WO2021193505A1 - Particule composite, procédé de production de particules composites, composition liquide, procédé de fabrication d'un stratifié, et procédé de fabrication d'un film - Google Patents

Particule composite, procédé de production de particules composites, composition liquide, procédé de fabrication d'un stratifié, et procédé de fabrication d'un film Download PDF

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WO2021193505A1
WO2021193505A1 PCT/JP2021/011654 JP2021011654W WO2021193505A1 WO 2021193505 A1 WO2021193505 A1 WO 2021193505A1 JP 2021011654 W JP2021011654 W JP 2021011654W WO 2021193505 A1 WO2021193505 A1 WO 2021193505A1
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particles
polymer
inorganic substance
composite
tetrafluoroethylene
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PCT/JP2021/011654
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English (en)
Japanese (ja)
Inventor
敦美 山邊
細田　朋也
渉 笠井
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Ａｇｃ株式会社
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Priority to KR1020227034471A priority Critical patent/KR20220158736A/ko
Priority to JP2022510466A priority patent/JP7511117B2/ja
Priority to CN202180018381.4A priority patent/CN115210300A/zh
Publication of WO2021193505A1 publication Critical patent/WO2021193505A1/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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Definitions

  • the present invention relates to composite particles containing a predetermined tetrafluoroethylene polymer and an inorganic substance and a method for producing the same, and a method for producing a liquid composition, a laminate, and a film using such composite particles.
  • Patent Document 1 As the composite particles of silica and a tetrafluoroethylene polymer, the aspects of Patent Document 1 and Patent Document 2 are known.
  • the tetrafluoroethylene polymer has extremely low polarity and low affinity with other components, it is highly difficult to interact with silica. Therefore, it is difficult for the composite particles of the above documents to take in a sufficient amount of silica. Further, since the composite particles of the above documents have low interaction between silica and the tetrafluoroethylene-based polymer, the stability of the composite particles themselves is not sufficient, and silica is likely to fall off from the composite particles.
  • An object of the present invention is to provide composite particles containing an arbitrary amount of an inorganic substance and having desired physical properties such as high polarity.
  • ⁇ 3> The composite particles of ⁇ 1> or ⁇ 2> above, wherein the inorganic substance is silica or boron nitride.
  • ⁇ 4> The composite particles of ⁇ 1> to ⁇ 3> above, wherein the composite particles are spherical or scaly.
  • ⁇ 5> The composite particle according to any one of ⁇ 1> to ⁇ 4>, which has the tetrafluoroethylene polymer as a core and the inorganic substance on the surface of the core.
  • ⁇ 6> The composite particles of ⁇ 5>, wherein the core of the tetrafluoroethylene polymer and the inorganic substance are each in the form of particles, and the average particle size of the core is larger than the average particle size of the inorganic substance.
  • ⁇ 7> Either of the above ⁇ 5> or ⁇ 6>, wherein the ratio of the fluorine element content to the inorganic element content on the surface of the composite particle measured by energy dispersive X-ray spectroscopy is less than 1. That composite particle.
  • ⁇ 8> The composite particle according to any one of ⁇ 1> to ⁇ 4>, which has the inorganic substance as a core and the tetrafluoroethylene-based polymer on the surface of the core.
  • ⁇ 9> The composite particles of ⁇ 8>, wherein the mass of the inorganic substance in the composite particles is larger than the mass of the tetrafluoroethylene-based polymer.
  • a method for producing composite particles which obtains the composite particles by colliding them at the above temperature and in a suspended state.
  • ⁇ 11> A method for producing the composite particles according to any one of ⁇ 1> to ⁇ 9>, wherein the particles of the tetrafluoroethylene-based polymer and the particles of the inorganic substance are made to collide with each other in a pressed or sheared state.
  • a method for producing composite particles which obtains the composite particles.
  • ⁇ 12> A liquid composition containing the composite particles according to any one of ⁇ 1> to ⁇ 9> and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid dispersion liquid.
  • the liquid dispersion medium is at least one liquid compound selected from the group consisting of water, amides, ketones and esters.
  • ⁇ 14> The liquid composition of ⁇ 12> or ⁇ 13> is applied to the surface of the base material layer and heated to form a polymer layer to obtain a laminate having the base material layer and the polymer layer.
  • a method for manufacturing a laminate A method for producing a film, wherein the composite particles according to any one of ⁇ 1> to ⁇ 9> and a fluoroolefin polymer are melt-kneaded and then extruded to obtain a film.
  • composite particles containing an arbitrary amount of inorganic substances and having desired physical properties such as high polarity can be obtained.
  • a liquid composition containing composite particles and having excellent dispersion stability, and excellent properties (electrical properties, low linear expansion properties, etc.) based on tetrafluoroethylene-based polymers and inorganic substances are highly provided.
  • a laminate and a film to be obtained are obtained.
  • the "average particle size (D50)" is a volume-based cumulative 50% diameter of an object (particle) determined by a laser diffraction / scattering method. That is, the particle size distribution of the object is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the group of particles of the object as 100%, and the particles at the point where the cumulative volume is 50% on the cumulative curve.
  • the diameter. “D90” is the volume-based cumulative 90% diameter of the object, measured in the same manner.
  • the "powder dynamic friction angle” is a value obtained by measuring an object by a measuring method specified in JIS Z 8835: 2016.
  • the “melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method.
  • the "glass transition point (Tg)” is a value measured by analyzing a polymer by a dynamic viscoelasticity measurement (DMA) method.
  • the "viscosity” is a value obtained by measuring the liquid composition under the condition of 25 ° C. and a rotation speed of 30 rpm using a B-type viscometer. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
  • the "thixo ratio" is calculated by dividing the viscosity ⁇ 1 obtained by measuring a liquid composition under the condition of a rotation speed of 30 rpm by the viscosity ⁇ 2 obtained by measuring the liquid composition under the condition of a rotation speed of 60 rpm.
  • the "unit” in the polymer may be an atomic group formed directly from the monomer, or may be an atomic group in which a part of the structure is converted by treating the obtained polymer by a predetermined method.
  • the unit based on monomer A contained in the polymer is also simply referred to as "monomer A unit".
  • the composite particle of the present invention is a particle containing a tetrafluoroethylene polymer having a melting temperature of 260 to 320 ° C. and an inorganic substance.
  • the tetrafluoroethylene polymer (hereinafter, also referred to as “F polymer”) contains a unit (PAVE unit) based on perfluoro (alkyl vinyl ether) (PAVE), and has a polar functional group (1) and a polymer (1). It is at least one selected from the group consisting of the polymer (2) containing 2.0 to 5.0 mol% of PAVE units with respect to all units and having no polar functional group.
  • This particle is a highly stable composite of an F polymer and an inorganic substance, which can contain an arbitrary amount of an inorganic substance and whose physical properties such as polarity can be appropriately adjusted. Its mechanism of action is not always clear, but it is thought to be as follows.
  • the F polymer not only has excellent shape stability such as fibril resistance, but also has a highly flexible conformation in which restrictions on molecular motion are relaxed at the single molecule level. Such F-polymers tend to form microspherulites at the molecular assembly level, and microconcavo-convex structures are likely to be formed on the surface thereof.
