2021008426 W JP 2021008426W WO 2021177402 A1 WO2021177402 A1 WO 2021177402A1
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Prior art keywords
liquid crystal
crystal polymer
polymer film
film
powder
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PCT/JP2021/008426
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English (en)
French (fr)
Japanese (ja)
Inventor
裕之 大幡
成道 牧野
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2022504456A priority Critical patent/JP7260054B2/ja
Priority to EP21763540.8A priority patent/EP4116360A4/en
Priority to CN202180013131.1A priority patent/CN115087692B/zh
Publication of WO2021177402A1 publication Critical patent/WO2021177402A1/ja
Priority to US17/900,341 priority patent/US20230002548A1/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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
    • 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
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • 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
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • 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
    • B29C43/006—Pressing and sintering powders, granules or 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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/24—Calendering
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/08—Transition metals
    • B29K2705/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/003—Layered products comprising a metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2250/00—Compositions for preparing crystalline polymers
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
    • 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

Definitions

  • the present invention relates to a liquid crystal polymer film and a method for producing the same.
  • Patent Document 1 describes a multi-axis oriented film produced from a liquid crystal polymer as a liquid crystal polymer film.
  • the polymer resin is melted, and the melt is extruded and sent to the next step.
  • the multi-axis oriented film for example, Vectra® film is described as having properties suitable for the electronic field such as a printed wiring board.
  • the liquid crystal polymer film described in Patent Document 1 is molded by a melt extrusion method.
  • the thermotropic liquid crystal polymer is extruded by raising the temperature to above the melting point.
  • Some liquid crystal polymers have a high melting point, and the melting point is close to the decomposition temperature of the liquid crystal polymer. If a liquid crystal polymer film is to be molded using such a liquid crystal polymer as a raw material by a melt extrusion method, the melting point is close to the decomposition temperature, so it is necessary to raise the temperature of the liquid crystal polymer to near the decomposition temperature. .. However, if an attempt is made to extrude the polymer resin in a state where the temperature has been raised to near the decomposition temperature, the polymer resin gels to form fish eyes or the like, or the polymer resin deteriorates. It cannot be molded into a film.
  • a polymer resin having a melting point sufficiently lower than the decomposition temperature is used as a raw material for producing a conventional liquid crystal polymer film.
  • Conventional liquid crystal polymer films manufactured from such polymer resins have low heat resistance.
  • a liquid crystal polymer film as a circuit board material is molded by a melt extrusion method, a pair of surface layers located on both surfaces in the thickness direction of the film and an inner layer located between the pair of surface layers.
  • the main orientation directions of the molecules constituting the liquid crystal polymer are different from each other. Therefore, there is a difference in the coefficient of thermal expansion between the pair of surface layers and the inner layer, for example, in one of the in-plane directions of the film.
  • the circuit board may be warped or deformed in an undulating manner due to heat from the outside.
  • the present invention has been made in view of the above problems, and an object of the present invention is to obtain a liquid crystal polymer film having improved heat resistance.
  • the liquid crystal polymer film based on the first aspect of the present invention contains a liquid crystal polymer, and as a raw material, it is heated to 400 ° C. in an inert atmosphere, cooled to room temperature at a temperature lowering rate of 40 ° C./min or more, and then again. It is made of a liquid crystal polymer molded product having an endothermic peak temperature of more than 330 ° C. when measured using a differential scanning calorimeter while heating at a heating rate of 40 ° C./min.
  • the liquid crystal polymer film based on the second aspect of the present invention is a liquid crystal film, and includes a pair of surface layers and an inner layer.
  • the pair of surface layers are located on one side surface and the other side surface in the thickness direction, respectively.
  • the inner layer is located between a pair of surface layers.
  • the main orientation direction of the molecules constituting the liquid crystal polymer contained in the pair of surface layers extends along the main orientation direction of the molecules constituting the liquid crystal polymer contained in the inner layer.
  • the heat resistance of the liquid crystal polymer film can be improved.
  • Example 1 It is a photograph which took the liquid crystal polymer powder in Example 1. It is a photograph which photographed the surface of the liquid crystal polymer fiber mat in Example 1.
  • liquid crystal polymer film according to the embodiment of the present invention contains a liquid crystal polymer.
  • the liquid crystal polymer is specifically a thermotropic liquid crystal polymer.
  • the material of the liquid crystal polymer is parahydroxybenzoic acid, 2,6-hydroxynaphthoic acid, hydroquinone, 4,4-dihydroxybiphenyl, 2,6-naphthalenedicarboxylic acid, terephthalic acid, or a block copolymer with isophthalic acid. be.
  • the molecule of the liquid crystal polymer has a negative coefficient of thermal expansion in the axial direction of the molecular axis and a positive coefficient of thermal expansion in the radial direction of the molecular axis.
  • the liquid crystal polymer according to this embodiment does not have an amide bond.
  • the liquid crystal polymer contained in the liquid crystal polymer film according to the embodiment of the present invention is heated to 400 ° C. in an inert atmosphere, cooled to room temperature at a temperature lowering rate of 40 ° C./min or more, and again at 40 ° C./min.
  • the endothermic peak temperature when measured using a differential scanning calorimeter while heating at a heating rate exceeds 330 ° C. Since the endothermic peak temperature exceeds 330 ° C., the heat resistance of the liquid crystal polymer film is improved. As a result, when the liquid crystal polymer film is used as the circuit board, it is possible to prevent the circuit board from being damaged by the repair using a soldering iron.
  • the liquid crystal polymer film according to the embodiment of the present invention is preferably made of a liquid crystal polymer molded product having an endothermic peak temperature of more than 330 ° C. as a raw material.
  • the melting point of the liquid crystal polymer is, for example, in the case of a combination of a monomer of parahydroxybenzoic acid and 4,6-hydroxynaphthoic acid, when 4,6-hydroxyhaftoeic acid is 75% by mass or more or 18% by mass or less. , Above 330 ° C.
  • the combination of monomers is not limited to this.
  • the endothermic peak temperature of the liquid crystal polymer contained in the liquid crystal polymer film is, for example, 400 ° C. or lower.
  • the endothermic peak temperature of the liquid crystal polymer molded product as a raw material is preferably 400 ° C. or lower.
  • the endothermic peak temperature in the present embodiment is preferably lower than the decomposition temperature of the liquid crystal polymer from the viewpoint of molding the liquid crystal polymer film.
  • the endothermic peak temperature measured as described above may be simply referred to as "melting point".
  • the thickness of the liquid crystal polymer film according to this embodiment is preferably, for example, 5 ⁇ m or more and 250 ⁇ m or less.
  • a test film having a width of 10 mm and a thickness of 25 ⁇ m collected from the liquid crystal polymer film is subjected to conditions of a load of 500 g, a radius of curvature of 0.2 mm, a bending / folding angle of 135 degrees, and a speed of 175 cpm.
  • the number of bendings required for the test film to be cut is 100 or more.
