WO2021241547A1 - Procédé de production d'une dispersion - Google Patents

Procédé de production d'une dispersion Download PDF

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Publication number
WO2021241547A1
WO2021241547A1 PCT/JP2021/019727 JP2021019727W WO2021241547A1 WO 2021241547 A1 WO2021241547 A1 WO 2021241547A1 JP 2021019727 W JP2021019727 W JP 2021019727W WO 2021241547 A1 WO2021241547 A1 WO 2021241547A1
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dispersion
filler
particles
liquid
polymer
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PCT/JP2021/019727
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English (en)
Japanese (ja)
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敦美 山邊
文 伊藤
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Ａｇｃ株式会社
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Priority to JP2022526565A priority Critical patent/JPWO2021241547A1/ja
Priority to CN202180038356.2A priority patent/CN115667377A/zh
Publication of WO2021241547A1 publication Critical patent/WO2021241547A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • 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
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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

Definitions

  • the present invention relates to a method for producing a dispersion containing particles of a tetrafluoroethylene polymer and a filler of an inorganic compound, and a method for producing composite particles by such a method.
  • Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) have excellent physical properties such as electrical properties, water and oil repellency, chemical resistance, and heat resistance, and are used in various industrial applications such as printed circuit boards.
  • PTFE polytetrafluoroethylene
  • As a coating agent used to impart the physical properties to the surface of the base material a dispersion liquid containing particles of a tetrafluoroethylene-based polymer is known.
  • the frequency of signals has been increasing, and there is a demand for materials having electrical characteristics such as low dielectric constant and low dielectric loss tangent and excellent insulation performance.
  • a dispersion liquid containing particles of a tetrafluoroethylene polymer has attracted attention. There is.
  • Patent Document 1 discloses a dispersion liquid of PTFE particles further containing an inorganic filler of ceramics from the viewpoint of improving dispersion stability.
  • an object of the present invention is to provide a method for producing a dispersion liquid having excellent dispersion stability and a method for producing composite particles constituting such a dispersion liquid.
  • the present invention has the following aspects.
  • a liquid composition containing heat-meltable tetrafluoroethylene polymer particles, an inorganic compound filler, and a polar liquid dispersion medium is sheared to obtain the tetrafluoroethylene polymer and the inorganic compound filler.
  • a method for producing a dispersion liquid which obtains a dispersion liquid containing the liquid dispersion medium.
  • the tetrafluoroethylene-based polymer contains a unit based on perfluoro (alkyl vinyl ether) and has a polar functional group, and the tetrafluoroethylene-based polymer has 2 units based on perfluoro (alkyl vinyl ether) for all units.
  • the mass ratio of the particles of the tetrafluoroethylene-based polymer to the filler of the inorganic compound in the liquid composition is 0.01 to 2.0, where the mass of the particles is 1 and the mass of the filler is 0.01 to 2.0.
  • the average particle size (volume-based cumulative 50% diameter) of the filler of the inorganic compound in the liquid composition is based on the average particle size (volume-based cumulative 50% diameter) of the particles of the tetrafluoroethylene-based polymer.
  • the production method according to any one of [1] to [8] which keeps the liquid viscosity during the shearing treatment at 100,000 mPa ⁇ s or less.
  • a dispersion liquid of a tetrafluoroethylene-based polymer having excellent dispersion stability. Further, from such a dispersion liquid, composite particles that contribute to the improvement of dispersion stability can be produced.
  • the dispersion liquid produced by the method of the present invention is excellent in physical properties such as electrical characteristics, and is useful as a constituent material of a printed circuit board, for example. Further, the composite particles obtained from the dispersion liquid are also useful as additives and modifiers for various varnishes (resist, ink, paint, etc.).
  • the "average particle size (D50)" is a volume-based cumulative 50% diameter of an object (particle, filler) determined by a laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the group of objects as 100%, and the particle size is the point where the cumulative volume is 50% on the cumulative curve. “D90” is the volume-based cumulative 90% diameter of the object, which is similarly measured.
  • the objects D50 and D90 are analyzed by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring instrument manufactured by HORIBA, Ltd.) after dispersing the object in water. Desired.
  • the "heat-meltable polymer” means a polymer exhibiting melt fluidity, and means a polymer having a temperature at which the melt flow rate is 0.1 to 1000 g / 10 minutes under the condition of a load of 49 N.
  • the "melting temperature” is the temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method.
  • the "viscosity of the dispersion liquid” is a viscosity measured using a B-type viscometer under the condition of 25 ° C. and a rotation speed of 30 rpm. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
  • the "thixotropic ratio” is a value calculated by dividing the viscosity ⁇ 1 of the dispersion liquid measured under the condition of a rotation speed of 30 rpm by the viscosity ⁇ 2 measured under the condition of a rotation speed of 60 rpm. The measurement of each viscosity is repeated 3 times, and the average value of the measured values for 3 times is used.
  • unit in a polymer is meant an atomic group based on the monomer formed by the polymerization of the monomers.
  • the unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by processing a polymer.