  • the molecular aggregate of the F polymer (single particles of the F polymer, etc.) is physically densely adhered to the inorganic substance while remaining stable without impairing its shape. It is also considered that the interaction between the densely adhered inorganic substances further promotes the adhesion of the inorganic substances and stabilizes the composite particles. As a result, it is considered that the particles have high stability while containing an arbitrary amount of inorganic substances, in other words, containing a large amount of inorganic substances, and have a high degree of physical characteristics of F polymer and inorganic substances. Be done.
  • the F polymer in the particles is a polymer containing TFE units and PAVE units.
  • CF 2 CFOCF 2 CF 3
  • the melting temperature of the F polymer is 260 to 320 ° C, preferably 285 to 320 ° C.
  • the glass transition point of the F polymer is preferably 75 to 125 ° C, more preferably 80 to 100 ° C.
  • the melt viscosity of the F polymer is preferably 1 ⁇ 10 2 to 1 ⁇ 10 6 Pa ⁇ s at 380 ° C., more preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s.
  • the melting temperature, the glass transition point, or the melting viscosity of the F polymer is within such a range, the above-mentioned mechanism of action is likely to be enhanced.
  • the polar functional group contained in the polymer (1) may be contained in the unit contained in the polymer, or may be contained in the terminal group of the polymer main chain.
  • Examples of the latter polymer include polymers having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and a polymer having a polar functional group prepared by plasma treatment or ionization line treatment. If the F polymer is the polymer (1), the polymer (1) and the inorganic substance are not only easily physically attached but also chemically easily adhered to each other in the particles, and the above-mentioned mechanism of action is enhanced. Cheap.
  • a hydroxyl group-containing group, a carbonyl group-containing group and a phosphono group-containing group are preferable, and a hydroxyl group-containing group and a carbonyl group-containing group are more preferable, and a carbonyl group is more preferable from the viewpoint of easily improving physical properties such as dispersibility of the particles.
  • the containing group is more preferable.
  • 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.
  • 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.
  • An imide residue (-C (O) NHC (O) -etc.) and 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 polymer (1) is preferably 500 to 5000, preferably 600 to 3000, per 1 ⁇ 10 6 carbon atoms in the main chain. More preferably, 800 to 1500 pieces are further preferable.
  • the number of carbonyl group-containing groups in the polymer (1) can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133. In this case, the chemical interaction between the polymer (1) and the inorganic substance is also enhanced, and the inorganic substance tends to adhere physically and chemically densely to the surface of the molecular assembly of the polymer (1).
  • the polymer (1) contains 90 to 99 mol% of TFE units, 0.5 to 9.97 mol% of PAVE units, and 0.01 to 3 mol of units based on a monomer having a polar functional group, based on all the units. %, It is preferable to contain each. Further, as the monomer having a polar functional group, itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter, also referred to as “NAH”) are preferable, and NAH is more preferable. Specific examples of the polymer (1) include the polymers described in WO 2018/16644.
  • the polymer (2) is composed of only TFE units and PAVE units, and contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units with respect to all the units. 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 units.
  • Such a polymer has a higher degree of freedom in molecular conformation, and the above-mentioned mechanism of action is likely to be enhanced.
  • the fact that the polymer (2) does not have polar functional groups means that the number of polar functional groups contained in the polymer is less than 500 per 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. Means.
  • the number of the polar functional groups is preferably 100 or less, more preferably less than 50.
  • the lower limit of the number of polar functional 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 a polar functional group as the terminal group of the polymer chain, and is derived from a polymer having a polar functional group (derived from the polymerization initiator).
  • a polymer having a polar functional group at the terminal group of the polymer chain, etc. may be fluorinated to produce the polymer. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314, etc.).
  • the particles may contain a polymer other than the F polymer.
  • the ratio of the F polymer to the polymer contained in the particles is preferably 80% by mass or more, more preferably 100% by mass.
  • the polymer other than the F polymer include heat-resistant resins such as aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
  • the inorganic substances in the particles are preferably oxides, nitrides, simple metals, alloys and carbons, and silicon oxide (silica) and metal oxides (berylium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide and oxidation. Titanium, etc.), boron nitride, and magnesium metasilicate (steatite) are more preferred, with inorganic oxides, steatite, and boron nitride containing at least one element selected from aluminum, magnesium, silicon, titanium, and zinc. Further preferred, silica and boron nitride are particularly preferred, and silica is most preferred. Further, the inorganic substance may be ceramics. As the inorganic substance, one kind may be used, or two or more kinds may be mixed and used. When two or more kinds of inorganic substances are mixed, two kinds of silica may be used, or silica and a metal oxide may be used.
  • the inorganic substance in the particles preferably contains silica.
  • the content of silica in the inorganic substance is preferably 50% by mass or more, more preferably 75% by mass or more.
  • the upper limit of the silica content is 100% by mass.
  • 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 (trimethylamines, etc.). Triethylamine etc.), paraffin wax, silane coupling agent, silicone, polysiloxane, aluminum, silicon, zirconium, tin, titanium, antimony and other oxides, their hydroxides, their hydrated oxides, their phosphoric acid Examples include salt.
  • silane coupling agent examples include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-.
  • Isocyanatepropyltriethoxysilane is preferred.
  • the specific surface area of inorganic matter is preferably 1 ⁇ 20m 2 / g, more preferably 5 ⁇ 8m 2 / g.
  • the interaction between the inorganic substance and the F polymer is likely to be enhanced.
  • the inorganic substance and the F polymer are more uniformly distributed, and the physical properties of both are easily balanced.
  • inorganic substances include silica filler (“Admafine (registered trademark)” series manufactured by Admatex Co., Ltd.) and zinc oxide surface-treated with an ester such as propylene glycol dicaprate (manufactured by Sakai Chemical Industry Co., Ltd.).
  • hydrophobic AEROSIL series RX200 ", etc.
  • Tarkufiller manufactured by Nippon Tarku Co., Ltd.
  • SG series, etc.
  • Steatite filler BST
  • BST Steatite filler
  • BST Boron nitride filler
  • UHP UHP
  • the shape of the inorganic substance is preferably particulate, preferably spherical, needle-like (fibrous), or plate (pillar).
  • Specific shapes of inorganic substances include spherical, scaly, layered, leafy, apricot kernel, columnar, chicken crown, equiaxed, leafy, mica, block, flat plate, wedge, rosette, and mesh. , Square columnar, preferably spherical and scaly.
  • the uniformity of distribution of the inorganic substance in the molded product (polymer layer or the like) is improved, and its function can be easily enhanced.
  • As the inorganic substance spherical silica and scaly boron nitride are preferable.
  • the spherical inorganic substance is preferably substantially spherical.
  • Approximately spherical means that when the particles are observed with a scanning electron microscope (SEM), the ratio of the minor axis to the major axis is 0.5 or more, and the proportion of spherical particles is 95% or more. do.
