WO2021095656A1 - Composition de poudre, film, et procédé de fabrication de film - Google Patents

Composition de poudre, film, et procédé de fabrication de film Download PDF

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Publication number
WO2021095656A1
WO2021095656A1 PCT/JP2020/041536 JP2020041536W WO2021095656A1 WO 2021095656 A1 WO2021095656 A1 WO 2021095656A1 JP 2020041536 W JP2020041536 W JP 2020041536W WO 2021095656 A1 WO2021095656 A1 WO 2021095656A1
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polymer
film
powder
inorganic filler
tetrafluoroethylene
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PCT/JP2020/041536
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English (en)
Japanese (ja)
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敦美 山邊
紀生 尾澤
佐藤　崇
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Ａｇｃ株式会社
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Priority to JP2021556069A priority Critical patent/JPWO2021095656A1/ja
Priority to CN202080078282.0A priority patent/CN114729198B/zh
Priority to KR1020227002018A priority patent/KR20220101067A/ko
Publication of WO2021095656A1 publication Critical patent/WO2021095656A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/071—Preforms or parisons characterised by their configuration, e.g. geometry, dimensions or physical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08L101/00—Compositions of unspecified macromolecular 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed

Definitions

  • the present invention relates to a predetermined powder composition, a predetermined film, and a method for producing the same.
  • JP-A-2002-265729 Japanese Unexamined Patent Publication No. 2003-171538 Japanese Unexamined Patent Publication No. 2003-200534 JP-A-2019-065061
  • Tetrafluoroethylene-based polymers have low surface tension, and their powders have extremely low affinity for aromatic polymers. Therefore, it is difficult for a molded product formed from a powder composition obtained by blending both powders to sufficiently have the physical characteristics of both polymers, not to mention the shape physical characteristics such as mechanical strength and processability due to layer separation and the like. ..
  • the present inventors have found that when the powder composition is further blended with other fillers, such a tendency tends to be remarkable, and the effect of blending the other fillers is unlikely to be exhibited.
  • An object of the present invention is suitable for forming a molded product containing a predetermined tetrafluoroethylene polymer, aromatic polymer and filler, which are not limited to shape physical characteristics such as mechanical strength, and which have a high degree of three-party physical characteristics.
  • the present invention provides a powder composition, a film having a high degree of physical characteristics of the three, and a method for producing the same.
  • the present invention has the following aspects.
  • Tetrafluoroethylene polymer powder containing a unit based on perfluoro (alkyl vinyl ether) or a unit based on hexafluoropropylene, a powder of an inorganic filler having a moth hardness of 3 to 9, and a thermoplastic aromatic material.
  • a powder composition comprising a polymer powder.
  • the tetrafluoroethylene-based polymer is a polymer having an oxygen-containing polar group, which contains a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether).
  • the content of the tetrafluoroethylene polymer, the content of the inorganic filler, and the content of the aromatic polymer are, in this order, 10 to 40% by mass, 5 to 40% by mass, and 20 to 85% by mass.
  • a method for producing a film wherein the powder composition according to any one of [1] to [10] is melt-extruded to obtain a film.
  • a tetrafluoroethylene-based polymer containing a unit based on perfluoro (alkyl vinyl ether) or a unit based on hexafluoropropylene, an inorganic filler having a hardness of 3 to 9 and a thermoplastic aromatic polymer.
  • the distribution amount of the tetrafluoroethylene-based polymer in the surface region in the thickness direction of the film is higher than the distribution amount of the tetrafluoroethylene-based polymer in the central region in the thickness direction of the film, [12]. the film.
  • the film of [12] or [13], wherein the distribution amount of the inorganic filler in the central region in the thickness direction of the film is higher than the distribution amount of the inorganic filler in the surface region in the thickness direction of the film.
  • each of the predetermined tetrafluoroethylene polymer powder, aromatic polymer powder and filler powder is contained, and the physical characteristics of the three parties are not limited to the shape physical properties such as mechanical strength.
  • a molded product such as a film having a high degree of the above can be obtained.
  • the "average particle size” is the volume-based cumulative 50% diameter of the object determined by the laser diffraction / scattering method.
  • the “melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak obtained by analyzing the polymer by the differential scanning calorimetry (DSC) method.
  • the "glass transition point” is a value measured by analyzing a polymer by a dynamic viscoelasticity measurement (DMA) method.
  • the “substantially spherical inorganic filler” is an inorganic particle in which the ratio of the minor axis to the major axis is 0.7 or more and the proportion of spherical particles is 95% or more when observed with a scanning electron microscope (SEM). Means a filler.
  • the powder composition of the present invention (hereinafter, also referred to as “the present composition”) is a unit based on perfluoro (alkyl vinyl ether) (PAVE) (PAVE unit) or a unit based on hexafluoropropylene (HFP) (HFP unit).
  • thermoplastic aromatic polymer also referred to as “TAr polymer”.
  • TFE polymer electrical properties such as low dielectric adjunct
  • TA polymer processing, optical properties, etc.
  • a molded product such as a film having a good balance with linear expandability and the like can be obtained. The reason is not always clear, but it can be considered as follows.