  • the unit based on the monomer a is also simply referred to as “monomer a unit”.
  • the production method of the present invention (hereinafter, also referred to as “this method”) is also referred to as particles (hereinafter, also referred to as “F powder”) of a heat-meltable tetrafluoroethylene polymer (hereinafter, also referred to as “F polymer”). ), A filler of an inorganic compound (hereinafter, also referred to as “inorganic filler”), and a liquid composition containing a polar liquid dispersion medium (hereinafter, also referred to as “dispersion medium”) are sheared to obtain the F powder. , A method for obtaining a dispersion containing the inorganic filler and the dispersion medium (hereinafter, also referred to as “the present dispersion”).
  • This dispersion has excellent dispersion stability. Further, when the dispersion liquid is air-dried on a glass plate and observed, composite particles in which the F powder and the inorganic filler are fused (hereinafter, also referred to as “main particles”. The inorganic filler adheres to the surface of the F powder). It was also confirmed for the first time that (including composite particles, etc.) existed. The reason why the dispersion stability of the dispersion liquid is improved and the reason why the particles are formed, and their correlation and mechanism of action are not necessarily clear, but are estimated as follows, for example.
  • F-polymers are not only superior in shape stability such as fibril resistance, but also have a high degree of freedom in which restrictions on molecular motion are relaxed at the monomolecular level. Has a formation. Since such an F polymer tends to form microspherulites at the molecular aggregate level, fine uneven structures are likely to be formed on the surface thereof, and the surface area is likely to be large. Therefore, it is considered that the molecular aggregate of the F polymer, typically the F powder, can physically adhere closely to the inorganic filler to form the present particles while remaining stable without damaging its shape.
  • F powder has low surface energy and low dispersion stability, but the particles in which the inorganic filler with high dispersion stability and the F powder are fused are mutual with other particles and the liquid dispersion medium as compared with the F powder. Easy to work. As a result, it is considered that the particles have excellent dispersion stability. As a result, since the particles have the physical characteristics of the F polymer and the physical characteristics of the inorganic filler and are excellent in stability, it is considered that a molded product having excellent electrical characteristics and the like could be formed from the dispersion liquid.
  • the D50 of the F powder is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the D50 of the F powder is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the D90 of the F powder is preferably 10 ⁇ m or less. In D50 and D90 in this range, the fluidity and dispersibility of the F powder become good, and the size of the composite particles existing in the dispersion liquid can be easily controlled so as to be difficult to settle.
  • the bulk density of the F powder is preferably 0.15 g / m 2 or more, more preferably 0.20 g / m 2 or more, from the viewpoint of the dispersion stability of the produced dispersion.
  • the bulk density of the F powder is preferably 0.50 g / m 2 or less, 0.35 g / m 2 or less is more preferable.
  • the F powder may contain a resin other than the F polymer, but it is preferable that the F polymer is the main component.
  • the content of the F polymer in the F powder is preferably 80% by mass or more, more preferably 100% by mass.
  • the resin include heat-resistant resins such as aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
  • the F polymer in this method is a heat-meltable polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE).
  • the melting temperature of the F polymer is preferably 260 to 325 ° C, more preferably 280 to 320 ° C. In such a case, the heat resistance of the molded product formed from the dispersion liquid obtained by the method of the present invention tends to be excellent.
  • the glass transition point of the F polymer is preferably 75 to 125 ° C, more preferably 80 to 100 ° C.
  • F polymer examples include polymers (PFA) containing TFE units and units based on perfluoro (alkyl vinyl ether) (PAVE) (PAVE units), and polymers (FEP) containing units based on TFE units and hexafluoropropene (HFP). Therefore, it is preferably PFA.
  • PFA polymers containing TFE units and units based on perfluoro (alkyl vinyl ether) (PAVE) (PAVE units)
  • FEP polymers containing units based on TFE units and hexafluoropropene (HFP). Therefore, it is preferably PFA.
  • PFA polymers
  • CF 2 CFOCF 3
  • the F polymer preferably has a polar functional group.
  • the polar functional group may be contained in a unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer.
  • an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, or an F polymer having a polar functional group obtained by subjecting the F polymer to plasma treatment or ionization line treatment can be used. Can be mentioned.
  • 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 from the viewpoint of dispersion stability of the dispersion produced by this method, and carbonyl.
  • Group-containing groups are more preferred.
  • the hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF 2 CH 2 OH, -C (CF 3 ) 2 OH and 1,2-glycol group (-CH (OH) CH 2 OH). ..
  • the carbonyl group-containing group is a group containing a carbonyl group (> C (O)), a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH 2 ), and an acid anhydride residue.
  • Groups (-C (O) OC (O)-), imide residues (-C (O) NHC (O)-etc.) and carbonate groups (-OC (O) O-) are preferred, and acid anhydride residues. Is more preferable.
  • the number of carbonyl group-containing groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, and more preferably 800 per 1 ⁇ 10 6 carbon atoms in the main chain. ⁇ 1500 pieces are more preferable.
  • the number of carbonyl group-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.