  • the circuit board can be a substrate for FPC (Flexible Printed Circuit), a vibrating board, an organic semiconductor substrate, an organic EL substrate, or a control. It can be suitably used for a swing plate. That is, the liquid crystal polymer film according to the present embodiment is preferably excellent not only in heat resistance but also in folding resistance from the viewpoint of being applicable to the above-mentioned base material and the like.
  • FPC Flexible Printed Circuit
  • the liquid crystal polymer film according to this embodiment preferably has a water absorption rate of 0.2% by mass or less when immersed in water at room temperature for 24 hours. As described above, when the water absorption rate is 0.2% by mass or less, the liquid crystal polymer film can be more preferably used as a circuit board member for high frequency. When the liquid crystal polymer film having a water absorption rate of 0.2% by mass or less is used as a circuit board member for high frequency, it is suppressed that the circuit board for high frequency contains water having an extremely high dielectric constant, and the relative dielectric constant and the relative dielectric constant are suppressed.
  • a liquid crystal polymer film made of a liquid crystal polymer having an amine-derived structure introduced into its molecular structure has a relatively high water absorption, and therefore has a water absorption rate of more than 0.2% by mass.
  • the liquid crystal polymer film according to this embodiment includes a pair of surface layers and an inner layer.
  • the pair of surface layers are located on one side surface and the other side surface in the thickness direction of the liquid crystal polymer film, respectively.
  • the inner layer is located between a pair of surfaces.
  • the main orientation direction of each of the molecules constituting the liquid crystal polymer contained in the pair of surface layers extends along the main orientation direction of each of the molecules constituting the liquid crystal polymer contained in the inner layer.
  • the main orientation direction of each of the molecules constituting the liquid crystal polymer contained in the pair of surface layers and the main orientation direction of each of the molecules constituting the liquid crystal polymer contained in the inner layer are the in-plane directions of the surface of the liquid crystal polymer film.
  • the liquid crystal polymer film according to the present embodiment does not substantially have a boundary surface between each of the pair of surface layers and the inner layer.
  • liquid crystal polymer film according to the present embodiment copper foil may be bonded to at least one surface, or copper foil may be bonded to both sides.
  • the liquid crystal polymer film according to the present embodiment can be used as one laminated molded body, for example, as FCCL (Flexible Copper Clad Laminates) capable of forming a circuit by the subtract method.
  • FCCL Flexible Copper Clad Laminates
  • the method for producing a liquid crystal polymer film according to an embodiment of the present invention includes, as a pre-step, a coarse pulverization step, a fine pulverization step, a coarse grain removal step, and a fibrosis step in this order.
  • a dispersion step, a matting step, a heating press step, and a metal foil removing step are provided.
  • a molded product of a liquid crystal polymer is prepared as a raw material.
  • the molded product of the liquid crystal polymer include uniaxially oriented pellets, biaxially oriented films, and powders of liquid crystal polymers.
  • the molded product of the liquid crystal polymer is preferably a pellet-shaped or powder-shaped liquid crystal polymer, which is cheaper than the film-shaped liquid crystal polymer, and more preferably the pellet-shaped liquid crystal polymer.
  • the molded product of the liquid crystal polymer does not include the liquid crystal polymer directly molded into a fibrous form by an electrolytic spinning method, a melt blow method, or the like.
  • the molded product of the liquid crystal polymer may contain a pellet-shaped liquid crystal polymer or a liquid crystal polymer processed into a fibrous form by crushing a powder-like liquid crystal polymer.
  • the melting point of the molded product of the liquid crystal polymer is preferably larger than 330 ° C, more preferably 350 ° C or higher. Thereby, a liquid crystal polymer film containing a liquid crystal polymer having a melting point of more than 330 ° C. can be obtained.
  • the film-shaped liquid crystal polymer is usually molded by the melt extrusion method.
  • a melt extrusion method for a liquid crystal polymer having a melting point higher than 330 ° C. a large amount of fish eyes of the liquid crystal polymer is generated or deterioration due to decomposition occurs.
  • the liquid crystal polymer needs to be heated to near the decomposition temperature and continuously kneaded. Therefore, it is not possible to use a film-shaped liquid crystal polymer having a melting point of more than 330 ° C. as a molded product of the liquid crystal polymer.
  • a coarsely pulverized liquid crystal polymer is obtained by coarsely pulverizing a molded product of the liquid crystal polymer.
  • a molded product of a liquid crystal polymer is roughly pulverized with a cutter mill device to obtain a coarsely pulverized liquid crystal polymer.
  • the particle size of the coarsely pulverized liquid crystal polymer is not particularly limited as long as it can be used as a raw material for the fine pulverization step described later.
  • the maximum particle size of the coarsely pulverized liquid crystal polymer is, for example, 3 mm or less.
  • the method for producing a liquid crystal polymer film in the present embodiment does not necessarily have to include a coarse pulverization step.
  • the molded product of the liquid crystal polymer can be used as a raw material for the fine pulverization step, the molded product of the liquid crystal polymer may be directly used as a raw material for the fine pulverization step.
  • a coarsely pulverized liquid crystal polymer is pulverized in a state of being dispersed in liquid nitrogen to obtain a granular finely pulverized liquid crystal polymer.
  • a medium is used to pulverize the coarsely pulverized liquid crystal polymer dispersed in liquid nitrogen.
  • the media is, for example, beads.
  • the pulverization method in which the liquid crystal polymer is dispersed in liquid nitrogen is different from the conventional freeze pulverization method.
  • the conventional freeze crushing method is a method of crushing the raw material to be crushed while pouring liquid nitrogen onto the raw material to be crushed and the main body of the crushing device, but most of the liquid nitrogen is vaporized at the time when the raw material to be crushed is crushed. ing. That is, in the conventional freeze-grinding method, most of the raw material to be crushed is not dispersed in liquid nitrogen at the time when the raw material to be crushed is crushed.
  • the raw material during pulverization located inside the pulverizer has a temperature much higher than the boiling point of liquid nitrogen, which is -196 ° C. That is, in the conventional freeze pulverization method, pulverization is carried out under the condition that the temperature inside the pulverizer is usually ⁇ 100 ° C. or higher and 0 ° C. or lower. In the conventional freeze pulverization method, even when liquid nitrogen is supplied as much as possible, the temperature inside the pulverizer is about ⁇ 150 ° C. at the lowest case.
  • the raw material to be crushed is pulverized in a state of being dispersed in liquid nitrogen
  • the raw material in a further cooled state can be pulverized as compared with the conventional freeze pulverization method.
  • the raw material to be pulverized can be pulverized at a temperature lower than -196 ° C., which is the boiling point of liquid nitrogen.
  • the brittle fracture of the raw material to be pulverized is repeated, so that the pulverization of the raw material proceeds.
  • the liquid crystal polymer that has become granular due to brittle fracture in liquid nitrogen is continuously impacted with a medium or the like in a brittle state.
  • a plurality of fine cracks are formed from the outer surface to the inside of the liquid crystal polymer obtained in the fine pulverization step of the present embodiment.