  • the TFE-based polymer can be said to be a thermoplastic and crystalline polymer, and is excellent in physical stress resistance and heat resistance, and the powder thereof has a predetermined hardness. Therefore, it is considered that the powder of the TFE-based polymer in the softened state is densely dispersed in the melted or softened TAr polymer while being pulverized and atomized by the hard inorganic filler during melt extrusion molding. Further, since the TFE polymer itself does not deteriorate (fibrilize or the like) during this dispersion, it is considered that the affinity between any of the components is not impaired.
  • the present composition when the present composition is subjected to melt extrusion molding, a molded product densely containing a hard inorganic filler having a sea-island structure composed of a sea phase containing a Tar polymer and a fine island phase containing a TFE-based polymer. Is also considered to be easily formed. Therefore, it is considered that the molded product obtained from the present composition is a molded product having a high degree of physical characteristics of the three (TFE-based polymer, TAr polymer and hard inorganic filler).
  • a molded product (film, etc.) obtained by melt extrusion molding of this composition has physical properties such as low dielectric constant, low dielectric loss tangent property, low linear expansion coefficient, adhesiveness, and moldability. doing.
  • a molded product can be suitably used as a material or member of a printed circuit board.
  • the dielectric constant of the molded product obtained from the present composition measured at 10 GHz is preferably 2.0 to 4.0.
  • the TFE-based polymer in the present invention is a polymer containing TFE units and PAVE units or HFP units, that is, a polymer containing TFE units and PAVE units (PFA-based polymer), or a polymer containing TFE units and HFP units (a polymer containing TFE units and HFP units). It is a FEP-based polymer), and is more preferable to be a PFA-based polymer from the viewpoint of being more excellent in physical stress resistance and heat resistance and forming fine spherulites in a molded product to further enhance the adhesiveness.
  • CF 2 CFOCF 3 (PMVE)
  • CF 2 CFOCF 2 CF 3
  • the melting temperature (melting point) of the TFE polymer is preferably 260 to 320 ° C, more preferably 285 to 320 ° C.
  • the glass transition point of the TFE polymer is preferably 75 to 125 ° C, more preferably 80 to 100 ° C.
  • the TFE-based polymer preferably further has units based on other monomers.
  • the other monomers include olefins (ethylene, propylene, etc.), chlorotrifluoroethylene, fluoroolefins (hexafluoropropylene, fluoroalkylethylene, etc.), and monomers having an oxygen-containing polar group described later.
  • the TFE-based polymer preferably has an oxygen-containing polar group.
  • the oxygen-containing polar group may be contained in the unit contained in the TFE-based polymer, or may be contained in the terminal group of the polymer main chain.
  • the latter TFE-based polymer includes a TFE-based polymer having an oxygen-containing polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, or an oxygen-containing polymer prepared by plasma treatment, ionization line treatment, or radiation treatment. Examples thereof include TFE-based polymers having a polar group.
  • oxygen-containing polar group a hydroxyl group-containing group, a carbonyl group-containing group, and a phosphono group-containing group are preferable, a hydroxyl group-containing group and a carbonyl group-containing group are more preferable, and a carbonyl group-containing group is particularly preferable.
  • a hydroxyl group-containing group an alcoholic hydroxyl group-containing group is preferable, and -CF 2 CH 2 OH, -C (CF 3 ) 2 OH and 1,2-glycol group (-CH (OH) CH 2 OH) are more preferable.
  • Examples of the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH 2 ), an acid anhydride residue (-C (O) OC (O)-), and the like.
  • a carbonate group (-OC (O) O-) are preferable, and an acid anhydride residue is more preferable.
  • the number of carbonyl group-containing groups in the TFE-based polymer is preferably 10 to 5000, more preferably 50 to 2000, per 1 ⁇ 10 6 main chain carbon atoms. ..
  • the number of carbonyl group-containing groups in the TFE-based polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.
  • the TFE-based polymer having an oxygen-containing polar group it is particularly preferable to have a unit based on a monomer having an oxygen-containing polar group.
  • a monomer having a hydroxyl group-containing group or a carbonyl group-containing group is preferable, and a monomer having a carbonyl group-containing group is more preferable.
  • the monomer having a carbonyl group-containing group include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter also referred to as “NAH”) and maleic anhydride.
  • TFE-based polymers include polymers containing TFE units, PAVE units and units based on monomers with oxygen-containing polar groups (1), 95.0-98.0 mol% TFE units and 2.0.
  • examples include polymers consisting of ⁇ 5.0 mol% PAVE units (2), polymers containing TFE units and PMVE units. These polymers are particularly excellent in physical stress resistance, and when the powder composition is subjected to melt extrusion molding, fine spherulites are formed and it is easy to form a molded product having better adhesiveness. ..
  • the polymer (1) a polymer containing a TFE unit and a PAVE unit and a monomer having a hydroxyl group-containing group or a carbonyl group-containing group is preferable.
  • the TFE unit is 90 to 98 mol%
  • the PAVE unit is 1.5 to 9.97 mol%
  • the unit based on the above monomer is 0.01 to 3 mol%, based on all the units.
  • Polymers containing each are preferable.
  • Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
  • the polymer (2) a polymer consisting of only TFE units and PAVE units is preferable.
  • the content of PAVE units in the polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the monomer units.
  • the polymer (2) preferably does not have an oxygen-containing polar group.
  • the polymer (2) does not have oxygen-containing polar groups when the number of oxygen-containing polar groups contained in the polymer is less than 500 per 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. It means that there is.