  • the F polymer comprises a polymer having a polar functional group (1) containing TFE units and PAVE units, or 2.0 to 5.0 mol% of PAVE units with respect to all units including TFE units and PAVE units.
  • the polymer (2) having no polar functional group is preferable.
  • These F-polymers not only have excellent dispersion stability of the particles, but are also difficult to be denatured even when the shearing treatment is performed by this method, and in the molded product (polymer layer, etc.) obtained from the produced dispersion liquid, these F polymers are used. It is easy to distribute more densely and uniformly. Further, it is easy to form fine spherulites in the molded product, and it is easy to improve the adhesion with other components. As a result, it is easier to obtain a molded product having excellent various physical properties such as electrical characteristics.
  • the polymer (1) is preferably a polymer containing TFE units, PAVE units and units based on a monomer having a polar functional group, and 90 to 99 mol% of these units are used in this order with respect to all units, 0. More preferably, the polymer contains 5.5 to 9.97 mol% and 0.01 to 3 mol%.
  • the presence of the polar functional group is preferable from the viewpoint of further improving the affinity and adhesion with the inorganic filler.
  • the monomer having a polar functional group itaconic anhydride, citraconic anhydride or 5-norbornen-2,3-dicarboxylic acid anhydride (hereinafter, also referred to as “NAH”) is preferable.
  • Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
  • the polymer (2) is composed of only TFE units and PAVE units, and preferably 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. ..
  • 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 polymer (2) does not have polar functional groups when the number of polar functional groups of the polymer is less than 500 with respect to 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. It means that there is.
  • 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 an F polymer having a polar functional group (derived from the polymerization initiator).
  • An F polymer or the like having a polar functional group at the terminal group of the main chain of the polymer may be fluorinated to produce the polymer.
  • Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314).
  • the inorganic filler is preferably particles of an inorganic compound.
  • the inorganic filler include fillers composed of oxides, nitrides, simple metals, alloys and carbon, and silicates (silicon oxide (silica), wollastonite, talc, mica) and metal oxides (oxidation). Fillers of beryllium, cerium oxide, aluminum oxide, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride and magnesium metasilicate (steatite) are preferred, and are selected from aluminum, magnesium, silicon, titanium and zinc.
  • Fillers of inorganic oxides containing at least one of the elements are more preferred, fillers of silica, titanium oxide, zinc oxide, steatite and boron nitride are even more preferred, and fillers of silica are particularly preferred.
  • the inorganic filler may be ceramics.
  • the inorganic filler one kind may be used, or two or more kinds may be mixed and used. When two or more kinds of inorganic fillers are mixed and used, two kinds of silica fillers may be mixed and used, or a silica filler and a metal oxide filler may be mixed and used.
  • the inorganic filler easily interacts with the F polymer, easily withstands the shearing force even when the shearing treatment is performed in this method, and easily improves the dispersion stability of the obtained dispersion liquid. Further, in the molded product formed from the dispersion liquid (for example, the polymer layer and the film described later), the physical characteristics based on the inorganic filler are remarkably likely to be exhibited.
  • the inorganic filler contains silica.
  • the content of silica in the inorganic filler is preferably 80% by mass or more, more preferably 90% by mass or more.
  • the upper limit of the silica content is 100% by mass.
  • the surface of the inorganic filler is 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 (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 Salt is mentioned.
  • the inorganic filler is surface-treated with a silane coupling agent.
  • the silane coupling agent include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane or 3-. Isocyanapropyltriethoxysilane is preferred. In this method, it is most preferable to use a silica filler surface-treated with a silane coupling agent as the inorganic filler.
  • the specific surface area of the inorganic filler is preferably 1 ⁇ 20m 2 / g, more preferably 5 ⁇ 8m 2 / g.
  • the inorganic filler examples 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.).
  • the shape of the inorganic filler includes granular, needle-like (fibrous), and plate-like, and specifically, spherical, scaly, layered, leaf-like, apricot kernel-like, columnar, chicken crown-like, equiaxed, and leaf-like.
  • examples include mica, block, flat plate, wedge, rosette, mesh, and prismatic. Of these, spherical and scaly are preferable, and spherical is more preferable.
  • the spherical inorganic filler is preferably substantially spherical. Approximately spherical means that when the inorganic filler is observed with a scanning electron microscope (SEM), the ratio of spherical particles having a ratio of the minor axis to the major axis of 0.5 or more is 95% or more. do. In the substantially spherical inorganic filler particles, 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 inorganic filler 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 likely to be expressed in a well-balanced manner.
  • the aspect ratio of the scaly inorganic filler is preferably 5 or more, 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 filler is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the average major axis is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the average minor axis is preferably 0.01 ⁇ m or more, 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 filler 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 likely to be balanced and expressed.
  • the scaly inorganic filler may have a single-layer structure or a multi-layer structure.
  • examples of the latter inorganic filler include an inorganic filler having a hydrophobic layer on the surface and a hydrophilic layer inside. Specific examples thereof include an inorganic filler 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 inorganic filler may be hollow.