  • the granular finely pulverized liquid crystal polymer obtained by the pulverization step preferably has a D50 of 50 ⁇ m or less as measured by a particle size distribution measuring device by a laser diffraction / scattering method. As a result, it is possible to prevent the granular finely pulverized liquid crystal polymer from being clogged with the nozzle in the fibrosis step shown below.
  • the coarse grain removing step coarse grains are removed from the granular finely pulverized liquid crystal polymer obtained in the above fine pulverization step. For example, by sieving a granular finely pulverized liquid crystal polymer with a mesh, a granular finely pulverized liquid crystal polymer under the sieve is obtained, and by removing the granular liquid crystal polymer on the sieve, a granular finely pulverized liquid crystal polymer is obtained.
  • the coarse particles contained can be removed.
  • the type of mesh may be appropriately selected, and examples of the mesh include those having a mesh opening of 53 ⁇ m.
  • the method for producing the liquid crystal polymer powder according to the present embodiment does not necessarily have to include a coarse grain removing step.
  • the granular liquid crystal polymer is crushed by a wet high pressure fracturing device to obtain a liquid crystal polymer powder.
  • the finely pulverized liquid crystal polymer is dispersed in the dispersion medium for the fibrosis step.
  • the finely pulverized liquid crystal polymer to be dispersed does not have to have coarse particles removed, but it is preferable that coarse particles have been removed.
  • Examples of the dispersion medium for the fibrosis step include water, ethanol, methanol, isopropyl alcohol, toluene, benzene, xylene, phenol, acetone, methyl ethyl ketone, diethyl ether, dimethyl ether, hexane, or a mixture thereof.
  • the finely pulverized liquid crystal polymer dispersed in the dispersion medium for the fibrosis process that is, the slurry-like finely pulverized liquid crystal polymer is passed through the nozzle in a state of being pressurized at a high pressure.
  • the shearing force or collision energy due to the high-speed flow at the nozzle acts on the liquid crystal polymer to crush the granular finely crushed liquid crystal polymer, and the fibrosis of the liquid crystal polymer progresses.
  • a liquid crystal polymer powder that can be used in the process can be obtained.
  • the nozzle diameter of the nozzle is preferably made as small as possible within a range in which clogging of the finely pulverized liquid crystal polymer does not occur in the nozzle. Since the granular finely pulverized liquid crystal polymer in the present embodiment has a relatively small particle size, the nozzle diameter in the wet high-pressure crusher used in the fibrosis step can be reduced.
  • the nozzle diameter is, for example, 0.2 mm or less.
  • the dispersion medium penetrates into the inside of the finely pulverized liquid crystal polymer through fine cracks by pressurization with the wet high pressure crusher. Then, when the slurry-like finely pulverized liquid crystal polymer passes through the nozzle and is located under normal pressure, the dispersion medium that has penetrated into the finely pulverized liquid crystal polymer expands in a short time. As the dispersion medium that has penetrated into the finely pulverized liquid crystal polymer expands, destruction proceeds from the inside of the finely pulverized liquid crystal polymer.
  • the granular liquid crystal obtained by the conventional freeze pulverization method is obtained by defibrating the granular finely pulverized liquid crystal polymer obtained in the fine pulverization step in the present embodiment. It is possible to obtain a liquid crystal polymer powder having a lower content of agglomerates and being in the form of fine short fibers than the liquid crystal polymer powder obtained by crushing a polymer.
  • the finely pulverized liquid crystal polymer may be crushed a plurality of times with a wet high pressure crusher to obtain a liquid crystal polymer powder. It is preferable that the number of times of crushing by the wet high pressure crusher is small. The number of times of crushing by the wet high pressure crusher may be, for example, 5 times or less.
  • the obtained liquid crystal polymer powder is used as a raw material for the post-process.
  • the details of the liquid crystal polymer powder that can be used in the method for producing a liquid crystal polymer film according to the embodiment of the present invention will be described.
  • the liquid crystal polymer powder contains at least the fiber part.
  • the fiber portion is a short fibrous particle having an aspect ratio of 10 times or more and 500 times or less, which is the ratio of the length in the longitudinal direction to the fiber diameter, and has an average diameter of 2 ⁇ m or less.
  • Such a liquid crystal polymer powder containing fine short fibrous fiber portions having an aspect ratio of 10 times or more and 500 times or less and an average diameter of 2 ⁇ m or less cannot be produced by a conventionally known production method.
  • a liquid crystal polymer powder containing a fiber portion having an aspect ratio of 10 times or more and 500 times or less cannot be produced only by an electrospinning method, which is a method for producing ultrafine continuous long fibers.
  • the liquid crystal polymer ultrafine elongated fibers of continuous long fibers produced by the electrospinning method are cut after spinning to shorten the fibers.
  • the liquid crystal polymer ultrafine long fibers of the continuous long fibers having an extremely small fiber diameter and an aspect ratio of about infinity.
  • the liquid crystal polymer ultrafine long fibers After cutting the continuous long fiber liquid crystal polymer ultrafine fibers produced by the electrospinning method, the liquid crystal polymer ultrafine long fibers have an aspect ratio of more than 500 times.
  • the value of the average diameter of the fiber portion is the average value of the fiber diameters of a plurality of fibrous particles constituting the fiber portion.
  • the liquid crystal polymer powder according to the present embodiment contains fine fibrous particles.
  • the fiber diameter can be measured from the image data of the fibrous particles obtained when the fibrous particles are observed with a scanning electron microscope.
  • the aspect ratio of the fiber portion is preferably 300 or less, more preferably 100 or less.
  • the average diameter of the fiber portion is preferably 1 ⁇ m or less.
  • the fibrous portion may be contained in the liquid crystal polymer powder as an agglomerated portion in which fibrous particles are aggregated. Further, in the fiber portion, the axial direction of the molecules of the liquid crystal polymer constituting the fiber portion and the longitudinal direction of the fiber portion coincide with each other. In the method for producing a liquid crystal polymer film according to the present embodiment, since the liquid crystal polymer powder is produced through the above fibrosis step, a plurality of domains formed by bundling the molecules of the liquid crystal polymer. Due to the fracture between the liquid crystal polymer molecules, the axial direction of the liquid crystal polymer molecules is strongly oriented along the longitudinal direction of the fiber portion.
  • the liquid crystal polymer powder preferably contains a lumpy portion that is not substantially fibrous at a content of 20% or less. Further, it is more preferable that the liquid crystal polymer powder does not contain a lump portion.
  • the content of the lumps is evaluated by the number of lumps relative to the number of agglomerates contained in the liquid crystal polymer powder.
  • the agglomerated portion having a maximum height of more than 10 ⁇ m is the agglomerated portion
  • the agglomerated portion having a maximum height of 10 ⁇ m or less is the fiber portion.
  • the lumpy portion may be contained in the liquid crystal polymer powder as an agglomerated portion containing the lumpy particles.
  • the lump is a liquid crystal polymer powder that is not substantially fibrous.
  • the lumpy portion may have a flat outer shape.