  • the number of oxygen-containing polar groups is preferably 100 or less, more preferably less than 50.
  • the lower limit of the number of oxygen-containing polar groups is usually 0.
  • the polymer (2) may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate an oxygen-containing polar group as the terminal group of the polymer chain, and a TFE-based polymer having an oxygen-containing polar group is fluorinated. May be manufactured.
  • the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314, etc.).
  • At least a part of the fine particles constituting the powder of the TFE-based polymer may be fine particles containing components other than the TFE-based polymer, but the fine particles made of the TFE-based polymer are preferable.
  • the components other than the TFE-based polymer include thermoplastic polymers.
  • the thermoplastic polymer may be a Tar polymer.
  • the thermoplastic polymer other than the TA polymer include TFE-based polymers and polymers other than the TA polymer, which will be described later.
  • the amount of the polymer component other than the TFE-based polymer is preferably 30% by mass or less, more preferably 15% by mass or less of the total polymer component. preferable.
  • the content of the TAr polymer is preferably 20% by mass or less, more preferably 10% by mass or less of the total polymer components.
  • At least a part of the fine particles constituting the powder of the TFE-based polymer may be fine particles of the TFE-based polymer containing an inorganic filler.
  • oxides, nitrides, simple metals, alloys and carbons are preferable, and silicon oxide (silica) and metal oxides (berylium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide and oxidation are preferable. Titanium etc.), boron nitride, and magnesium metasilicate (steatite) are more preferable, silica and boron nitride are more preferable, and silica is particularly preferable.
  • the inorganic filler may be a hard inorganic filler, but in that case, it is a part of the total amount of the hard inorganic filler contained in the powder composition of the present invention, and the other is a powder of the hard inorganic filler.
  • the fine particles containing the TFE polymer and the inorganic filler preferably have the TFE polymer as the core and the particles having the inorganic filler on the surface of the core. Such particles are obtained, for example, by coalescing (colliding, agglomerating, etc.) particles of a TFE-based polymer and particles of an inorganic filler.
  • the TFE-based polymer is a powder containing fine particles containing the TFE-based polymer and the inorganic filler
  • the TFE-based polymer is likely to be uniformly dispersed in the TA polymer during melt molding.
  • the amount of the inorganic filler in the powder is preferably 50% by mass or less with respect to the powder. , 40% by mass or less is more preferable.
  • the amount of the hard inorganic filler is preferably 40% by mass or less, more preferably 30% by mass or less with respect to the powder.
  • the fine particles constituting the powder of the TFE polymer contain additives such as an organic filler, an organic pigment, a metal soap, a surfactant, an ultraviolet absorber, a lubricant, and a silane coupling agent, which will be described later. May be good.
  • the amount of the additive in the powder is preferably 10% by mass or less, more preferably 5% by mass or less, based on the powder.
  • the average particle size of the powder of the TFE polymer (that is, the average particle size of the fine particles constituting the powder of the TFE polymer) is preferably 0.1 to 200 ⁇ m, more preferably 1 to 100 ⁇ m.
  • the pulverization of the powder of the TFE polymer by the hard inorganic filler progresses to a high degree, and it is easy to form a molded product having a more dense sea-island structure.
  • the hard inorganic filler in the present invention is an inorganic filler having a Mohs hardness of 3 to 9.
  • the Mohs hardness of the hard inorganic filler is preferably 5 or more, and more preferably 6 or more. In this case, in the melt extrusion molding, the pulverization of the powder of the TFE-based polymer by the hard inorganic filler is highly likely to proceed.
  • the hard inorganic filler may contain a component other than the inorganic component, but is preferably composed of an inorganic component. Examples of components other than the inorganic components include organic compounds such as organic substances used in surface treatment agents described later and soft inorganic compounds such as boron nitride.
  • an inorganic filler composed of aluminum nitride, beryllium oxide (berilia), silicon oxide (silica), cerium oxide, aluminum oxide (alumina), magnesium oxide (magnesia), zinc oxide or titanium oxide is preferable.
  • the hard inorganic filler may consist of two or more kinds of inorganic components.
  • the hard inorganic filler preferably contains silicon oxide.
  • the hard inorganic filler containing silicon oxide not only has a high hardness, but also tends to enhance the interaction with the TFE polymer. Therefore, it is easy to form a molded product having a more dense sea-island structure from the molded product containing such an inorganic filler in melt extrusion molding. In addition, its low line expansion is particularly likely to occur.
  • the content of silicon oxide in the hard inorganic filler is preferably 50% by mass or more, more preferably 75% by mass or more.
  • the content of silicon oxide is preferably 100% by mass or less.
  • berylia filler Mohs hardness: 9
  • magnesia filler Mohs hardness: 5.5
  • silica filler Mohs hardness: 7
  • silica filler is more preferable.
  • the silica filler is preferably a molten silica filler or an amorphous silica filler. In this case, the molded product tends to have the low thermal expansion property.
  • At least a part of the surface of the hard inorganic filler may be surface-treated.
  • the surface treatment agent used for such surface treatment include polyhydric alcohols (trimethylolethane, pentaeristol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkanolamines, amines (trimethylamine, etc.). Triethylamine etc.), paraffin wax, silane coupling agent, silicone, polysiloxane, and metal oxides such as aluminum, silicon, zirconium, tin, titanium, antimony, hydroxides of those metals, hydration oxidation of those metals Examples include phosphates of those metals.