  • the average particle size (D50) of the hollow inorganic filler is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the average particle size is more preferably 10 ⁇ m or less, further preferably 5 ⁇ m or less.
  • the average pore diameter of the pores of the hollow inorganic filler is preferably 10 to 1000 nm, more preferably 50 to 100 nm.
  • the average pore diameter the pore diameters of a plurality of pores (100) are obtained by direct observation with a scanning electron microscope (SEM) or the like, and the average value thereof is taken as the average pore diameter. In the case of irregularly shaped holes, the maximum diameter of the holes is the hole diameter.
  • the apparent specific gravity of the hollow inorganic filler is preferably 100 g / L or less, more preferably 30 to 60 g / L, from the viewpoint of sufficiently increasing the porosity.
  • the apparent specific gravity of the hollow inorganic filler is obtained from the mass and volume of the inorganic filler when it is charged into a measuring cylinder (capacity: 250 mL).
  • a hollow silica filler is preferable.
  • the inorganic filler may be an isotropic filler or an anisotropic filler.
  • the isotropic filler means a filler having the same physical properties (mechanical strength, electrical characteristics, thermal conductivity, etc.) regardless of the direction, and the anisotropic filler means a filler having different physical properties depending on the direction. ..
  • the average particle size (D50) of the inorganic filler is preferably 20 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the average particle size is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more.
  • the inorganic filler is a mixture of two kinds of inorganic fillers, it is preferable that the average particle diameters of the two kinds of inorganic fillers are different from each other.
  • the average particle size of the inorganic filler (1) is the inorganic filler (2).
  • the average particle size of the particles is preferably more than 1 times, more preferably 1.5 times or more.
  • the average particle size of the inorganic filler (1) is preferably 10 times or less, more preferably 5 times or less the average particle size of the inorganic filler (2).
  • the mass ratio of the content of the inorganic filler (2) to the content of the inorganic filler (1) is preferably 1.5 times or more, and more preferably 2 times or more.
  • the mass ratio is preferably 5 times or less.
  • the inorganic filler is less likely to be removed from the molded product formed from the present dispersion, and the surface of the molded product tends to be excellent in smoothness.
  • the molded product tends to have excellent low dielectric loss tangent properties.
  • the polar liquid dispersion medium is preferably a compound that is liquid at 25 ° C., which is classified as polar under atmospheric pressure, and is at least one polar compound selected from amides, ketones and esters. Is more preferable. It is considered that when such a dispersion medium is used, the inorganic filler alone does not have an excessive affinity in the liquid composition, and both the F powder and the inorganic filler can maintain a constant dispersed state. On the other hand, such a constant dispersed state can be said to be an unstable state that can be changed by an external stimulus. It is estimated that composite particles will be produced.
  • the boiling point of the dispersion medium is preferably in the range of 50 to 240 ° C. As the dispersion medium, one type may be used alone, or two or more types may be used in combination.
  • Dispersion media include water, N, N-dimethylformamide, N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N-methyl-2.
  • -Pyrrolidone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone, butyl acetate, methyl isopropyl ketone, methyl ethyl ketone can be mentioned.
  • the inorganic filler is a silane cup having at least a part of its surface having at least one group selected from the group consisting of an amino group, a vinyl group and a (meth) acryloyloxy group. It is preferably surface-treated with a ring agent, and more preferably surface-treated with phenylaminosilane.
  • the dispersion medium is a protonic compound such as water, it is preferable that the inorganic filler is not surface-treated.
  • the dispersion medium may contain a non-polar solvent as long as the effect of the present invention is not impaired.
  • the dispersion medium contains a non-polar solvent such as toluene
  • a non-polar solvent such as toluene
  • at least a part of the surface of the inorganic filler is hydrophobized, and at least one selected from the group consisting of an alkyl group and a phenyl group. It is preferably surface-treated with a silane coupling agent having a group.
  • the content of the dispersion medium in the liquid composition is preferably 30 to 90% by mass, more preferably 50 to 80% by mass.
  • the total content of the F powder and the inorganic filler in the liquid composition is preferably 40% by mass or more, more preferably 50 to 80% by mass, based on the total mass of the liquid composition.
  • the mass ratio of the F powder to the inorganic filler in the liquid composition is preferably 0.01 to 2.0, with the mass of the F powder being 1.
  • the liquid composition preferably contains 20 to 40% by mass of F powder and 5 to 40% by mass of an inorganic filler.
  • the liquid composition can be prepared by mixing F powder, an inorganic filler and a dispersion medium.
  • a mixing method the F powder and the inorganic filler are collectively added to the dispersion medium and mixed; the F powder and the inorganic filler are sequentially added to the dispersion medium and mixed; the F powder and the inorganic filler are mixed in advance.
  • a method of mixing the obtained mixture and the dispersion medium; a method of premixing the F powder and the dispersion medium, a method of premixing the inorganic filler and the dispersion medium, and further mixing the two obtained mixtures; and the like can be mentioned.