  • the ratio of the minor axis to the major axis is preferably 0.5 or more, more preferably 0.8 or more. The above ratio is preferably less than 1.
  • the inorganic substance and the F polymer are more uniformly distributed in the molded product (polymer layer or the like), and the physical properties of both are more easily balanced.
  • the aspect ratio of the scaly inorganic substance is preferably 5 or more, and more preferably 10 or more.
  • the aspect ratio is preferably 1000 or less.
  • the average major axis (average value of the diameter in the longitudinal direction) of the scaly inorganic substance is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the average major axis is preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the average minor axis (average value of the diameter in the lateral direction) is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the average minor axis is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the inorganic substance and the F polymer are more uniformly distributed, and the physical properties of both are more easily balanced.
  • the scaly inorganic substance may have a single-layer structure or a multi-layer structure.
  • Examples of the latter inorganic substance include an inorganic substance having a hydrophobic layer on the surface and a hydrophilic layer inside. Specific examples thereof include an inorganic substance having a hydrophobic layer, a hydrophilic layer (moisture-containing layer), and a hydrophobic layer in this order.
  • the water content of the hydrophilic layer is preferably 0.3% by mass or more.
  • the D50 of the particles is preferably 40 ⁇ m or less, more preferably 10 ⁇ m or less, further preferably 6 ⁇ m or less, and particularly preferably 4 ⁇ m or less.
  • the D50 of the particles is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or more.
  • the D90 of the present particles is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and particularly preferably 10 ⁇ m or less. When D50 and D90 of the present particles are within such a range, the dispersion stability of the present particles in the liquid composition and the physical properties of the molded product (polymer layer or the like) obtained from the liquid composition are more likely to be improved.
  • the powder dynamic friction angle of the particles is preferably 40 degrees or less, more preferably 30 degrees or less, still more preferably 20 degrees or less.
  • the powder friction angle of the particles is preferably 5 degrees or more. In such a case, the particles are less likely to aggregate, and the dispersion stability of the particles in the liquid composition is likely to be improved. In addition, the particles can be easily dispersed in the liquid composition with less force. When the F polymer is the polymer (1), the particles are likely to develop such a powder dynamic friction angle.
  • This particle is a method in which F polymer particles and inorganic particles collide with each other in a suspended state at a temperature equal to or higher than the melting temperature of the F polymer (hereinafter, also referred to as “dry method A”), and the F polymer particles and the inorganic substance. (Hereinafter, also referred to as “dry method B”), the F polymer particles are brought into contact with the inorganic particles in a liquid to solidify the F polymer particles. It is preferable to produce the particles by a method of allowing the particles (hereinafter, also referred to as “wet method”) or the like.
  • the F polymer particles and the inorganic particles are supplied in a high temperature turbulent atmosphere, and stress is applied between them by collision between the F polymer particles and the inorganic particles to form a composite.
  • a dry method A may be called a hybridization treatment.
  • the atmosphere is formed by gas. Examples of the gas that can be used include air, oxygen gas, nitrogen gas, argon gas, or a mixed gas thereof.
  • the particles of the F polymer and the particles of the inorganic substance may be collectively supplied under the atmosphere as a premixed mixture, or may be separately supplied under the atmosphere.
  • the particles do not agglomerate with each other.
  • a method of suspending particles in a medium gas or liquid
  • a mixture of gas and liquid may be used as a medium.
  • F polymer particles and inorganic particles may be supplied into the atmosphere, and the F polymer particles and the inorganic particles are suspended in the medium. Later, the medium may be heated to form a high temperature turbulent atmosphere.
  • the particles are sandwiched between the inner wall of the container and the stirring body while stirring the particles by a stirring body (for example, a stirring blade) that rotates at high speed in a cylindrical container.
  • a stirring body for example, a stirring blade
  • a device for applying stress for example, "hybridization system” manufactured by Nara Machinery Co., Ltd.
  • the temperature of the atmosphere is preferably equal to or higher than the melting temperature of the F polymer, more preferably 260 to 400 ° C, still more preferably 320 to 380 ° C.
  • the aggregates may be crushed prior to being supplied in a high temperature atmosphere.
  • the method for crushing the agglomerates include a method using a jet mill, a pin mill, and a hammer mill.
  • the dry method B for example, F polymer particles and inorganic particles are pressed against the inner peripheral surface (receiving surface) of the tubular rotating body rotating around the central axis by centrifugal force, and separated from the inner peripheral surface at a small distance.
  • a pressing force or a shearing force is applied to the particles to form a composite.
  • Such a dry method B may be called a mechanofusion treatment.
  • the atmosphere inside the cylindrical rotating body can be an inert gas atmosphere or a reducing gas atmosphere.
  • the temperature of the atmosphere is preferably not less than the melting temperature of the F polymer, more preferably 100 ° C. or less.
  • the separation distance between the inner peripheral surface of the tubular rotating body and the inner piece is appropriately set according to the average particle size of the F polymer particles and the inorganic particles. This separation distance is usually preferably 1 to 10 mm.
  • the rotation speed of the cylindrical rotating body is preferably 500 to 10000 rpm. In this case, it is easy to increase the production efficiency of the particles.
  • the inorganic particles contain a large amount of agglomerates in which the primary particles are agglomerated with each other, the agglomerates are disassembled in the same manner as described in the above dry method A prior to being supplied into the cylindrical rotating body. You may crush it.
  • the rotating shaft is arranged in the horizontal direction, and a rotary tank having an elliptical (odd) cross section and a crushing and mixing chamber is provided, and the rotary shaft is rotatably inserted into the crushing and mixing chamber of the rotary tank. It can also be carried out by using a crushing / mixing device provided with a crushing / mixing blade which is arranged concentrically with the rotation axis of the rotary tank and has an elliptical (odd shape) cross section.
  • F polymer particles and inorganic particles are pressed between the short-diameter portion of the crushing / mixing chamber and the long-diameter portion of the crushing / mixing blade, and a pressing force or a shearing force is applied to the particles to form a composite. do.
  • the rotation direction of the rotary tank and the rotation direction of the crushing / mixing blade are preferably opposite to each other, and the rotation speed of the rotary tank is preferably set to be slower than the rotation speed of the crushing / mixing blade.
  • the pulverizing and mixing chamber and the pulverizing and mixing blade have irregularly shaped cross sections, and a momentary pressing force or an inorganic pressing force is applied to F polymer particles and inorganic particles that flow by dropping due to their own weight in the pulverizing and mixing chamber. Shear force can be applied repeatedly. Therefore, the particles can be pulverized and mixed in a short time while reducing the adverse effect of heat on the particles, so that the particles having the desired characteristics can be easily obtained.
  • inorganic particles are added to and mixed with a dispersion containing F polymer particles. Specifically, after the inorganic particles are dispersed in a liquid dispersion medium, this is added to a dispersion liquid containing F polymer particles and mixed.
  • a method is advantageous for mixing inorganic particles with F-polymer particles. If the mixed liquid containing the F polymer particles and the inorganic particles is destabilized and the solidification is caused, the F polymer particles and the inorganic particles are composited.