  • silane coupling agent a silane coupling agent having a functional group is preferable, and 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-Methoxyloxypropyltriethoxysilane and 3-isocyanatepropyltriethoxysilane are more preferred.
  • the average particle size of the hard inorganic filler powder (that is, the average particle size of the fine particles constituting the hard inorganic filler powder) is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more. Further, 10 ⁇ m or less is preferable, 2 ⁇ m or less is more preferable, and 1 ⁇ m or less is particularly preferable.
  • the average particle size of the hard inorganic filler is preferably equal to or less than the average particle size of the powder of the TFE polymer. If the average particle size of the hard inorganic filler powder is within such a range, the powder of the TFE polymer is highly pulverized by the melt extrusion molding, and a molded product having a finer sea-island structure is formed.
  • a combination of a hard inorganic filler powder having an average particle size of more than 0.10 ⁇ m and 1 ⁇ m or less and a TFE polymer powder having an average particle size of 1 ⁇ m or more and 3 ⁇ m or less is preferable.
  • the shape of the fine particles constituting the hard inorganic filler is preferably substantially spherical.
  • the ratio of the minor axis to the major axis is preferably 0.8 or more, more preferably 0.9 or more. The above ratio is preferably less than 1.
  • the powder of the hard inorganic filler composed of substantially spherical fine particles tends to enhance the interaction with each component in melt extrusion molding.
  • Suitable specific examples of the hard inorganic filler powder include silica fillers having an average particle size of 1 ⁇ m or less (such as the “Admafine” series manufactured by Admatex), and an average particle size of more than 0.10 ⁇ m and 0.5 ⁇ m. Examples thereof include spherical fused silica (“SFP” series manufactured by Denka Co., Ltd., etc.) described below.
  • SFP spherical fused silica
  • aromatic polyimide, aromatic polyamideimide, aromatic polyester, aromatic polyesteramide, polyphenylene ether and polyphenylene sulfide are preferable.
  • a liquid crystal polymer is preferable.
  • the liquid crystal polymer is a Tar polymer that forms an anisotropic molten phase, and is generally called a thermotropic liquid crystal polymer.
  • Specific examples of the liquid crystal polymer include thermoplastic and liquid crystalline aromatic polyester and aromatic polyester amide.
  • the former is often referred to as a thermotropic liquid crystal polyester, and the latter is often referred to as a thermotropic liquid crystal polyester amide.
  • An imide bond, a carbonate bond, a carbodiimide bond, an isocyanate bond, or the like may be further introduced into the liquid crystal polymer.
  • the TFE polymer and the hard inorganic filler are highly dispersed in the TA polymer to form a molded product. Therefore, the anisotropy of the physical properties derived from the liquid crystal polymer in the flow direction (MD direction) of the molded product, which is likely to occur when the Tar polymer is a liquid crystal polymer, is alleviated by the highly dispersed TFE polymer or hard inorganic filler. Easy to be done. In other words, a molded product (film or the like) obtained by melt extrusion molding from the present composition in which the Tar polymer is a liquid crystal polymer tends to be highly isotropic.
  • the molded product As a result, while having the physical characteristics peculiar to the liquid crystal polymer (mechanical properties such as strength, elasticity and vibration absorption, and electrical properties such as dielectric properties), the decrease in tensile strength and thermal expansion due to anisotropy is suppressed. It is easy to obtain the molded product. In particular, it is easy to obtain a molded product such as a film having excellent dimensional stability during immersion in a chemical solution or heat treatment.
  • the anisotropic molten phase of the liquid crystal polymer may be confirmed, for example, by placing the polymer sample on a hot stage, heating the polymer sample in a nitrogen gas atmosphere, and observing the transmitted light of the polymer sample.
  • the melting temperature (melting point) of the liquid crystal polymer is preferably 250 to 370 ° C, more preferably 270 to 350 ° C.
  • Specific examples of the TAr polymer, which is a liquid crystal polymer include "Laperos” manufactured by Polyplastics, "Vectra” manufactured by Celanese, "UENOLCP” manufactured by Ueno Fine Chemicals Industry, and “Sumika Super LCP” manufactured by Sumitomo Chemical Co., Ltd. Examples include “XYDAR” manufactured by SOLVAY SPECIALTY POLYMERS, "Zider” manufactured by JX Nikko Nisseki Energy Co., Ltd., and "Siberus” manufactured by Toray Industries, Inc.
  • the powder of the Tar polymer is a powder composed of fine particles containing the Tar polymer in a proportion of 50% by mass or more, and a powder composed of fine particles containing the Tar polymer in a proportion of 60 to 100% by mass is preferable.
  • the fine particles constituting the powder may be fine particles containing components other than the Tar polymer.
  • Such components include thermoplastic polymers other than TAr polymers, fibrous inorganic fillers, fibrous organic fillers, non-fibrous inorganic fillers, non-fibrous organic fillers, organic pigments, metal soaps, surfactants, and ultraviolet rays. Additives such as absorbents, lubricants and silane coupling agents can be mentioned.
  • the thermoplastic polymer other than the Tar polymer may be a TFE-based polymer
  • the non-fibrous inorganic filler may be a hard inorganic filler.