  • the liquid crystal polymer powder in the present embodiment preferably has a D50 value of 13 ⁇ m or less measured by particle size measurement using a particle size distribution measuring device by a laser diffraction / scattering method.
  • the liquid crystal polymer powder used as a raw material in the post-process is not limited to the one produced in the pre-process described above.
  • the post-process will be described.
  • the dispersion step which is the first step of the subsequent step
  • the above-mentioned liquid crystal polymer powder is dispersed in a dispersion medium to form a paste or a slurry.
  • the liquid crystal polymer powder can be dispersed in a highly viscous dispersion medium. As a result, a homogeneous liquid crystal polymer film can be produced.
  • Examples of the dispersion medium used in the dispersion step include water, tarpineol or ethanol, and a mixture thereof.
  • tarpineol is used as the dispersion medium
  • a paste-like liquid crystal polymer powder can be obtained.
  • a mixture of ethanol and water is used as the dispersion medium, a slurry-like liquid crystal polymer can be obtained.
  • the longitudinal direction of the fiber portion in the liquid crystal polymer powder dispersed in the dispersion medium is not oriented in a specific direction in the dispersion medium.
  • the film-like liquid crystal polymer film produced by the melt extrusion method is further added. May be stretched. However, even with this stretching, the main orientation direction of the molecules located in the inner layer of the liquid crystal polymer film is not changed from the state of being inclined in the thickness direction of the film to the in-plane direction. Furthermore, in the liquid crystal polymer film produced by the melt extrusion method and stretching, the main orientation direction of the molecules in the surface layer is inclined in the flow direction (MD) with respect to the main orientation direction of the molecules in the inner layer.
  • MD flow direction
  • the ratio of the flow direction (MD) component to the vertical direction (TD) component in the main orientation direction of the molecule is different between the surface layer and the inner layer. Are different from each other. Therefore, in the liquid crystal polymer film produced by the melt extrusion method and stretching, the main orientation direction of the molecules in the surface layer and the main orientation direction of the molecules in the inner layer are different from each other. Further, in the stretching step, the liquid crystal polymer film may be cut because the melt tension of the liquid crystal polymer film is low.
  • the paste-like or slurry-like liquid crystal polymer powder is dried to form a liquid crystal polymer fiber mat.
  • the matting step includes, for example, a coating step and a drying step.
  • paste-like liquid crystal polymer powder is applied to metal foil such as copper foil.
  • a paste-like liquid crystal polymer powder is applied onto a metal foil such as copper foil as described above, but instead of the metal foil, a polyimide film, a PTFE (polytetrafluoroethylene) film, a glass fiber woven fabric, or the like is used.
  • a composite sheet made of a reinforcing material and a heat-resistant resin may be used. This facilitates the industrial production of liquid crystal polymer films.
  • the paste-like liquid crystal polymer applied to the copper foil is heated and dried to vaporize the dispersion medium.
  • the dispersion medium may be vaporized by suction.
  • a liquid crystal polymer fiber mat is formed on a metal foil such as a copper foil.
  • the thickness of the liquid crystal polymer fiber mat is smaller than the thickness of the entire paste-like liquid crystal polymer formed on the copper foil.
  • the total thickness of the paste-like liquid crystal polymer powder is about 700 ⁇ m, and the thickness of the liquid crystal polymer fiber mat is, for example, about 150 ⁇ m.
  • the orientation of the fiber portion in the polymer powder in the longitudinal direction changes. Specifically, among the fiber portions, the fiber portion having a longitudinal direction in the direction along the thickness direction of the entire paste-like liquid crystal polymer powder is tilted so that the longitudinal direction faces the in-plane direction of the copper foil. Therefore, there is anisotropy in the longitudinal direction of the fiber portion in the molded liquid crystal polymer fiber mat.
  • the dispersion medium may be vaporized by further applying a paste-like liquid crystal polymer on the liquid crystal polymer fiber mat formed on the metal foil by the drying step and then drying the paste-like liquid crystal polymer.
  • the coating step and the drying step may be repeatedly provided in this order. Thereby, a liquid crystal polymer fiber mat having a desired basis weight can be obtained.
  • the liquid crystal polymer fiber mat has voids between the liquid crystal polymer powders. Further, as described above, the longitudinal direction of the fiber portion in the liquid crystal polymer powder is inclined toward the in-plane direction of the copper foil as a whole, so that the porosity of the liquid crystal polymer fiber mat is relatively small.
  • the liquid crystal polymer fiber mat in the present embodiment is formed so that the fiber portions of the liquid crystal polymer powder are intertwined with each other.
  • a spherical liquid crystal polymer powder When a conventional granular liquid crystal polymer powder having no fiber portion like the liquid crystal polymer powder in the present embodiment, for example, a spherical liquid crystal polymer powder is matted, it is matted by the same method as the above matting step. However, since the orientation of the spherical liquid crystal polymer does not change, the axial direction of the liquid crystal polymer molecules contained in the molded liquid crystal polymer fiber mat is not oriented in a specific direction. Further, the liquid crystal polymer mat matted with the above spherical liquid crystal polymer powder has a lower porosity than the liquid crystal polymer fiber mat in the present embodiment.
  • a slurry-like liquid crystal polymer powder may be molded into a liquid crystal polymer fiber mat by a papermaking method.
  • a papermaking method it is not necessary to use a special dispersion medium used in the coating process, for example, expensive tarpineol.
  • the dispersion medium used in the dispersion step can be recovered and reused.
  • the liquid crystal polymer film can be produced at low cost by the above papermaking method.
  • a slurry-like liquid crystal polymer powder is made on a mesh, a non-woven fabric-like microporous sheet, or a woven fabric. Then, the slurry-like liquid crystal polymer arranged on the mesh is heated and dried to obtain a liquid crystal polymer fiber mat.
  • a liquid crystal polymer film is obtained by heat pressing the liquid crystal polymer fiber mat.
  • the liquid crystal polymer fiber mat is heat pressed together with the copper foil.
  • the heat pressing step also serves as a step of joining the liquid crystal polymer film and the copper foil to each other, the liquid crystal polymer film in the state where the copper foil is joined can be obtained at low cost.
  • the heat pressing step it is preferable to heat press at a temperature approximately 5 ° C. to 15 ° C. lower than the melting point of the liquid crystal polymer constituting the liquid crystal polymer powder. If heat pressing is performed at a temperature approximately 5 ° C. to 15 ° C. lower than the endothermic peak temperature, sintering of the liquid crystal polymers can easily proceed.
  • a polyimide film, a PTFE film, or a reinforcing material such as a glass fiber woven fabric and a heat-resistant resin are formed as a release film between the press machine used in the heat pressing process and the liquid crystal polymer fiber mat.
  • a composite sheet or the like may be sandwiched between them.
  • an additional copper foil may be sandwiched between the press machine and the liquid crystal polymer fiber mat. This makes it possible to obtain a liquid crystal polymer film in which copper foils are bonded to both sides.