  • the inorganic substance is silica
  • colloidal silica can be preferably used for the particles of the inorganic substance.
  • the dispersion liquid containing the particles of the F polymer may be stirred during the addition of the inorganic particles or after the addition is completed.
  • the device used for this stirring include a stirring device provided with blades (stirring blades) such as propeller blades, turbine blades, paddle blades, and shell-shaped blades.
  • the stirring speed at this time may be such that the inorganic particles can be efficiently dispersed in the dispersion liquid containing the F polymer particles, and it is not necessary to apply a high shearing force to the F polymer particles.
  • the F polymer particles From the viewpoint of further enhancing the adhesion (adhesiveness) of the F polymer particles to the inorganic particles, it is preferable to perform surface treatment prior to or at the same time as mixing with the inorganic particles.
  • the surface treatment include plasma treatment, corona discharge treatment, etching treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, and ozone exposure treatment, and plasma treatment (particularly low-temperature plasma treatment) is preferable.
  • plasma treatment particularly low-temperature plasma treatment
  • the dry method A and the dry method B when the particles of the F polymer collide with the particles of the inorganic substance, heat is easily transferred uniformly to these particles, and the densification and spheroidization of the particles proceed. Easy and preferable.
  • the sphericity of the particles is preferably 0.5 or more.
  • Preferable embodiments of the particles include an aspect in which an F polymer is used as a core and an inorganic substance is attached to the surface of the core (hereinafter, also referred to as “aspect I”), and an inorganic substance is used as a core and F is formed on the surface of the core.
  • aspects I an F polymer is used as a core and an inorganic substance is attached to the surface of the core
  • an inorganic substance is used as a core and F is formed on the surface of the core.
  • examples thereof include a mode in which a polymer is attached (hereinafter, also referred to as “Phase II”).
  • the “core” means the core (central part) necessary for forming the particle shape of the present particle, and does not mean the main component in the composition of the present particle.
  • the deposit (inorganic substance or F polymer) adhering to the surface of the core may be adhered only to a part of the surface of the core, or may be adhered to most or the entire surface thereof.
  • the deposits cling to the surface of the core like dust, in other words, a large part of the surface of the core is exposed.
  • the deposits are evenly sprinkled on the surface of the core or are in a state of covering the surface of the core, and the particles are formed from the core and the shell covering the core. It can be said that it has a core-shell structure.
  • the core of the F polymer and the inorganic substance are each in the form of particles.
  • the core of the F polymer may be composed of a single particle of the F polymer, or may be composed of an aggregate of the particles of the F polymer.
  • the particles of aspect I are preferably produced by the dry method A or the dry method B.
  • the D50 of the F polymer particles it is preferable to set the D50 of the F polymer particles to be larger than the D50 of the inorganic particles, and to set the amount of the F polymer particles to be larger than the amount of the inorganic particles. If the particles are produced by the dry method A or the dry method B in such a relationship, the particles of the aspect I can be easily obtained.
  • the D50 of the inorganic particles is preferably 0.0001 to 0.5, more preferably 0.0001 to 0.1, still more preferably 0.002 to 0.02, based on the D50 of the F polymer particles.
  • Specific preferred embodiments include an embodiment in which the D50 of the F powder particles is more than 20 ⁇ m and the D50 of the inorganic particles is 10 ⁇ m or less, and a D50 of the F powder particles is more than 2 ⁇ m and the D50 of the inorganic particles is. Examples thereof include a mode in which the D50 of the F powder particles is 1 ⁇ m or less, and a mode in which the D50 of the F powder particles is more than 1 ⁇ m and the D50 of the inorganic particles is 0.1 ⁇ m or less.
  • the amount of the inorganic particles is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the F polymer particles.
  • the upper limit is preferably 50 parts by mass, more preferably 25 parts by mass, and even more preferably 5 parts by mass.
  • the D50 of the core of the F polymer is larger than the D50 of the inorganic particles
  • the mass of the F polymer in the inorganic particles is larger than the mass of the inorganic substance.
  • the surface of the core of the F polymer is coated with a larger amount of inorganic particles, so that the particles of aspect I have a core-shell structure. Further, in this case, agglutination of F powder particles is suppressed, and composite particles (main particles) in which inorganic particles are attached to a core composed of single F powder particles can be easily obtained.
  • the particles of the inorganic substance are preferably spherical or scaly, preferably spherical, and more preferably substantially true spherical.
  • the ratio of the minor axis to the major axis is preferably 0.6 or more, more preferably 0.8 or more. The above ratio is preferably less than 1.
  • the term "spherical” includes not only a true spherical shape but also a slightly distorted spherical shape. When such highly spherical inorganic particles are used, the inorganic substance and the F polymer are more uniformly distributed in the molded product (polymer layer or the like), and the physical properties of both are more easily balanced.
  • the D50 of the inorganic particles is preferably in the range of 0.001 to 10 ⁇ m, more preferably in the range of 0.001 to 0.3 ⁇ m, further preferably 0.005 to 0.2 ⁇ m, and 0.01 to 0. 1 ⁇ m is particularly preferable.
  • the particle size distribution of the inorganic particles is preferably 3 or less, more preferably 2.9 or less, using the value of D90 / D10 as an index.
  • D10 is a volume-based cumulative 10% diameter of the object, which is measured in the same manner as D50 and D90. A narrow particle size distribution is preferable from the viewpoint of facilitating control of the fluidity of the obtained particles.
  • the inorganic particles it is preferable that at least a part of the surface of the inorganic particles is surface-treated, and it is more preferable that the inorganic particles are surface-treated with a silazane compound such as hexamethyldisilazane or a silane coupling agent. ..
  • a silazane compound such as hexamethyldisilazane or a silane coupling agent. ..
  • silane coupling agent include the above-mentioned compounds.
  • one kind of inorganic particles may be used, or two or more kinds may be mixed and used.
  • the average particle diameter of each inorganic particle may be different from each other, and the mass ratio of the content of each inorganic particle can be appropriately set according to the desired function.
  • the D50 of the core of the F polymer is preferably 0.1 ⁇ m or more, and more preferably more than 1 ⁇ m.
  • the upper limit thereof is preferably 100 ⁇ m, more preferably 50 ⁇ m, and even more preferably 10 ⁇ m.
  • the D50 of the inorganic particles is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more.
  • the upper limit thereof is preferably 10 ⁇ m, more preferably 1 ⁇ m, and even more preferably 0.1 ⁇ m.
  • the proportion of the F polymer in the particles of the aspect I is preferably 50 to 99% by mass, more preferably 75 to 99% by mass.
  • the proportion of the inorganic substance is preferably 1 to 50% by mass, more preferably 1 to 25% by mass.
  • the ratio of the fluorine element content to the inorganic element content on the surface of the particles of the embodiment I measured by energy dispersive X-ray spectroscopy is preferably less than 1, preferably 0.5 or less. Is more preferable, and 0.1 or less is further preferable. The above ratio is preferably 0 or more.
  • the target elements in this measurement are four elements, carbon element, fluorine element, oxygen element and silicon element, and the ratio (unit: Atomic%) of each element of fluorine element and silicon element to the total is determined by each element. This is the case when the content is used.