  • Ingredients other than TA polymer include glass fiber, carbon fiber (PAN-based carbon fiber, pitch-based carbon fiber), organic synthetic fiber (aromatic polyamide fiber, etc.), metal fiber (stainless fiber, aluminum fiber, etc.), inorganic fiber. Fibrous fillers such as (silicon carbide fiber, potassium titanate fiber, alumina fiber, etc.) and natural ore-based fiber (walasnite, asbestos, etc.) are preferable.
  • the content of the fibrous filler in the powder is preferably 40% by mass or less, more preferably 35% by mass or less.
  • the content of the thermoplastic polymer in the powder is preferably 40% by mass or less, more preferably 20% by mass or less of the total polymer components.
  • the thermoplastic polymer is a TFE-based polymer, it is preferably 20% by mass or less, more preferably 10% by mass or less of the total polymer components.
  • the content of such additives in the powder is preferably 30% by mass or less, more preferably 15% by mass or less.
  • the amount of the hard inorganic filler is preferably 20% by mass or less, more preferably 10% by mass or less with respect to the powder.
  • the average particle size of the tar polymer powder (that is, the average particle size of the fine particles constituting the tar polymer powder) is preferably 0.1 to 200 ⁇ m, more preferably 1 to 100 ⁇ m.
  • the TFE polymer and the hard inorganic filler are dispersed in the Tar polymer, and it is easy to form a molded product having a dense sea-island structure.
  • the present composition may further contain powders other than TFE-based polymer powders, hard inorganic filler powders, and TAr polymer powders.
  • powders other than TFE-based polymer powders include powders of thermoplastic polymers other than TFE polymers and TAr polymers, powders of polymers other than thermoplastic polymers, and powders of fillers other than hard inorganic fillers (such as the inorganic fillers and organic fillers).
  • Etc. can be mentioned.
  • the organic filler include fibrous organic fillers made of polymer fibers that do not melt in melt extrusion molding.
  • thermoplastic polymer examples include polyolefin polymers (polyethylene, polypropylene, polybutylene, acid-modified polyethylene, acid-modified polypropylene, acid-modified polybutylene, etc.) and fluoropolymers other than TFE-based polymers (polyfluorovinylidene, polytetrafluoro).
  • polystyrene-based polymers polystyrene, polyacrylonitrile styrene, polyacrylonitrile butadiene styrene, etc.
  • polycarbonate-based polymers poly (meth) acrylic-based polymers, polyvinyl chloride, polyarelliton-based polymers, polyurethane-based polymers.
  • the polymer powder other than the thermoplastic polymer include a powder made of a cured product of a thermosetting resin, a powder of non-thermomeltable polytetrafluoroethylene, and the like.
  • the powder of the organic filler examples include powders composed of aromatic polyamide fibers, polyaramid fibers, polyparaphenylene benzoxazole fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, polyethylene fibers and the like.
  • the content of the other powder in the present composition is preferably 30% by mass or less, more preferably 15% by mass or less.
  • the composition is particularly preferably composed of three types of powders: a TFE-based polymer powder, a hard inorganic filler powder, and a TAr polymer powder.
  • the content ratio of the powders of these three substances in the following composition refers to the ratio in the composition composed of these three types of powders.
  • the content of the TFE polymer in the present composition is preferably 5% by mass or more, more preferably 10% by mass or more. Further, 50% by mass or less is preferable, and 40% by mass or less is more preferable.
  • the content of the Tar polymer in the present composition is preferably 10% by mass or more, more preferably 20% by mass or more. Further, 90% by mass or less is preferable, and 80% by mass or less is more preferable.
  • the content of the TAr polymer in the present composition is preferably higher than the content of the TFE-based polymer. That is, the present composition preferably contains a Tar polymer as a main polymer component. In this case, since the interaction with the TFE-based polymer is likely to be enhanced, it is easy to form a molded product having a finer sea-island structure in melt extrusion molding. In addition, its low line expansion is particularly likely to occur.
  • the content of the hard inorganic filler in the present composition is preferably 5% by mass or more, more preferably 10% by mass or more. Further, 50% by mass or less is preferable, and 40% by mass or less is more preferable.
  • the ratio of the content of the hard inorganic filler to the content of the TFE polymer in the present composition is preferably 0.2 to 1.0, more preferably 0.2 to 0.6. In this case, in melt extrusion molding, the powder of the TFE polymer is highly pulverized, and it is easy to obtain a molded product in which the hard inorganic filler is highly dispersed. In addition, it is easy for the molded product to have the physical characteristics of the three parties.
  • the contents of the TFE polymer, the Tar polymer, and the hard inorganic filler in the present composition are preferably 10 to 40% by mass, 5 to 40% by mass, and 20 to 85% by mass in this order.
  • the present composition is preferably produced by dry blending each component.
  • a mixing device such as a tumbler, a Henschel mixer, a hopper, a Banbury mixer, a roll, or a lavender can be used.
  • the present composition is preferably used for melt extrusion molding, and is preferably molded into a film by melt extrusion molding.
  • the melt extrusion molding is preferably carried out by a method using a T-die, and the composition charged from the hopper is melt-kneaded in an extruder (uniaxial screw or biaxial screw) and installed at the tip of the extruder. It is more preferable to carry out by a method of extruding from the T-die to form a film.