  • a liquid crystal polymer film in which copper foils are bonded to both sides can be used as a double-sided copper-clad FCCL.
  • the external dimensions of the liquid crystal polymer film formed by the heat press process when viewed from the thickness direction, that is, the plane dimensions along the film surface, are substantially the same as those of the liquid crystal polymer fiber mat before the heat press. Then, among the fiber portions of the liquid crystal polymer powder in the liquid crystal polymer fiber mat, the fiber portions having a longitudinal direction in the direction along the thickness direction of the liquid crystal polymer fiber mat are pushed down in the in-plane direction of the copper foil by the heating press. Be heated. Since the liquid crystal polymer constituting the liquid crystal polymer powder has the axial direction of the molecules in the longitudinal direction of the fiber portion, the axial direction of the molecules of the liquid crystal polymer is also pushed down in the in-plane direction of the copper foil.
  • the main orientation direction of the molecules of the liquid crystal polymer is along the in-plane direction of the copper foil, that is, the in-plane direction of the liquid crystal polymer film.
  • the axial direction of the molecule is random, and depending on the proportion of the lumpy portion contained in the liquid crystal polymer film, there is a portion in which the axial direction of the molecule of the liquid crystal polymer is oriented in the thickness direction of the liquid crystal polymer film.
  • the liquid crystal polymer powder in the liquid crystal polymer fiber mat may be joined to each other while the fiber portions are entwined with each other.
  • the liquid crystal polymer in the liquid crystal polymer film has a structure in which each molecule is entangled with each other.
  • the fiber portion has a larger surface area than the spherical liquid crystal polymer having the same volume, the bonding area when the liquid crystal polymer powders are bonded to each other by the heat pressing step is also large.
  • the toughness and folding resistance of the liquid crystal polymer film according to the present embodiment are improved.
  • the thickness of the liquid crystal polymer film is thinner than that of the liquid crystal polymer fiber mat.
  • the liquid crystal polymer mat obtained by matting a conventional granular liquid crystal polymer powder having no fiber portion like the liquid crystal polymer powder in the present embodiment, for example, a spherical liquid crystal polymer powder is provided in the longitudinal direction.
  • the fiber portion having the axial direction of the molecular axis is not included. Therefore, even if such a liquid crystal polymer mat is heat-pressed, the axial direction of the molecules constituting the liquid crystal polymer in the liquid crystal polymer film is not pushed down. Therefore, even if a liquid crystal polymer film is produced using the liquid crystal polymer powder using the conventional granular liquid crystal polymer powder having no fiber portion, the main orientation direction of each of the molecules constituting the liquid crystal polymer is the liquid crystal polymer film. It does not follow the in-plane direction of.
  • the bonding area when the liquid crystal polymer powders are bonded to each other is extremely large. It becomes smaller. Therefore, in a liquid crystal polymer film manufactured by using a conventional liquid crystal polymer powder having no fiber portion, stress is concentrated on a joint portion between the liquid crystal polymer powders when an external force is applied. Since the joint area of the joint portion is small, the liquid crystal polymer film is broken at the joint portion when an external force is applied. As described above, the liquid crystal polymer film produced by using the conventional liquid crystal polymer powder having no fiber portion has low strength and low toughness and folding resistance. The liquid crystal polymer film cannot be used as a base material, a diaphragm or a vibration damping plate for FPC.
  • the liquid crystal polymer molecules contained in each of the pair of surface layers of the liquid crystal polymer film flow while being in direct contact with a jig such as a die. , It is strongly oriented in the flow direction (MD), which is one of the in-plane directions of the liquid crystal polymer film.
  • MD flow direction
  • the liquid crystal polymer molecules contained in the inner layer of the conventional liquid crystal polymer film have a weak orientation in the flow direction (MD) of the liquid crystal polymer film.
  • the main orientation direction of the liquid crystal polymer film contained in the inner layer is inclined in the vertical direction (TD) orthogonal to the flow direction (MD) in the in-plane direction of the liquid crystal polymer film.
  • the liquid crystal polymer film immediately after being formed using the conventional melt extrusion direction has a boundary surface between each of the pair of surface layers and the inner layer. Further, in the liquid crystal polymer film immediately after being molded by the melt extrusion method, this may be further stretched or the like.
  • the liquid crystal polymer film immediately after being molded by the melt extrusion method as described above since the liquid crystal polymer molecules in the pair of surface layers are strongly oriented in the flow direction (MD), the inner layer is formed even after the above stretching.
  • the main orientation direction of the liquid crystal polymer molecules in the above is not parallel to the main orientation direction of the liquid crystal polymer molecules in the pair of surface layers.
  • the liquid crystal polymer film produced by the melt extrusion method has the main orientation directions of the molecules constituting the liquid crystal polymer contained in the pair of surface layers and the molecules constituting the liquid crystal polymer contained in the inner layer.
  • the main orientation directions are not parallel to each other.
  • an interface is formed between the pair of surface layers of the liquid crystal polymer film and the inner layer, and peeling is likely to occur along the interface.
  • the metal foil bonded to the liquid crystal polymer film may be removed by etching or the like. As a result, a single liquid crystal polymer film to which the metal foil is not bonded can be obtained.
  • the method for producing a liquid crystal polymer film according to an embodiment of the present invention includes a dispersion step, a matting step, and a heat pressing step.
  • the dispersion step liquid crystal polymer powder containing fiber portions having an aspect ratio of 10 times or more and 500 times or less, which is the ratio of the length in the longitudinal direction to the fiber diameter, and having an average diameter of 2 ⁇ m or less. Is dispersed in a dispersion medium to form a slurry.
  • the matting step the slurry-like liquid crystal polymer powder is dried to form a liquid crystal polymer fiber mat.
  • the heat pressing step a liquid crystal polymer film is obtained by heat pressing the liquid crystal polymer fiber mat.
  • a liquid crystal polymer film can be produced from a fine short fibrous liquid crystal polymer powder that cannot be realized by a conventional liquid crystal polymer powder, so that a liquid crystal polymer film suitable as a circuit board can be obtained. Further, as a raw material, a liquid crystal polymer having a melting point of more than 330 ° C. can be adopted, and a liquid crystal polymer film containing a liquid crystal polymer having a melting point of more than 330 ° C. can be produced.
  • Example 1 In Example 1, first, as a raw material liquid crystal polymer molded product, a film-shaped liquid crystal polymer having a thickness of 250 ⁇ m and having molecules biaxially oriented in the plane direction is charged into a cutter mill device. Coarsely crushed. The melting point of the liquid crystal polymer used in Example 1 is 315 ° C. A coarsely pulverized film-like liquid crystal polymer was discharged from a discharge hole having a diameter of 3 mm provided in a cutter mill device to obtain a coarsely pulverized liquid crystal polymer.
  • the coarsely pulverized liquid crystal polymer was finely pulverized with a liquid nitrogen bead mill (LNM-08 manufactured by IMEX).