  • the liquid composition is prepared by a procedure in which F powder is dispersed in a dispersion medium in advance, and then particles of an inorganic filler are added as they are (directly) or in a state of being dispersed in a dispersion medium and mixed. After the particles of the inorganic filler are dispersed in the dispersion medium in advance, the liquid composition is prepared by adding the F powder as it is (directly) or in the state of being dispersed in the dispersion medium and mixing them. It is advantageous and preferable from the viewpoint of mixing the powder and the particles of the inorganic filler and dispersing them more uniformly.
  • the F powder is added at the same time as the dispersion medium in advance, or the F powder is dispersed. It is preferable to add it to the previous dispersion medium in advance.
  • Examples of the method of shearing the liquid composition include a stirring device equipped with blades (stirring blades) such as propeller blades, turbine blades, paddle blades, and shell-shaped blades in a single axis or multiple axes, a henshell mixer, and a pressurized kneader.
  • blades such as propeller blades, turbine blades, paddle blades, and shell-shaped blades in a single axis or multiple axes
  • a henshell mixer such as a henshell mixer, and a pressurized kneader.
  • Turbine mixer or planetary mixer Turbine mixer or planetary mixer; ball mill, attritor, basket mill, sand mill, sand grinder, dyno mill (bead mill using crushing medium such as glass beads or zirconium oxide beads), dispermat, SC mill, spike mill or Mixing with a disperser using media such as an agitator mill; using a disperser that does not use media such as high-pressure homogenizers such as microfluidizers, nanomizers, and ultimateizers, ultrasonic homogenizers, resolvers, dispersers, and high-speed impeller dispersers. Mixing is included.
  • high-pressure homogenizers such as microfluidizers, nanomizers, and ultimateizers, ultrasonic homogenizers, resolvers, dispersers, and high-speed impeller dispersers. Mixing is included.
  • the shearing process is preferably under high shear conditions. "High shear” means, in the case of agitation, agitation at a rate greater than at least 300 rpm.
  • the shearing treatment may be started during the addition of the particles of the inorganic filler to the liquid composition containing the F powder, or may be performed after the addition is completed. By continuously performing these shearing treatments for a sufficient time, a dispersion liquid having excellent dispersion stability can be formed.
  • the liquid temperature of the liquid composition containing F powder during the shearing treatment is preferably kept at 70 ° C. or lower, more preferably 50 ° C. or lower. When the liquid temperature is maintained at such a temperature, the obtained dispersion is difficult to thicken and gel. In addition, the particles are easily formed, and the obtained dispersion is likely to have excellent dispersion stability.
  • the liquid temperature is preferably maintained above 0 ° C., more preferably above 10 ° C.
  • the liquid viscosity of the liquid composition containing F powder during the shearing treatment is preferably kept at 100,000 mPa ⁇ s or less, and from the viewpoint of obtaining a dispersion liquid having excellent dispersion stability, it is kept at 10,000 mPa ⁇ s or less. Is more preferable.
  • the liquid viscosity of the liquid composition during the shearing treatment is preferably 1 mPa ⁇ s or more, and more preferably 10 mPa ⁇ s or more.
  • the flow form of the liquid composition in the shearing treatment is preferably an ascending flow.
  • the ascending flow may be an ascending flow in any of a swirling flow, a vertical circulation flow, and a radiating flow.
  • the flow form may be adjusted by a baffle plate or the like, or the flow form may be eccentric by adjusting the installation position and the installation angle of the processing device (stirring machine, stirring tank, etc.).
  • the liquid composition may further contain a silane coupling agent.
  • a silane coupling agent When the liquid composition contains a silane coupling agent, the F powder and the inorganic filler are more firmly bonded to each other, making it easier to obtain the particles in which the F powder or the inorganic filler is less likely to be removed, resulting in dispersion stability. It is easy to obtain an excellent dispersion.
  • the silane coupling agent include compounds similar to those of the above-mentioned silane coupling agent, which can be used in the surface treatment of the inorganic filler.
  • the liquid composition further contains a silane coupling agent, the content thereof is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more.
  • the content is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.
  • the ratio of the content of the silane coupling agent to the content of the F powder in the liquid composition is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.05 or more.
  • the above ratio is preferably 0.3 or less, more preferably 0.1 or less.
  • the liquid composition may or may not further contain a surfactant.
  • a surfactant the content thereof is preferably 1 to 15% by mass, and 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 acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group.
  • a glycol-based surfactant a glycol-based surfactant, an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant is preferable, and a silicone-based surfactant is more preferable.
  • the nonionic surfactant one kind may be used, or two or more kinds may be used. When two kinds of nonionic surfactants are used, the nonionic surfactants are preferably a silicone-based surfactant and a glycol-based surfactant.
  • surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafuck” series (manufactured by DIC), and “Unidyne” series (Daikin).
  • the liquid composition may further contain a resin material other than the F polymer.
  • a resin material may be thermosetting or thermoplastic, may be modified, may be dissolved in the liquid composition and the present dispersion, or may not be dissolved and dispersed. good.