  • the film obtained by melt extrusion is preferably further stretched. This gives a more isotropic film.
  • the stretching treatment is a treatment in which the film is softened at a temperature equal to or lower than its melting point and stretched in one direction (1 axis: MD direction) or 2 directions (2 axes: MD direction and TD direction).
  • the stretching treatment is more preferably a biaxial stretching treatment from the viewpoint of obtaining an isotropic film.
  • Examples of the stretching method include an inflation method and a flat method. As the flat method, either simultaneous biaxial stretching or sequential biaxial stretching can be adopted.
  • the obtained film may be further subjected to a laminating treatment, a stretching treatment, a cooling treatment and a peeling treatment.
  • the laminating treatment is a treatment of laminating a release film on both sides or one side of the obtained film to form a laminated body.
  • the laminating method include a thermocompression bonding method and a surface treatment method, in which a thermocompression bonding roll, a thermal press device, and a laminator are used.
  • a thermocompression bonding roll when a thermocompression bonding roll is used, the obtained film and the release film may be laminated and passed through the thermocompression bonding roll for thermocompression bonding.
  • a hot press device is used, the film obtained on the bottom plate of the hot press device and the release film may be laminated and thermocompression bonded to cool the film.
  • the composition in a molten state extruded from the T die is supplied to the gap between the two release films, and the laminate is formed in the gap between the thermocompression bonding rolls. Good.
  • a coextrusion method using a multilayer die is used, a multilayer body in which the film formed from the present composition and the release film are each layered can be formed.
  • the material of the release film is polyethylene, polypropylene, polyether ether ketone, polyether sulfone, polyimide, polyetherimide, polyarylate, polycarbonate, polystyrene, polyvinyl chloride, polyester, polyamide, polyamideimide, thermoplastic polyimide, polyphenylene sulfide.
  • the thickness of the release film is preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m.
  • the stretching treatment is a treatment for obtaining a stretched product by stretching the laminated body while softening the release film layer of the laminated body obtained by the laminating treatment. This stretching treatment may be carried out continuously.
  • the cooling treatment is a treatment for cooling the stretched product obtained by the stretching treatment. Cooling may be natural cooling, or a cooling roll or the like may be used.
  • the peeling treatment is a treatment for peeling the peeling film from the cooled stretched product. The peeling process can be performed by a 90 ° peeling method or a 180 ° peeling method. By such a series of treatments, a film having a more suppressed coefficient of thermal expansion can be obtained from the present composition.
  • Inflation molding may be used in the molding of the film.
  • inflation molding the melt-kneaded product of the present composition extruded from an annular die (round die, circular die) is stretched in two directions (MD direction and TD direction), so that the isotropic property of the film is likely to be improved. ..
  • insulation molding since the melt-kneaded product is mechanically stretched in two directions by taking up and expanding, it is easy to mold a film in which polymer molecules are oriented in two directions. Further, at this time, a film having a structure similar to that of the above-mentioned laminate may be formed by inflation molding. That is, the composition and other thermoplastic polymers are melt-extruded from a cyclic die and inflation-molded to form a laminate.
  • the laminate that can be formed at this time is a two-layer laminate (type 1) composed of a film layer formed from one of the present compositions and one release film layer, and one piece between the two release film layers.
  • a three-layer laminate in which a film layer formed from the composition is sandwiched (type 2), and a three-layer laminate in which one release film layer is sandwiched between two film layers formed from the present composition (type 2). 3) is mentioned, and a type 1 laminate or a type 3 laminate is preferable.
  • the thickness of the film layer formed from the present composition in these laminates is preferably 3 to 150 ⁇ m.
  • the thickness of the release film layer is preferably at least twice the thickness of the film layer.
  • the film of the present invention (hereinafter, also referred to as "the present film”) contains a TFE-based polymer, an inorganic filler having a moth hardness of 3 to 9, a TAr polymer, a sea phase containing a TAr polymer, and a TFE-based polymer. It has a sea-island structure composed of an island fauna including.
  • the definitions of TFE-based polymers, hard inorganic fillers, and TAr polymers in the film are similar to those in the composition, including the preferred range.
  • the TFE-based polymer, the hard inorganic filler, and the TAr polymer may be uniformly distributed or may be unevenly distributed.
  • the distribution amount of the TFE-based polymer in the surface region in the thickness direction of the film is preferably higher than the distribution amount of the TFE-based polymer in the central region in the thickness direction of the film. In this case, the physical properties (particularly, the dielectric properties such as low dielectric contact and the adhesiveness) caused by the TFE polymer in this film are likely to be remarkably exhibited.
  • the distribution amount of the hard inorganic filler in the central region in the thickness direction of the film is preferably higher than the distribution amount of the hard inorganic filler in the surface region in the thickness direction of the film. In this case, the physical characteristics (particularly, low line expansion) caused by the hard inorganic filler in this film are likely to be remarkably exhibited.
  • the thickness of this film is preferably 5 to 1000 ⁇ m, more preferably 10 to 200 ⁇ m.
  • the film is preferably produced by melt extrusion of the composition. In this case, it is easy to manufacture films of various arbitrary embodiments described above without impairing processability such as mechanical strength and bendability.