  • a liquid nitrogen bead mill In pulverization with a liquid nitrogen bead mill, the vessel volume is 0.8 L, beads made of zirconia having a diameter of 5 mm are used as media, the amount of media charged is 500 mL, 30 g of coarsely pulverized liquid crystal polymer is charged, and rotation is performed.
  • the pulverization treatment was carried out at several 2000 rpm for 120 minutes.
  • a coarsely pulverized liquid crystal polymer is dispersed in liquid nitrogen to perform a wet pulverization treatment.
  • the coarsely pulverized liquid crystal polymer was pulverized with a liquid nitrogen bead mill to obtain a granular finely pulverized liquid crystal polymer.
  • the particle size of this finely pulverized liquid crystal polymer was measured.
  • the finely pulverized liquid crystal polymer was dispersed in a dispersion medium. Enekin was used as the dispersion medium. Then, the finely pulverized liquid crystal polymer dispersed in the dispersion medium is subjected to sonication for 10 seconds, and then set in a particle size distribution measuring device (manufactured by HORIBA, Ltd., LA-950) by a laser diffraction / scattering method to obtain a particle size. Measurements were made. The value of D50 of the finely pulverized liquid crystal polymer was 23 ⁇ m.
  • the finely pulverized liquid crystal polymer was sieved with a mesh having an opening of 53 ⁇ m to remove coarse particles contained in the finely pulverized liquid crystal polymer, and the finely pulverized liquid crystal polymer that had passed through the mesh was recovered.
  • the yield of the finely pulverized liquid crystal polymer by removing the coarse particles was 85% by mass.
  • the finely pulverized liquid crystal polymer from which the coarse particles had been removed was dispersed in a 20 wt% ethanol aqueous solution.
  • the ethanol slurry in which the finely pulverized liquid crystal polymer was dispersed was repeatedly pulverized five times under the conditions of a nozzle diameter of 0.2 mm and a pressure of 200 MPa using a wet high-pressure crusher to form fibers.
  • the wet high pressure fracturing apparatus NanoVita (registered trademark) C-ES008 manufactured by Yoshida Kikai Kogyo Co., Ltd. was used.
  • a liquid crystal polymer powder dispersed in an aqueous ethanol solution was obtained.
  • FIG. 1 is a photograph of the liquid crystal polymer powder in Example 1. As shown in FIG. 1, it can be seen that a fine fibrous liquid crystal polymer powder was obtained by crushing the finely pulverized liquid crystal polymer by visual inspection with a photograph. The photographs in FIG. 1 and FIG. 2 shown below were taken with a scanning electron microscope.
  • tarpineol having a mass 20 times the mass of the dispersed liquid crystal polymer powder was added to the ethanol aqueous solution in which the above liquid crystal polymer powder was dispersed. Then, water and ethanol were vaporized and removed by heating the aqueous solution with stirring. As a result, a liquid crystal polymer powder dispersed in tarpineol was obtained. That is, the liquid crystal polymer powder was made into a paste by dispersing it in tarpineol, which is a dispersion medium.
  • a paste-like liquid crystal polymer was applied onto the roughened surface of an electrolytic copper foil (FWJ-WS-12, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 12 ⁇ m. Then, the electrolytic copper foil coated with the paste-like liquid crystal polymer powder is heated to 130 ° C. on a hot plate to vaporize the tarpineol as a dispersion medium, and the paste-like liquid crystal polymer powder on the electrolytic copper foil is vaporized. It was dried. In this way, a thin liquid crystal polymer fiber mat was formed on the electrolytic copper foil.
  • an electrolytic copper foil FWJ-WS-12, manufactured by Furukawa Electric Co., Ltd.
  • the paste-like liquid crystal polymer powder was further applied onto the thin liquid crystal polymer fiber mat.
  • the applied paste-like liquid crystal polymer powder was dried in the same manner as when the previously applied paste-like liquid crystal polymer was dried. By repeating the above coating and drying a plurality of times in this way, a liquid crystal polymer fiber mat adjusted to have a basis weight of 35 g / m 2 was molded on the electrolytic copper foil.
  • FIG. 2 is a photograph of the surface of the liquid crystal polymer fiber mat in Example 1. As shown in FIG. 2, it can be seen that the liquid crystal polymer fiber mat was obtained by repeating the application and the drying even by visual inspection by a photograph. In this example, the porosity of the liquid crystal polymer fiber mat was about 85%.
  • the liquid crystal polymer fiber mat formed on the electrolytic copper foil was heat-pressed together with the electrolytic copper foil using a vacuum heating press device (KVHC, manufactured by Kitagawa Seisakusho). Specifically, first, a release film was laminated on the side of the liquid crystal polymer fiber mat formed on the electrolytic copper foil on the side opposite to the electrolytic copper foil side. As the release film, a polyimide film (manufactured by Toray DuPont, Kapton (registered trademark) 100H) was used. Then, a liquid crystal polymer fiber mat on which a release film was laminated was set in a vacuum heating press device at room temperature.
  • KVHC vacuum heating press device
  • the set liquid crystal polymer fiber mat was pressed together with the release film and the electrolytic copper foil at a pressing pressure of 0.2 MPa, and the temperature was raised to 305 ° C. at a rate of 7 ° C./min. After reaching 305 ° C., the liquid crystal polymer film was pressed together with the release film and the electrolytic copper foil at a press pressure of 6 Mpa for 5 minutes while maintaining the temperature at 305 ° C. After completion of the heating press, the release film was removed to obtain a liquid crystal polymer film formed on the electrolytic copper foil.
  • the electrolytic copper foil bonded to the liquid crystal polymer film was removed by etching with an aqueous solution of ferric chloride. As a result, a liquid crystal polymer film was obtained.
  • the thickness of the liquid crystal polymer film was 25 ⁇ m.
  • Example 3 a liquid crystal polymer film was obtained in the same manner as in Example 1. (Example 3)
  • Example 3 instead of the film-shaped liquid crystal polymer charged into the cutter mill device in the coarse crushing step of Example 1, a uniaxially oriented pellet-shaped liquid crystal polymer is used as a raw material liquid crystal polymer molded body in the cutter mill device. A crudely pulverized liquid crystal polymer was obtained.
  • Example 3 in the heating press step, the temperature of the liquid crystal polymer fiber mat together with the release film and the electrolytic copper foil was raised to 345 ° C. at a rate of 7 ° C./min, and after reaching 345 ° C., while maintaining the temperature at 345 ° C., the press pressure was set to 6 Mpa and the press was performed for 5 minutes. Other conditions are the same as those of the heating press step in Example 1.
  • Example 4 in the heating press step, the temperature of the liquid crystal polymer fiber mat together with the release film and the electrolytic copper foil was raised to 385 ° C. at a rate of 7 ° C./min, and after reaching 385 ° C., while maintaining the temperature at 385 ° C., the press pressure was set to 6 Mpa and the press was performed for 5 minutes. Other conditions are the same as those of the heating press step in Example 1.