  • resin materials include tetrafluoroethylene polymers other than F polymers, aromatic polyimides, aromatic polyamic acids which are aromatic polyimide precursors, aromatic maleimides, acrylic resins, phenol resins, liquid crystal polyesters, and liquid crystal polyester amides.
  • Polyimide resin modified polyphenylene ether, polyfunctional cyanic acid ester resin, polyfunctional maleimide-cyanic acid ester resin, polyfunctional maleimide, aromatic elastomers such as styrene elastomer, vinyl ester resin, urea resin, diallyl phthalate resin, melamine.
  • polytetrafluoroethylene-based polymer other than the F polymer polytetrafluoroethylene is preferable.
  • the liquid composition preferably further contains an aromatic polymer.
  • the aromatic polymer is preferably aromatic polyimide, aromatic polyamideimide, aromatic maleimide, polyphenylene ether, aromatic polyamic acid, or aromatic elastomer (styrene elastomer or the like), and is a thermoplastic aromatic polyimide. Is more preferable.
  • the adhesiveness and low linear expansion property of the molded product formed from the present dispersion are further improved, but also the liquid properties (viscosity, thixotropic ratio, etc.) of the present dispersion are balanced, and the handling property is improved. Easy to improve.
  • examples of the styrene elastomer include copolymers of styrene and conjugated diene or (meth) acrylic acid esters (styrene-butadiene rubber, styrene-based core-shell type copolymers, styrene-based block copolymers, etc.), and rubber and plastic.
  • Styrene elastomers having both properties, which are plasticized by heating and exhibit flexibility, are preferred.
  • the resin material is a tetrafluoroethylene polymer other than the F polymer.
  • the content thereof is preferably 40% by mass or less with respect to the entire liquid composition.
  • the dispersion liquid produced by this method has a thixotropic agent, a viscosity modifier, a defoaming agent, a dehydrating agent, a plasticizer, a weather resistant agent, and an oxidation, as long as the effects of the present invention are not impaired.
  • Other components such as inhibitors, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, flame retardants, and various fillers may be further contained.
  • the D50 of the composite particles (main particles) present in the present dispersion is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
  • the D50 of the particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 3 ⁇ m or more.
  • the D90 of the present particles is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • an F polymer particle (F powder) is used as a core, and an inorganic filler is attached to the surface of the core (hereinafter, “Aspect I”). Also referred to as), there is an embodiment in which an inorganic filler is used as a core and F powder is adhered to the surface of the core (hereinafter, also referred to as “Aspect II”), and the particles of Aspect I are preferable.
  • the "core” means a core (central part) necessary for forming the particle shape of the composite particle, and does not mean the main component in the composition of the composite particle.
  • the deposit (inorganic filler or F powder) adhering to the surface of the core may be adhered only to a part of the surface of the core, or may be attached 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 such composite particles are formed from the core and the shell covering the core. It can be said that it has a core-shell structure.
  • an inorganic filler having a hardness higher than that of the F polymer and having high dispersion stability is exposed on the surface.
  • the F polymer is less likely to be denatured, and the fluidity of the composite particles and their handleability are likely to be improved.
  • the dispersion stability of the composite particles tends to increase.
  • the core of the F powder and the inorganic filler are preferably in the form of particles, respectively.
  • the core of the F powder may be composed of a single particle of the F powder or an aggregate of the F powder.
  • the D50 of the F powder is set to be larger than the D50 of the particles of the inorganic filler, and the amount of the F powder is set to be larger than the amount of the particles of the inorganic filler. If the dispersion liquid is produced by the method of the present invention with such a relationship set, it is easy to obtain the composite particles of the aspect I.
  • the D50 of the particles of the inorganic filler is preferably 0.0001 to 0.5, more preferably 0.01 to 0.3, based on the D50 of the F powder. Specifically, it is preferable that the D50 of the F powder is more than 1 ⁇ m and the D50 of the particles of the inorganic filler is 0.1 ⁇ m or less.
  • the amount of particles of the inorganic filler 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 F powder.
  • 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 powder is larger than the D50 of the particles of the inorganic filler, and the mass of the F polymer occupying the same is larger than the mass of the inorganic filler.
  • the surface of the core of the F powder is covered with a larger amount of particles of the inorganic filler, and the composite particles of the aspect I have a core-shell structure.
  • the aggregation of the F powder particles is suppressed, and it is easy to obtain composite particles (main particles) in which the particles of the inorganic filler are attached to the core composed of the single F powder particles.
  • the inorganic filler is preferably spherical particles, more preferably substantially spherical particles.
  • the dispersibility stability of the obtained composite particles tends to increase.
  • 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 "sphere" includes not only a true sphere but also a slightly distorted sphere.
  • the inorganic filler 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 likely to be expressed in a well-balanced manner.
  • the average particle size (D50) of the particles of the inorganic filler is preferably in the range of 0.001 to 0.3 ⁇ m, more preferably 0.005 to 0.2 ⁇ m, still more preferably 0.01 to 0.1 ⁇ m.