  • the particles of the aspect I of the mass ratio are particles whose surface is highly coated with an inorganic substance, and not only have excellent particle physical characteristics (dispersity in liquid, etc.) due to the inorganic substance, but are also formed from the particles.
  • the molded product is likely to have the physical characteristics of an inorganic substance and the physical characteristics of an F polymer to a high degree.
  • the particles of Aspect I may be further surface-treated depending on the physical characteristics of the inorganic substance adhering to the surface.
  • Specific examples of such surface treatment include a method of surface-treating the particles of aspect I in which the inorganic substance contains silica with siloxanes (polydimethylsiloxane or the like) or a silane coupling agent.
  • Such surface treatment can be carried out by mixing the dispersion liquid in which the particles are dispersed with the siloxanes or the silane coupling agent, reacting the siloxanes or the silane coupling agent, and recovering the particles.
  • the silane coupling agent the above-mentioned compounds are preferable. According to such a method, not only the amount of surface silica of the present particles can be adjusted, but also the surface physical characteristics thereof can be further adjusted.
  • the inorganic core is preferably in the form of particles. In this case, the surface of the inorganic core of the particles is easily covered with the F polymer, and thus it is easy to prevent the particles from agglutinating.
  • the particles of aspect II are also preferably produced by the dry method A or the dry method B.
  • the D50 of the inorganic particles is set to be larger than the D50 of the F polymer particles, and the amount of the inorganic particles is set to be larger than the amount of the F polymer particles. If the particles are produced by the dry method A or the dry method B in such a relationship, the particles of the second aspect can be easily obtained.
  • the D50 of the F polymer particles is preferably 0.0001 to 0.02, more preferably 0.002 to 0.1, based on the D50 of the inorganic particles.
  • the amount of F polymer particles is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by weight of the inorganic particles.
  • the upper limit is preferably 50 parts by mass, more preferably 10 parts by mass, and even more preferably 3 parts by mass.
  • the D50 of the inorganic core is larger than the D50 of the F polymer particles, and the mass of the inorganic substance occupying the D50 is larger than the mass of the F polymer.
  • the surface of the inorganic core is coated with a larger amount of F polymer particles, so that the particles of aspect II have a core-shell structure.
  • the D50 of the inorganic core is preferably 0.1 ⁇ m or more, more preferably more than 1 ⁇ m.
  • the upper limit is preferably 30 ⁇ m, more preferably 6 ⁇ m.
  • the proportion of the inorganic substance in the particles of the second aspect is preferably 50 to 99% by mass, more preferably 60 to 90% by mass.
  • the proportion of the F polymer is preferably 1 to 50% by mass, more preferably 10 to 40% by mass.
  • the liquid composition of the present invention (hereinafter, also referred to as "the present composition”) is a composition containing the present particles and a liquid dispersion medium, in which the present particles are dispersed in the liquid dispersion medium.
  • the particles can exhibit a sufficiently high polarity and can be stably dispersed even if a large amount is added to the liquid dispersion medium.
  • a molded product polymer layer, film, etc. formed from such a liquid composition
  • the F polymer and the inorganic substance are more uniformly distributed, and the physical properties of the F polymer (electrical properties, adhesiveness, etc.) and the physical properties of the inorganic substance are obtained. (Low line swelling, etc.) is highly likely to occur.
  • the liquid dispersion medium in the present invention is a liquid compound that functions as a dispersion medium for the particles and is inert at 25 ° C.
  • the liquid dispersion medium may be water or a non-aqueous dispersion medium.
  • the liquid dispersion medium may be one kind or two or more kinds. In this case, dissimilar liquid compounds are preferably compatible.
  • the boiling point of the liquid dispersion medium is preferably 125 to 250 ° C. In this range, when the liquid dispersion medium is removed from the liquid composition, the particles are highly fluidized and densely packed, and as a result, a dense molded product (polymer layer or the like) is likely to be formed.
  • the liquid dispersion medium at least one liquid compound selected from the group consisting of water, amides, ketones and esters is preferable from the viewpoint of enhancing the dispersion stability of the particles in the composition, and water, N-methyl- 2-Pyrrolidone, ⁇ -butyrolactone, methyl ethyl ketone, cyclohexanone and cyclopentanone are more preferred.
  • the liquid dispersion medium contains an aprotic polar solvent such as N-methyl-2-pyrrolidone
  • at least a part of the surface of the inorganic substance in the particles is composed of an amino group, a vinyl group and a (meth) acryloyloxy group. It is preferably surface-treated with a silane coupling agent having at least one group selected from the group, and more preferably surface-treated with phenylaminosilane.
  • the liquid dispersion medium contains a non-polar solvent such as toluene
  • at least a part of the surface of the inorganic substance in the particles is preferably hydrophobized, and at least selected from the group consisting of an alkyl group and a phenyl group.
  • the liquid dispersion medium contains a protic polar solvent such as water
  • the inorganic substances in the particles are preferably not surface-treated.
  • the present composition tends to have excellent dispersion stability.
  • the content of the particles in the composition is preferably 1 to 50% by mass, more preferably 10 to 40% by mass.
  • the content of the liquid dispersion medium in the present composition is preferably 50 to 99% by mass, more preferably 60 to 90% by mass.
  • the composition preferably further contains a surfactant from the viewpoint of further improving the dispersion stability of the particles, suppressing particle sedimentation, and improving the handleability.
  • the surfactant is preferably nonionic.
  • the hydrophilic moiety of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
  • the hydrophobic moiety of the surfactant preferably has an alkyl group, an acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group.
  • a polyoxyalkylene alkyl ether As the surfactant, a polyoxyalkylene alkyl ether, an acetylene-based surfactant, a silicone-based surfactant and a fluorine-based surfactant are preferable, and a silicone-based surfactant is more preferable.
  • the silicone-based surfactant may be used in combination with a polyoxyalkylene alkyl ether.
  • surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafuck” series (manufactured by DIC), and “Unidyne” series (Daikin).
  • the viscosity of the present composition is preferably 50 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more.
  • the viscosity of the composition is preferably 1000 mPa ⁇ s or less, more preferably 800 mPa ⁇ s or less.
  • the thixotropy of the present composition is preferably 1.0 or more.
  • the thixotropy of the present composition is preferably 3.0 or less, more preferably 2.0 or less. In this case, since the present composition is not only excellent in coatability but also excellent in homogeneity, it is easy to form a more dense molded product (polymer layer or the like).
  • the present composition may further contain a polymer other than the F polymer or a precursor thereof.
  • polymers or precursors thereof include polytetrafluoroethylene (PTFE), polymers containing TFE units and PAVE units (PFA), polymers containing TFE units and units based on hexafluoropropylene (FEP), TFE units and the like.
  • PTFE polytetrafluoroethylene
  • PFA polymers containing TFE units and units based on hexafluoropropylene
  • FEP hexafluoropropylene
  • TFE units and the like Polymers containing ethylene-based units (ETFE), polyvinylidene fluoride (PVDF), polyimides, polyarylates, polysulfones, polyallylsulfones, polyamides, polyetheramides, polyphenylene ethers, polyphenylene sulfides, polyallyl ether ketones, polyamideimides.