  • Example 4 in the heating press step, the temperature of the liquid crystal polymer fiber mat together with the release film and the electrolytic copper foil was raised to 385 ° C. at a rate of 7 ° C./min, and after reaching 385 ° C., while maintaining the temperature at 385 ° C., the press pressure was set to 6 Mpa and the press was performed for 5 minutes. Other conditions are the same as those of the heating press step in Example 1.
  • Example 6 In Example 6, first, a liquid crystal polymer powder is obtained in the same manner as in Example 3. Then, ethanol and water were further added to the aqueous ethanol solution in which the liquid crystal polymer powder was dispersed in the dispersion step, if necessary, to prepare a slurry-like liquid crystal polymer powder for the matting step. Specifically, a slurry-like liquid crystal polymer powder containing 2.18 g of liquid crystal polymer powder with respect to 30 L of a 50 wt% ethanol aqueous solution was obtained. That is, the liquid crystal polymer powder was dispersed in ethanol, which is a dispersion medium, to form a slurry.
  • a slurry-like liquid crystal polymer powder was formed into a liquid crystal polymer fiber mat by a papermaking method. Specifically, first, a slurry-like liquid crystal polymer powder was produced on a microporous sheet using a square sheet machine 2556 manufactured by Kumagai Riki Co., Ltd. The microporous sheet was made of a wet non-woven fabric of polyester microfiber and had a basis weight of 14 g / m 2 . Then, a liquid crystal polymer fiber mat having a basis weight of 35 g / m 2 was formed on the microporous sheet by heating and drying at a temperature of 100 ° C. using a hot air dryer.
  • an electrolytic copper foil manufactured by Furukawa Electric Co., Ltd., FWJ-WS-12
  • FWJ-WS-12 an electrolytic copper foil having a thickness of 12 ⁇ m
  • the liquid crystal polymer fiber mat placed on the electrolytic copper foil was peeled off from the microporous sheet, and then heat-pressed in the heat-pressing step.
  • the liquid crystal polymer fiber mat was pressed with a release film and electrolytic copper foil.
  • Other conditions are the same as in Example 3.
  • a liquid crystal polymer film was obtained by the same manufacturing method as in Example 2.
  • Comparative Example 1 In Comparative Example 1, first, in the same manner as in Example 1, a biaxially oriented film-shaped liquid crystal polymer was coarsely pulverized with a cutter mill device to obtain a coarsely pulverized liquid crystal polymer.
  • the coarsely pulverized liquid crystal polymer was finely pulverized using a dry freeze pulverizer (Hosokawa Micron Co., Ltd., Linlex Mill (registered trademark)).
  • a dry freeze pulverizer Hosokawa Micron Co., Ltd., Linlex Mill (registered trademark)
  • liquid nitrogen is supplied to the inside of the apparatus together with the coarsely pulverized liquid crystal polymer.
  • the nitrogen supplied to the inside of the device is vaporized instantaneously, the nitrogen exists as a gas inside the device.
  • the finely pulverized liquid crystal polymer was sieved with a mesh having an opening of 25 ⁇ m to remove coarse particles, and the finely pulverized liquid crystal polymer that had passed through the mesh was recovered.
  • Comparative Example 2 In Comparative Example 2, first, in the same manner as in Example 1, a biaxially oriented film-shaped liquid crystal polymer was roughly pulverized with a cutter mill device to obtain a coarsely pulverized liquid crystal polymer.
  • the coarsely pulverized liquid crystal polymer was finely pulverized using the same dry freeze pulverizer as in Comparative Example 1 to obtain a finely pulverized liquid crystal polymer having a D50 value of 25 ⁇ m.
  • This finely pulverized liquid crystal polymer was sieved with a mesh having an opening of 53 ⁇ m to remove coarse particles, and the finely pulverized liquid crystal polymer that had passed through the mesh was recovered.
  • a liquid crystal polymer film was obtained by the same manufacturing method as the step in Example 1 for the steps after the fibrosis step of fiberizing the finely pulverized liquid crystal polymer from which the coarse particles had been removed using a wet high pressure fracturing device.
  • the average diameter of the liquid crystal polymer powder used as a raw material in the subsequent process was measured.
  • the liquid crystal polymer powder to be measured was dispersed in ethanol to prepare a slurry containing 0.01 wt% liquid crystal polymer powder.
  • the slurry was prepared so that the water content in the slurry was 1 wt% or less.
  • the slurry on the slide glass was naturally dried.
  • the liquid crystal polymer powder was placed on the slide glass by allowing the slurry to air dry.
  • the above region was set according to the size of each particle of the liquid crystal polymer so that the number of image data would be 100 or more. Further, for each particle of the liquid crystal polymer, in order to suppress omission of image data collection and occurrence of measurement error, the magnification of the scanning electron microscope is appropriately changed to 500 times, 3000 times, or 10000 times, and the above is described. Image data was collected.
  • the longitudinal dimension and the width dimension of each particle of the liquid crystal polymer powder were measured.
  • a path that can be taken on one particle of the liquid crystal polymer powder photographed in each of the above image data that is, from one end of the particle through substantially the center of the particle to the opposite end of the one end.
  • the direction along the longest route was defined as the longitudinal direction.
  • the dimension of the length of the longest path was measured as the dimension in the longitudinal direction.
  • the dimensions of one particle of the liquid crystal polymer powder in the direction orthogonal to the longitudinal direction were measured at three points different from each other in the longitudinal direction. The average value of the dimensions measured at these three points was taken as the widthwise dimension per particle of the liquid crystal polymer powder.
  • one particle of the liquid crystal polymer powder whose longitudinal dimension is 10 times or more of the width dimension is defined as a fibrous particle constituting the fiber portion. That is, the fiber diameter of the particles constituting the liquid crystal polymer powder in the fiber portion is the width direction dimension of the liquid crystal polymer powder. Then, with respect to the fibrous particles constituting the fiber portion, the fiber diameters of 100 fibrous particles were measured. The value obtained by averaging the measurement results of these fiber diameters was taken as the average diameter of the fiber portion.
  • the longitudinal dimension to the width dimension is the aspect ratio, which is the ratio of the longitudinal length to the fiber diameter.
  • the aspect ratio of the 100 fibrous particles was measured, and the value obtained by averaging the measurement results of each particle was taken as the aspect ratio of the fiber portion.
  • Comparative Example 1 the average diameter and aspect ratio of the fiber portion of the finely pulverized liquid crystal polymer used as a starting material in the subsequent process were measured. These measuring methods were measured in the same manner as the methods for measuring the average diameter and the aspect ratio of the fiber portion of the liquid crystal polymer powder in each of Examples 1 to 4 and Comparative Example 2.
  • the liquid crystal polymer powder to be evaluated was collected in the state of a slurry immediately after crushing by a wet high pressure crusher. Ethanol was additionally mixed with the collected slurry-like liquid crystal polymer powder to further dilute the slurry-like liquid crystal polymer powder. Ethanol was additionally mixed until the content of the liquid crystal polymer powder in the slurry was diluted to 0.01 wt% or less. The diluted slurry was dropped onto a slide glass and then left at room temperature to vaporize ethanol, which is a dispersion medium of the slurry. In this way, the liquid crystal polymer powder was placed on the slide glass.