  • the average particle size (D50) is within such a range, the handleability and fluidity of the composite particles are likely to be improved, and the dispersion stability is likely to be improved.
  • the particle size distribution of the particles of the inorganic filler is preferably 3 or less, and 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. In such a case, it is easy to control the fluidity of the obtained composite particles.
  • the surface of the particles of the inorganic filler is surface-treated, and it is more preferable that the particles are surface-treated with a silazane compound such as hexamethyldisilazane, a silane coupling agent, or the like.
  • a silazane compound such as hexamethyldisilazane
  • a silane coupling agent such as hexamethyldisilazane
  • silane coupling agent include the above-mentioned compounds.
  • one kind of inorganic filler particles may be used, or two or more kinds of particles may be mixed and used.
  • the average particle diameter of each inorganic filler may be different from each other, and the mass ratio of the content of each inorganic filler can be appropriately set according to the desired function.
  • the D50 of the core of the F powder is preferably 0.1 ⁇ m or more, more preferably more than 1 ⁇ m.
  • the upper limit is preferably 100 ⁇ m, more preferably 50 ⁇ m, and even more preferably 10 ⁇ m.
  • the D50 of the particles of the inorganic filler is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more.
  • the upper limit is preferably 1 ⁇ m, more preferably 0.1 ⁇ m.
  • the ratio of the F polymer to the composite particles of the aspect I is preferably 50 to 99% by mass, more preferably 75 to 99% by mass.
  • the proportion of the inorganic filler is preferably 1 to 50% by mass, more preferably 1 to 25% by mass.
  • the composite particles of Aspect I may be further surface-treated depending on the physical properties of the inorganic filler adhering to the surface.
  • Specific examples of such surface treatment include a method of surface-treating the composite particles of Embodiment I 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 composite particles are dispersed with the siloxanes or the silane coupling agent, reacting the siloxanes or the silane coupling agent, and recovering the composite particles.
  • the silane coupling agent the above-mentioned silane coupling agent having a functional group is preferable. According to such a method, the surface physical characteristics of the composite particles can be further adjusted.
  • the core of the inorganic filler is preferably in the form of particles.
  • the surface of the core of the inorganic filler is easily covered with the F powder.
  • the core of the inorganic filler may be composed of a single particle of the inorganic filler or may be composed of an aggregate of the inorganic filler.
  • the D50 of the particles of the inorganic filler is preferably 0.0001 to 0.5, more preferably 0.01 to 0.3, based on the D50 of the particles of the inorganic filler.
  • the amount of F powder is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the particles of the inorganic filler.
  • the upper limit is preferably 50 parts by mass, more preferably 10 parts by mass.
  • the D50 of the core of the inorganic filler is preferably 0.1 ⁇ m or more, more preferably more than 1 ⁇ m.
  • the upper limit is preferably 30 ⁇ m, more preferably 10 ⁇ m.
  • the proportion of the inorganic filler in the composite particles of Embodiment II 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 means for removing the dispersion medium from the dispersion liquid and isolating the particles it is preferable to use heating, depressurization or filtration. These means may be used in combination as appropriate.
  • Specific examples of the means for isolating the particles include (1) distilling off the dispersion medium under atmospheric pressure or reduced pressure to concentrate, filtering and drying as necessary; (2) controlling the temperature of the dispersion. While the particles are agglomerated, or after coagulation / crystallization by adding an electrolyte, a coagulant, a coagulation aid, etc., they are separated and dried by filtration or the like; (3) The dispersion medium can volatilize the dispersion.
  • the dispersion is centrifuged and then dried.
  • the drying means include vacuum drying, high frequency drying, and hot air drying.
  • the dispersion may be diluted with a dispersion medium to adjust the total content of the F polymer and the inorganic filler in the dispersion in advance.
  • a method in which the dispersion liquid is frozen and then the dispersion medium is preferably sublimated and removed under a reduced pressure atmosphere to obtain the composite particles is more preferable.
  • Freezing is preferably performed at a temperature lower than 0 ° C. Specifically, it is preferable to expose the dispersion liquid to an atmosphere at a temperature equal to or lower than the melting point of the dispersion medium used, for example, ⁇ 100 to ⁇ 10 ° C., and freeze it. Freezing is preferably completed within 8 hours from the viewpoint of suppressing the sedimentation of the components of the dispersion liquid. Further, from the viewpoint of suppressing non-uniformity of the frozen product due to rapid freezing, it is preferable to freeze the dispersion liquid for 10 minutes or more.
  • the removal of the dispersion medium from the frozen dispersion (frozen product) by sublimation may be performed under conditions in which the dispersion is suppressed from melting.
  • the temperature at which the dispersion medium is sublimated is preferably less than 0 ° C., specifically, the frozen product is preferably exposed to an atmosphere of ⁇ 100 to 0 ° C.
  • the pressure for sublimation is usually a reduced pressure atmosphere, preferably a reduced pressure atmosphere of 0 to 1 ⁇ 10 2 Pa.
  • the time for sublimating the dispersion medium is usually 4 to 72 hours. Examples of the device used for sublimation include a centrifuge, a shelf dryer and the like.