  • this composition also contains a thioxifying agent, a viscosity modifier, a defoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, and an antistatic agent.
  • a thioxifying agent such as agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, and various fillers may be further contained.
  • the present composition is applied to the surface of the base material layer and heated to form a polymer layer, and the base material layer and the polymer are formed.
  • a laminate having a layer is obtained. More specifically, in the present method 1, the composition is applied to the surface of the base material layer to form a liquid film, and the liquid film is heated to remove the liquid dispersion medium to form a dry film. Further, by heating the dry film and firing the F polymer, a laminate having a polymer layer containing the F polymer and an inorganic substance on the surface of the base material layer can be obtained.
  • the temperature for heating the liquid coating is preferably 120 ° C. to 200 ° C.
  • the temperature for heating the dry film is preferably 250 ° C. to 400 ° C., more preferably 300 to 380 ° C.
  • Examples of each heating method include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays.
  • a metal substrate copper, nickel, aluminum, titanium, metal foil such as an alloy thereof, etc.
  • a resin film PTFE, polyimide, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, polyphenylene, etc.
  • prepreg precursor of fiber-reinforced resin substrate
  • the coating methods include spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain Mayer bar method, and slot die coating.
  • the law can be mentioned.
  • the thickness of the polymer layer is preferably 0.1 to 150 ⁇ m. Specifically, when the base material layer is a metal foil, the thickness of the polymer layer is preferably 1 to 30 ⁇ m. When the base material layer is a resin film, the thickness of the polymer layer is preferably 1 to 150 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the present composition may be applied to only one surface of the base material layer, or may be applied to both sides of the base material layer. In the former, a laminate having a base material layer and a polymer layer on one surface of the base material layer is obtained, and in the latter, a laminate having a polymer layer on both the surfaces of the base material layer and the base material layer. Is obtained.
  • Such a laminate includes a metal foil, a metal-clad laminate having a polymer layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having a polymer layer on both surfaces of the polyimide film. Can be mentioned.
  • a metal foil with a carrier containing two or more layers of metal foil may be used.
  • the metal foil with a carrier includes a carrier copper foil (thickness: 10 to 35 ⁇ m) and an ultrathin copper foil (thickness: 2 to 5 ⁇ m) laminated on the carrier copper foil via a release layer. Copper foil can be mentioned. By using such a copper foil with a carrier, it is possible to form a fine pattern by an MSAP (modified semi-additive) process.
  • the release layer a metal layer containing nickel or chromium or a multilayer metal layer in which the metal layers are laminated is preferable. Specific examples of the metal foil with a carrier include the trade name "FUTF-5DAF-2" manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd.
  • the outermost surface of the laminate in this method 1 may be further surface-treated in order to further improve its adhesiveness.
  • the surface treatment method include annealing treatment, corona treatment, plasma treatment, ozone treatment, excimer treatment, and silane coupling treatment.
  • the conditions for the annealing treatment are preferably 120 to 180 ° C., a pressure of 0.005 to 0.015 MPa, and a time of 30 to 120 minutes.
  • the gas used for the plasma treatment include oxygen gas, nitrogen gas, rare gas (argon and the like), hydrogen gas, ammonia gas and vinyl acetate. One type of these gases may be used, or two or more types may be used in combination.
  • Another substrate may be further laminated on the outermost surface of the laminated body in the present method 1.
  • substrates include a heat-resistant resin film, a prepreg which is a precursor of a fiber-reinforced resin plate, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer.
  • the prepreg is a sheet-like substrate in which a base material (toe, woven cloth, etc.) of reinforcing fibers (glass fibers, carbon fibers, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.
  • the heat-resistant resin film is a film containing one or more heat-resistant resins.
  • heat-resistant resin examples include polyimide, polyallylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, and liquid crystal polyester amide.
  • Polyimide particularly aromatic polyimide is preferred.
  • Examples of the laminating method include a method of heat-pressing the laminated body and another substrate.
  • the hot press conditions are preferably such that the temperature is 120 to 400 ° C., the atmospheric pressure is a vacuum of 20 kPa or less, and the press pressure is 0.2 to 10 MPa.
  • the laminate in Method 1 has a polymer layer having excellent electrical properties, and is therefore suitable as a printed circuit board material.
  • the laminate in the present invention can be used as a flexible metal-clad laminate or a rigid metal-clad laminate in the production of a printed circuit board, and in particular, can be suitably used in the production of a flexible printed circuit board as a flexible metal-clad laminate. ..
  • a printed circuit board is obtained by etching a metal foil of a laminate (metal foil with a polymer layer) in which the base material layer is a metal foil to form a transmission circuit. Specifically, a method of etching a metal foil to process it into a predetermined transmission circuit, or a method of processing a metal foil into a predetermined transmission circuit by an electrolytic plating method (semi-additive method (SAP method), MSAP method, etc.). Can be used to manufacture printed circuit boards.
  • a printed circuit board manufactured from a metal foil with a polymer layer has a transmission circuit formed from the metal foil and a polymer layer in this order.
  • the configuration of the printed circuit board includes a transmission circuit / polymer layer / prepreg layer and a transmission circuit / polymer layer / prepreg layer / polymer layer / transmission circuit.
  • an interlayer insulating film may be formed on the transmission circuit, a solder resist may be laminated on the transmission circuit, or a coverlay film may be laminated on the transmission circuit.
  • These interlayer insulating films, solder resists and coverlay films may be formed from the present composition.
  • the particles and the fluoroolefin polymer are melt-kneaded and then extrusion-molded to obtain a film. Since the particles contain an F polymer that has a high interaction (compatibility) with the fluoroolefin polymer, both are uniformly melt-kneaded, and in the obtained film, the F polymer, the fluoroolefin polymer, and the inorganic substance are uniformly mixed. Distributed, physical characteristics (particularly electrical properties) due to F polymers and fluoroolefin polymers and physical properties due to inorganic substances (low linear expansion, etc.) are highly likely to be expressed.
  • the fluoroolefin polymer to be melt-kneaded with the particles may be an F polymer or a polymer containing a unit based on a fluoroolefin other than the F polymer.
  • fluoroolefin polymer examples include PTFE, PFA, FEP, ETFE and PVDF.
  • the PFA may be an F polymer or a PFA other than the F polymer.
  • the melting temperature (melting point) of the fluoroolefin polymer is preferably 160 to 330 ° C.
  • the glass transition point of the fluoroolefin polymer is preferably 45 to 150 ° C.
  • the fluoroolefin polymer preferably has a polar functional group. Both the F polymer and the fluoroolefin polymer preferably have a polar functional group.
  • the types and introduction methods of the polar functional groups are the same as those in the above-mentioned F polymer, including suitable types and introduction methods.
  • Melt-kneading of the particles and the TFE-based polymer is performed using, for example, a uniaxial kneader.