  • As a method for producing the film it is preferable to use the T die coating method. Specifically, the melt-kneaded composition is discharged from the T die in a molten state and brought into contact with a cooling roll to form a film. Is preferable. It is preferable that the melt-kneaded composition is heated and held in a non-contact heating unit before coming into contact with the cooling roll. It is preferable that the composition cooled by the cooling roll is formed into a film while being conveyed by the conveying roller, and is wound by the take-up roll to be formed into a long film.
  • the present film has a metal layer formed on its surface to form a metal-clad laminate.
  • the metal include various metals such as copper, nickel, aluminum, silver, gold and tin, and alloys thereof (stainless steel and the like).
  • Examples of such a metal-clad laminate include a single-sided metal-clad laminate having a metal layer and the present film in this order, a metal layer, and a double-sided metal-clad laminate having the present film layer and the metal layer in this order. Further, these metal-clad laminates may have further another layer (prepreg layer, glass member layer, ceramic member layer, other resin film layer).
  • a metal foil is attached to the surface of this film by a laminating method or a thermocompression bonding method, or a metal layer is formed on the surface of this film by a sputtering method or a vapor deposition method.
  • Method, method of forming a metal layer on the surface of this film by electroless plating or electrolytic plating after electroless plating, printing method using metal conductive ink (screen printing method, inkjet method, A method of forming a metal layer on the surface of the present film by the ion plating method) can be mentioned.
  • the metal foil a copper foil such as a rolled copper foil or an electrolytic copper foil is preferable.
  • the surface of the film may be surface-treated in order to further improve the adhesiveness with the metal layer.
  • Examples of the surface treatment include plasma treatment, corona treatment, flame treatment, and itro treatment.
  • Such a metal-clad laminate can be used as a material or member for a printed circuit board, a high heat dissipation substrate, an antenna substrate, or the like.
  • a printed circuit board can be obtained by etching the metal layer of the metal-clad laminate to form a pattern circuit.
  • an interlayer insulating film may be formed on the pattern circuit, and a pattern circuit may be further formed on the interlayer insulating film.
  • a solder resist may be laminated on the pattern circuit, or a coverlay film may be laminated.
  • the coverlay film is typically composed of a base film and an adhesive layer formed on the surface thereof, and the surface on the adhesive layer side is attached to the printed circuit board.
  • This film may be used as the base film of the coverlay film.
  • an interlayer insulating film (adhesive layer) using this film may be formed on the pattern circuit, and a polyimide film may be laminated as a coverlay film.
  • PFA-based powder 1 Contains 98.0 mol%, 0.1 mol%, and 1.9 mol% of TFE units, NAH units, and PPVE units in this order, and contains a carbonyl group-containing group as the main chain carbon number.
  • Powder (average particle size: 2.0 ⁇ m) composed of 1000 PFA-based polymers (melting temperature: 300 ° C.) per 1 ⁇ 10 6 pieces
  • PFA-based powder 2 A powder (average particle size) composed of a PFA-based polymer (melting temperature: 305 ° C.) having 40 carbonyl group-containing groups per 1 ⁇ 10 6 main chain carbon atoms, which is composed of TFE units and PPVE units.
  • Aromatic powder 1 Liquid crystal polymer powder that is an aromatic polymer containing 30% by mass of glass fiber (melting temperature: 320 ° C; manufactured by Ueno Fine Chemicals Industry, "UENO LCP 6030G”)
  • Inorganic filler 1 Silica filler having a Mohs hardness of 7 and a substantially spherical shape (average particle size: 0.5 ⁇ m; manufactured by Admatex, “Admafine SO-C2”)
  • Inorganic filler 2 Silica filler having a Mohs hardness of 7 and a substantially spherical shape (average particle size: 5 ⁇ m)
  • the evaluation of the dimensional stability of the film was based on JIS C 6488: 1996. From the widthwise edge of the obtained film, a 30 cm square square sample having two sides along the flow direction and two sides along the width direction was cut out. Line segments with a length of 25 cm are drawn on the diagonal lines of the surface of this sample (the 45 ° direction in which the angle formed by the flow direction is 45 ° and the 135 ° direction orthogonal to the 45 ° direction), and each line segment is drawn. Punch holes were formed around both ends of the. The sample was immersed in an aqueous iron chloride solution, the distance between the centers of the two punch holes before and after immersion was measured, and the expansion / contraction rate of the film in the oblique direction during etching was determined.
  • the sample was heat-treated at 150 ° C. for 30 minutes and then cooled to 25 ° C., and the distance between the centers of the two punch holes before and after the heat treatment was measured to determine the expansion / contraction rate of the film in the oblique direction during the heat treatment. ..
  • a powder composition 1 was prepared by dry-blending PFA-based powder 1 (20 parts by mass), aromatic powder 1 (100 parts by mass), and hard inorganic filler 1 (15 parts by mass).
  • the powder composition 1 was put into a twin-screw extruder (manufactured by Technobel Co., Ltd., "KZW15TW-45MG"), melt-kneaded (screw rotation speed: 200 rpm, set resin temperature: 370 ° C.), and a T-die installed at the tip thereof.