  • the liquid crystal polymer powder placed on the slide glass was observed with a laser microscope (manufactured by KEYENCE, VK-8700) at a magnification of 100 times. From the observation, it was confirmed that the liquid crystal polymer powder contained a plurality of agglutinating portions in Examples 1 and 2 and Comparative Example 2.
  • the maximum height of each of the plurality of agglomerates was measured.
  • the method of measuring the maximum height of the agglomerated portion will be described below.
  • a contour diagram of the height of the aggregated portion arranged on the slide glass with the surface of the slide glass as the reference height was created. The contour diagram was created so that the inclination of the slide glass was corrected so that the surface of the slide glass on the liquid crystal polymer powder side became horizontal.
  • the liquid crystal polymer powder to be measured 30 agglomerates were selected by the above microscopic observation, and the maximum height of each of these agglutinates was measured. Then, it was determined that the agglomerated portion having the maximum height of 10 ⁇ m was a lumpy portion in which the liquid crystal polymer was not fibrous. Then, in the liquid crystal polymer powder, the ratio of the number of lumpy portions to the number of agglomerated portions whose maximum height was measured was evaluated as the content of the lumpy portions contained in the liquid crystal polymer powder.
  • Comparative Example 1 the content of the lumpy portion contained in the finely pulverized liquid crystal polymer was evaluated with respect to the finely pulverized liquid crystal polymer used as a starting material in the subsequent process.
  • the content of the lumpy portion in Comparative Example 1 was evaluated in the same manner as the method for evaluating the content of the lumpy portion contained in the liquid crystal polymer powder in each of Examples 1 and 2 and Comparative Example 2.
  • the average value of the separation distances of each of these four corners was taken as the absolute value of the amount of warpage. If the liquid crystal polymer film is located on the side opposite to the glass plate side of the sample when the sample is allowed to stand on the glass plate as described above, the amount of warpage is set to a positive value and the glass plate of the sample is set. When the copper foil was located on the side opposite to the side, the amount of warpage was set to a negative value.
  • solder heat resistant temperature test The solder heat resistant temperature was measured for each of the liquid crystal polymer films according to Examples 1 to 4 and Comparative Examples 1 and 2. First, each liquid crystal polymer film after the copper foil was removed in the copper foil removing step was placed on a silicone rubber having a thickness of 5 mm. The tip of a soldering iron heated to 250 ° C. was pressed against the liquid crystal polymer film on the silicone rubber. When the liquid crystal polymer film was not deformed or perforated, the temperature of the trowel was further raised to 10 ° C., and the soldering iron tip was pressed again. This heating and pressing was repeated until the liquid crystal polymer film was deformed or perforated. The highest temperature of the tip when no deformation or perforation occurred was defined as the solder heat resistant temperature. As the soldering iron, Hakko Soldering Iron Station FX951-51 manufactured by Hakko Co., Ltd. was used.
  • Table 1 shows the results of measurement of the average diameter and average aspect ratio of the fiber portion and the evaluation of the content of the lump portion for the raw material of the post-process in each Example and each Comparative Example, and MIT for the liquid crystal polymer film.
  • the results of the folding fatigue test, the warp amount test, the solder heat resistant temperature test, and the relative permittivity measurement are shown.
  • the liquid crystal polymer films according to Examples 1 to 4 are short fibrous particles having an aspect ratio of 10 times or more and 500 times or less, which is the ratio of the length in the longitudinal direction to the fiber diameter. It is produced by using a liquid crystal polymer powder containing a fiber portion having an average diameter of 2 ⁇ m or less as a raw material for a subsequent process.
  • the content of the substantially non-fibrous lumpy portion contained in the liquid crystal polymer powder is 20% or less.
  • the amount of warpage of the liquid crystal polymer films according to Examples 1 to 4 was as small as 8 mm or less. Therefore, the liquid crystal polymer films according to Examples 1 to 4 can be suitably used as a circuit board.
  • the finely pulverized liquid crystal polymer which is the raw material for the post-process of Comparative Example 1
  • the liquid crystal polymer powder which is the raw material of the post-process of Comparative Example 2 has an average diameter of 5 ⁇ m of the fiber portion, which is more than 2 ⁇ m. The aspect ratio could not be measured because the length of the fiber portion in the longitudinal direction was too long.
  • the liquid crystal polymer film was warped so as to curl, and the amount of warpage could not be measured. Further, the liquid crystal polymer film according to Comparative Example 2 has a large warp amount of 20 mm and is not suitable for use as a circuit board.
  • the liquid crystal polymer powder used in the production of the liquid crystal polymer films according to Examples 1 to 4 can further contain a liquid crystal polymer having a melting point of more than 330 ° C.
  • the melting points of the liquid crystal polymer molded product and the liquid crystal polymer powder used in the production are 350 ° C. Therefore, the melting points of the liquid crystal polymer films according to Examples 3 and 4 are also 350 ° C., and the melting points are over 330 ° C., so that the solder heat resistant temperature is 330 ° C.
  • the solder heat resistant temperatures were significantly improved as compared with the solder heat resistant temperatures of 250 ° C. and 280 ° C., respectively, of the liquid crystal polymer films according to Comparative Examples 1 and 2.
  • each of the liquid crystal polymer films according to Examples 1 to 4 has an MIT folding resistance of 100 times or more, and the folding resistance is improved. Therefore, it was confirmed that these liquid crystal polymer films have sufficient flexibility as a base material for a flexible substrate and a diaphragm.
  • the liquid crystal polymer film according to Comparative Example 1 was very brittle, and the liquid crystal polymer film cracked when it was etched to collect a test film. Therefore, the test film could not be collected from the liquid crystal polymer film according to Comparative Example 1, and the MIT folding fatigue resistance test could not be performed. Further, the liquid crystal polymer according to Comparative Example 2 had an MIT folding resistance of 10 times, which was significantly less than 100 times.

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JPWO2024029207A1 (https=) * 2022-08-03 2024-02-08
WO2024257396A1 (ja) * 2023-06-13 2024-12-19 株式会社村田製作所 積層フィルムおよび積層フィルムの製造方法
US12617908B2 (en) 2022-08-03 2026-05-05 Murata Manufacturing Co., Ltd. Liquid crystal polymer film, laminated body including the liquid crystal polymer film, and method of producing liquid crystal polymer film

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WO2022220079A1 (ja) * 2021-04-14 2022-10-20 株式会社村田製作所 繊維マットの製造方法、および繊維マット
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JP7639951B2 (ja) 2022-08-03 2025-03-05 株式会社村田製作所 液晶ポリマーフィルムおよびこれを備えた積層体、ならびに、液晶ポリマーフィルムの製造方法
US12617908B2 (en) 2022-08-03 2026-05-05 Murata Manufacturing Co., Ltd. Liquid crystal polymer film, laminated body including the liquid crystal polymer film, and method of producing liquid crystal polymer film
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