  • the uniaxial kneader has a cylinder and one screw rotatably provided in the cylinder. If a uniaxial kneader is used, it is easy to prevent deterioration of the F polymer and the TFE polymer during melt kneading.
  • the effective length (L / D) represented by the ratio of the total length L to the diameter D is preferably 30 to 45.
  • the rotation speed of the screw is preferably 10 to 50 ppm.
  • the melt-kneaded product is discharged from a T-die arranged at the tip of the cylinder. After that, the melt-kneaded product discharged from the T-die comes into contact with a plurality of cooling rolls to solidify and form a film.
  • the obtained long film is wound on a take-up roll.
  • the thickness of the film is preferably 5 to 150 ⁇ m, more preferably 10 to 100 ⁇ m.
  • the shape of the film may be long or leafy.
  • the length of the elongated film in the longitudinal direction is preferably 100 m or more.
  • the upper limit of the length in the longitudinal direction is usually 2000 m.
  • the length of the long shape in the lateral direction is preferably 1000 mm or more.
  • the upper limit of the length in the lateral direction is usually 3000 mm.
  • a laminate having a polymer layer formed from the film and the base material layer can be obtained.
  • the conditions for the hot press are preferably such that the temperature is 120 to 300 ° C., the atmospheric pressure is a vacuum of 20 kPa or less, and the press pressure is 0.2 to 10 MPa.
  • the aspects of the substrate layer, the printed circuit board using the laminate, and the multilayer printed circuit board are the same as those in the above-mentioned method 1 including the preferable aspects.
  • the inflation film may be manufactured by using a round die instead of the T die.
  • the present invention is not limited to the configuration of the above-described embodiment.
  • the composite particles and the liquid composition of the present invention may be added with any other composition or may be replaced with any composition exhibiting the same function in the composition of the above-described embodiment, respectively. ..
  • the method for producing composite particles, the method for producing a laminate, and the method for producing a film of the present invention may additionally have any other step in the configuration of the above-described embodiment, and have the same operation. May be replaced with any step that results in.
  • -Non-F polymer particles Particles composed of a non-F polymer (melting temperature: 305 ° C.) containing 98.7 mol% and 1.3 mol% of TFE units and PPVE units in this order and having no polar functional group.
  • -PTFE particles Fibril-like non-thermally meltable PTFE particles (D50: 2.4 ⁇ m)
  • -Particles of F polymer 1 Particles composed of F polymer 1 (D50: 25 ⁇ m)
  • the number of carbonyl group-containing groups per 1 ⁇ 10 6 carbon atoms in the main chain is 1000 for the F polymer 1 and 40 for the F polymer 2.
  • the melt viscosities of F-polymer 1 and F-polymer 2 at 380 ° C. are in the range of 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s, and the glass transition points of F-polymer 1 and F-polymer 2 are 80.
  • -Silica particles 1 Spherical particles made of silica (D50: 0.5 ⁇ m, substantially spherical)
  • -Silica particles 2 Spherical particles made of silica surface-treated with a silane coupling agent (D50: 0.03 ⁇ m, substantially spherical)
  • -Boron nitride particles scaly particles made of boron nitride (D50: 7.0 ⁇ m, aspect ratio: 1000 or less)
  • Example 2 Fabrication of composite particles (Example 1) A mixture of 98 parts by mass of F polymer 1 particles 1 and 2 parts by mass of silica particles 1 was prepared. Next, the mixture was charged into a powder processing apparatus (mechanofusion apparatus) including a cylindrical rotating body having a receiving surface on the inner peripheral surface and an inner piece arranged at a minute distance from the receiving surface. After that, the cylindrical rotating body was rotated at high speed around the central axis. The centrifugal force generated at this time pressed the particles against the receiving surface, introduced the mixture into the narrow space (pressing space) between the receiving surface and the inner piece, and collided the particles in a sheared state for treatment. The temperature of the atmosphere of the cylindrical rotating body during the treatment was maintained at 100 ° C.
  • a powder processing apparatus mechanofusion apparatus
  • the obtained processed product was a fine powder. Further, as a result of analyzing this powder with an optical microscope, it was a composite particle 1 having a core-shell structure in which the F polymer 1 was used as a core and silica particles 1 were adhered to the surface of the core to form a shell.
  • the ratio of the fluorine element content on the surface of the composite particle to the silicon element content (hereinafter, also referred to as “F / Si ratio”) measured by energy dispersion type X-ray spectroscopy was 0.006.
  • the target elements in the measurement are four elements, carbon element, fluorine element, oxygen element and silicon element, and the ratio (unit: Atomic%) of each element of fluorine element and silicon element to the total is the content of each element.
  • the amount was taken.
  • the shape of the composite particle 1 was spherical, its D50 was 20 ⁇ m, and the powder dynamic friction angle was 18 degrees.
  • the composite particle 1 is manufactured, and subsequently, a mixture of 98 parts by mass of F polymer 1 particles 1 and 2 parts by mass of silica particles 1 is charged into the mechanofusion device without cleaning the mechanofusion device. When a processed product was obtained, the particles were the same as those of the composite particle 1.
  • Example 2 Composite particles 2 were obtained in the same manner as in Example 1 except that the mixture was prepared with 95 parts by mass of F polymer 1 particles 1 and 5 parts by mass of silica particles 1. The F / Si ratio of the composite particle 2 was 0.337, and its D50 was 30 ⁇ m.
  • Example 3 A composite particle 3 was obtained in the same manner as in Example 1 except that the mixture was prepared with 75 parts by mass of F polymer 1 particles 1 and 25 parts by mass of silica particles 1. The F / Si ratio of the composite particle 3 was 0.672, and its D50 was 40 ⁇ m.
  • Example 4 Composite particles 4 were obtained in the same manner as in Example 2 except that the particles 1 of the F polymer 1 were changed to the particles of the F polymer 2.
  • the F / Si ratio of the composite particle 4 was 0.555, its D50 was 35 ⁇ m, and the powder friction angle was 25 degrees.
  • Example 5 Composite particles 5 were obtained in the same manner as in Example 1 except that the particles 1 of the F polymer 1 were changed to the particles of the non-F polymer.
  • the F / Si ratio of the composite particle 5 was more than 1, the D50 of the composite particle 5 was 50 ⁇ m, and the powder friction angle was 45 degrees.
  • Example 6 The treatment was carried out in the same manner as in Example 1 except that the particles 1 of the F polymer 1 were changed to the particles of PTFE.
  • the obtained processed product was a non-particulate mass.
  • Example 7 A composite particle 7 was obtained in the same manner as in Example 1 except that the mixture was prepared with 10 parts by mass of F polymer 1 particles 1 and 90 parts by mass of silica particles 1. As a result of analysis with an optical microscope, the composite particles 7 were composite particles having a core-shell structure in which silica was used as a core and F polymer 1 was adhered to the surface of the core to form a shell.
  • Example 8 Composite particles 8 were obtained in the same manner as in Example 1 except that the silica particles 1 were changed to silica particles 2. The F / Si ratio of the composite particle 8 was 0.005, its D50 was 5.5 ⁇ m, and the powder dynamic friction angle was 16 degrees.