  • the film 1 showed high adhesiveness to the copper foil, and its dielectric constant was 2.9, which was excellent in dielectric properties. Further, the stretch ratio in the diagonal direction of the film in the etching of the film 1 and the stretch ratio (absolute value) in the diagonal direction of the film in the heat treatment are both less than 0.1%, and the film 1 has dimensional stability. It was excellent. [Examples 2 to 4] Films 2 to 4 were obtained in the same manner as in Film 1, except that the types and amounts of the respective powders and inorganic fillers were changed as shown in Table 1 below.
  • each film was measured as follows and evaluated according to the following criteria. Each film and a solid copper foil were placed facing each other and heat-pressed (temperature: 340 ° C., pressing force: 15 kN / m) to obtain a laminate having a film layer and a copper foil layer. A rectangular test piece having a length of 100 mm and a width of 10 mm was cut out from this laminated body. The copper foil layer was peeled from the film layer to a position 50 mm from one end in the length direction of the test piece.
  • the test piece When peeling, the test piece is peeled 90 degrees at a tensile speed of 50 mm / min using a tensile tester (manufactured by Orientec) with the position 50 mm from one end in the length direction as the center, and the measurement distance is 10 mm to 30 mm. The average load up to was measured and used as the peel strength (N / cm).
  • N / cm The peel strength is 10 N / cm or more.
  • the peel strength is 5 N / cm or more and less than 10 N / cm.
  • X The peel strength is less than 5 N / cm.
  • the films 1 to 4 are the sea containing the liquid crystal polymer 1. It had a sea-island structure composed of a phase and an island phase containing PFA-based polymer 1 or 2. Further, in the films 1 to 3, the distribution amount of the PFA-based polymer in the surface region in the film thickness direction was higher than the distribution amount of the PFA-based polymer in the central region in the film thickness direction.
  • the powder composition of the present invention and the film of the present invention have high frequency characteristics, particularly electronic devices (radars, network routers, backplanes, wireless infrastructures, automobile sensors, engines) that require reduction of transmission loss in the millimeter wave band. It is useful as a material or member of a printed circuit board used for (management sensor, etc.).

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Abstract

L'invention fournit une composition de poudre qui est excellente en termes de caractéristiques diélectriques, et qui est adaptée à un moulage par extrusion de matière fondue d'un film comportant des propriétés d'adhésion, des propriétés d'usinage et des propriétés de faible dilatation linéaire, et fournit également un film adapté à un matériau de carte de circuit imprimé.　Plus précisément, l'invention concerne une composition de poudre qui contient une poudre de polymère à base de tétrafluoroéthylène contenant une unité basée sur un perfluoro(alkylvinyléther) ou une unité basée sur un hexafluoropropylène, une poudre de charge inorganique de dureté Mohs comprise entre 3 et 9, et une poudre de polymère aromatique thermoplastique, et concerne également un film qui possède au moins une structure mer-îlots contenant les composants ci-dessus, et configurée par une phase mer contenant ledit polymère aromatique et une phase îlots contenant ledit polymère à base de tétrafluoroéthylène.
PCT/JP2020/041536 2019-11-11 2020-11-06 Composition de poudre, film, et procédé de fabrication de film WO2021095656A1 (fr)

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WO2005083007A1 (fr) * 2004-03-02 2005-09-09 Polyplastics Co., Ltd. Composition de résine cristalline liquide
WO2014171029A1 (fr) * 2013-04-17 2014-10-23 ダイセル・エボニック株式会社 Composition de résine résistante à la lumière ainsi que corps moulé associé
WO2015016370A1 (fr) * 2013-07-31 2015-02-05 住友化学株式会社 Composition de polyester à cristaux liquides
JP2018177931A (ja) * 2017-04-11 2018-11-15 Ａｇｃ株式会社 樹脂組成物および成形品

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US6153303A (en) * 1997-08-26 2000-11-28 Dupont Mitsui Fluorochemicals Tetrafluoroethylene copolymer composition for coating metal articles
JP3530829B2 (ja) 2001-03-12 2004-05-24 日本ピラー工業株式会社 電子部品用フッ素樹脂組成物
JP4014964B2 (ja) 2001-10-24 2007-11-28 三井・デュポンフロロケミカル株式会社 フッ素樹脂積層体及びその製造方法
JP2003171538A (ja) 2001-12-07 2003-06-20 Dainippon Ink & Chem Inc 液晶ポリエステル樹脂組成物
EP2949705A4 (fr) * 2013-01-23 2016-08-17 Toray Industries Composition de résine de sulfure de polyphénylène, procédé pour produire celle-ci, et article moulé de celle-ci
WO2017179542A1 (fr) * 2016-04-11 2017-10-19 旭硝子株式会社 Stratifié, carte imprimée et procédé pour produire un stratifié
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

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JPH09278966A (ja) * 1996-04-10 1997-10-28 Du Pont Mitsui Fluorochem Co Ltd 金属基材被覆用組成物
WO2005083007A1 (fr) * 2004-03-02 2005-09-09 Polyplastics Co., Ltd. Composition de résine cristalline liquide
WO2014171029A1 (fr) * 2013-04-17 2014-10-23 ダイセル・エボニック株式会社 Composition de résine résistante à la lumière ainsi que corps moulé associé
WO2015016370A1 (fr) * 2013-07-31 2015-02-05 住友化学株式会社 Composition de polyester à cristaux liquides
JP2018177931A (ja) * 2017-04-11 2018-11-15 Ａｇｃ株式会社 樹脂組成物および成形品

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