  • Example 9 First, a mixture of 70 parts by mass of F polymer 1 particles 2 and 30 parts by mass of boron nitride particles was prepared. Next, a powder processing device (hybridization system) that applies stress by sandwiching particles between the inner wall of the container and the agitator while stirring the particles with a stirring blade that rotates at high speed in a cylindrical container. The mixture was put into. Then, the particles 2 of the F polymer 1 and the particles of boron nitride were made to collide with each other while being suspended in an atmosphere of high temperature turbulence, and a stress was applied between them to perform a composite treatment. The temperature inside the apparatus during the treatment was maintained at 100 ° C.
  • the composite particles 9 had a core-shell structure in which F polymer 1 was used as a core and boron nitride particles were adhered to the surface of the core to form a shell.
  • the shape of the composite particle 9 was spherical, its D50 was 35 ⁇ m, and the powder dynamic friction angle was 26 degrees.
  • each of the composite particles 1 to 4, 7 to 9 and N-methyl-2-pyrrolidone (NMP) were put into a pot, and then zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to prepare a liquid composition. Next, a liquid composition was applied to the surface of the long copper foil using a bar coater to form a liquid film. Next, the metal foil on which the liquid film was formed was passed through a drying oven at 120 ° C. for 5 minutes and dried by heating to obtain a dry film. Then, the dry film was heated at 380 ° C. for 3 minutes in a nitrogen oven. As a result, a laminate having a copper foil and a polymer layer containing a melt-fired polymer and an inorganic substance on the surface thereof was obtained.
  • NMP N-methyl-2-pyrrolidone
  • the warp of the laminated body was evaluated by cutting out a 180 mm square test piece from the laminated body, measuring the test piece by the measuring method specified in JIS C 6471: 1995, and evaluating according to the following criteria.
  • X The coefficient of linear expansion was ⁇ 20 ppm / ° C. or higher.
  • the composite particles of the present invention are excellent in dispersion stability in a liquid composition.
  • a liquid composition can be used for producing a molded product (laminate, film, etc.) having physical characteristics based on an F polymer and characteristics based on an inorganic substance.
  • the molded product of the present invention is useful as an antenna part, a printed substrate, an aircraft part, an automobile part, a sports tool, a food industry product, a paint, a cosmetic, and the like.
  • Heat dissipation member, etc. wire coating material (aircraft wire, etc.), electrically insulating tape, insulating tape for oil excavation, material for printed substrate, separation film (precision filtration film, ultrafiltration film, back-penetration film, ion exchange film) , Dialysis membrane, gas separation membrane, etc.), electrode binder (for lithium secondary battery, fuel cell, etc.), copy roll, furniture, automobile dashboard, cover for home appliances, sliding member (load bearing, sliding shaft, etc.) Valves, bearings, gears, cams, belt conveyors, food transport belts, etc.), tools (shovels, shavings, cuttings, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container coverings. , It is useful as an outer surface covering material for heat exchangers (fins, heat transfer tubes, etc.) of refrigerating equipment and the like.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

La présente invention aborde le problème consistant à fournir une particule composite contenant une quantité arbitraire d'une substance inorganique et ayant des propriétés physiques souhaitées telles qu'une grande polarité.　Une particule composite selon la présente invention contient : un polymère à base de tétrafluoroéthylène ayant une température de fusion de 260 à 320 °C ; et une substance inorganique, le polymère à base de tétrafluoroéthylène étant au moins un polymère choisi dans le groupe constitué par un polymère à base de tétrafluoroéthylène contenant un motif à base de perfluoro(alkylvinyléther) et ayant un groupement fonctionnel polaire, et un polymère à base de tétrafluoroéthylène contenant, par rapport à l'ensemble des motifs, 2,0 à 5,0 % en moles d'un motif à base de perfluoro(alkylvinyléther) et n'ayant pas de groupement fonctionnel polaire.
PCT/JP2021/011654 2020-03-25 2021-03-22 Particule composite, procédé de production de particules composites, composition liquide, procédé de fabrication d'un stratifié, et procédé de fabrication d'un film WO2021193505A1 (fr)

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KR1020227034471A KR20220158736A (ko) 2020-03-25 2021-03-22 복합 입자, 복합 입자의 제조 방법, 액상 조성물, 적층체의 제조 방법 및 필름의 제조 방법
JP2022510466A JP7511117B2 (ja) 2020-03-25 2021-03-22 複合粒子、複合粒子の製造方法、液状組成物、積層体の製造方法及びフィルムの製造方法
CN202180018381.4A CN115210300A (zh) 2020-03-25 2021-03-22 复合粒子、复合粒子的制造方法、液态组合物、层叠体的制造方法及膜的制造方法

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JP2014502284A (ja) * 2010-09-24 2014-01-30 グリーン， ツイード オブ デラウェア， インコーポレイテッド 高温への適用に適したフッ素含有エラストマー組成物
WO2016017801A1 (fr) * 2014-08-01 2016-02-04 旭硝子株式会社 Poudre de résine ainsi que procédé de fabrication de celle-ci, corps composite, corps moulé, procédé de fabrication de corps moulé en céramique, plaque stratifiée métallique, carte de circuit imprimé, et préimprégné
WO2017135168A1 (fr) * 2016-02-02 2017-08-10 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié feuille métallique-gaine, feuille de résine, carte de circuit imprimé, et dispositif à semi-conducteur
JP2019035027A (ja) * 2017-08-16 2019-03-07 富士ゼロックス株式会社 粉体塗料、塗装品及び塗装品の製造方法
WO2019112017A1 (fr) * 2017-12-07 2019-06-13 Ａｇｃ株式会社 Poudre, peinture en poudre et procédé de production de stratifié

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JP6442281B2 (ja) 2014-12-26 2018-12-19 株式会社アドマテックス シリカ被覆有機物粒子およびその製造方法並びに樹脂組成物
JP6809911B2 (ja) 2017-01-20 2021-01-06 矢崎総業株式会社 差電圧測定装置

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JP2014502284A (ja) * 2010-09-24 2014-01-30 グリーン， ツイード オブ デラウェア， インコーポレイテッド 高温への適用に適したフッ素含有エラストマー組成物
WO2016017801A1 (fr) * 2014-08-01 2016-02-04 旭硝子株式会社 Poudre de résine ainsi que procédé de fabrication de celle-ci, corps composite, corps moulé, procédé de fabrication de corps moulé en céramique, plaque stratifiée métallique, carte de circuit imprimé, et préimprégné
WO2017135168A1 (fr) * 2016-02-02 2017-08-10 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié feuille métallique-gaine, feuille de résine, carte de circuit imprimé, et dispositif à semi-conducteur
JP2019035027A (ja) * 2017-08-16 2019-03-07 富士ゼロックス株式会社 粉体塗料、塗装品及び塗装品の製造方法
WO2019112017A1 (fr) * 2017-12-07 2019-06-13 Ａｇｃ株式会社 Poudre, peinture en poudre et procédé de production de stratifié

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