  • examples of the electrolyte include inorganic salts such as potassium nitrate, sodium nitrate, sodium carbonate, and sodium hydrogen carbonate.
  • examples of the coagulant or coagulation aid include nitrate, hydrochloric acid, sulfuric acid, magnesium chloride, calcium chloride, sodium chloride, aluminum sulfate, magnesium sulfate and barium sulfate.
  • the dispersion liquid may be agitated at the time of coagulation / crystallization to adjust the polymer content and pH of the dispersion liquid, or a pH adjuster and an organic solvent may be added to the dispersion liquid.
  • Examples of the pH adjusting agent include sodium carbonate, sodium hydrogencarbonate, ammonia, ammonium salts, and urea.
  • Examples of the organic solvent include alcohol and acetone.
  • the above means (3) is preferably performed by spraying the dispersion liquid in an atmosphere at a temperature at which the dispersion medium sufficiently volatilizes.
  • a method of spraying the dispersion liquid vertically on a system in which an inert gas such as nitrogen gas having a temperature of more than 100 ° C. is circulated above the vertical direction and drying the mixture is preferable.
  • An apparatus such as a crystallization tower can be used for such a method.
  • the particles can be stably dispersed even if a large amount is added to the liquid dispersion medium. Further, in the molded product (polymer layer, film, etc.) formed from the liquid composition, the F polymer and the inorganic filler are more uniformly distributed, and the physical properties (electrical characteristics, adhesiveness, etc.) of the F polymer and the inorganic filler are obtained. (Low line swelling, etc.) is highly likely to occur.
  • the viscosity of the dispersion liquid produced by this method is preferably 50 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more, further preferably 5000 mPa ⁇ s or more, and particularly preferably 10,000 mPa ⁇ s or more.
  • the viscosity of this dispersion is preferably 100,000 mPa ⁇ s or less, more preferably 50,000 mPa ⁇ s or less, and even more preferably 20,000 mPa ⁇ s or less.
  • the present dispersion has excellent coatability and easily forms a molded product (polymer layer or the like) having an arbitrary thickness.
  • the inorganic filler is less likely to aggregate and is easily uniformly distributed in the molded product formed from the dispersion, so that the physical characteristics of the F polymer and the inorganic filler are different. It is highly balanced and easy to develop.
  • the viscosity of the dispersion liquid produced by this method is preferably 50 mPa ⁇ s or more, and more preferably 100 mPa ⁇ s or more.
  • the viscosity of this dispersion is preferably 100,000 mPa ⁇ s or less, more preferably 10,000 mPa ⁇ s, and even more preferably 1000 mPa ⁇ s or less.
  • the present dispersion is preferable because it has excellent dispersion stability.
  • the inorganic filler is a non-spherical anisotropic filler, its dispersion stability is more likely to be improved by the above-mentioned mechanism of action.
  • the inorganic filler tends to be randomly oriented and the physical properties tend to be the same regardless of the direction. For example, it is easy to obtain a layer or film whose mechanical strength and electrical characteristics are equivalent in the plane direction and the vertical direction of the layer or film.
  • the viscosity of this dispersion may be adjusted by further mixing a liquid dispersion medium after shearing treatment.
  • the thixotropic ratio of the dispersion liquid produced by this method is preferably 1.0 or more.
  • the thixotropic ratio of this dispersion is preferably 3.0 or less, more preferably 2.0 or less.
  • the present dispersion is excellent in coatability and homogeneity, and it is easy to form a more dense molded product (polymer layer or the like).
  • the total content of the F powder and the inorganic filler in the present dispersion is preferably 40% by mass or more, more preferably 50 to 80% by mass, based on the total mass of the present dispersion.
  • the dispersion stability is improved, and the F powder and the inorganic filler can be contained in the dispersion liquid at a high concentration. Therefore, a molded product such as a coating film can be formed from the dispersion liquid with high uniformity, and the physical characteristics of the F polymer and the physical characteristics of the inorganic filler can be easily expressed in a highly balanced manner.
  • the component sedimentation rate is preferably 60% or more, preferably 70% or more, and more preferably 80% or more.
  • the dispersion liquid produced by this method is applied to the surface of the sheet base material layer to form a liquid film, and the liquid film is heated to remove the dispersion medium to form a dry film, and the dry film is further heated. Then, by firing the F polymer, a laminate having a polymer layer containing the F polymer and an inorganic filler (hereinafter, also referred to as “F layer”) on the surface of the sheet base material layer can be obtained.
  • F layer inorganic filler
  • a metal substrate copper, nickel, aluminum, titanium, metal foil such as an alloy thereof, etc.
  • a heat-resistant resin film polyimide, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, etc.
  • a film containing one or more of heat-resistant resins such as polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, and liquid crystal polyester amide, which may be a single-layer film or a multilayer film).
  • Prepreg precursor of fiber reinforced resin substrate
  • any method may be used as long as a stable liquid film (wet film) composed of the present dispersion liquid is formed on the surface of the sheet base material, and the coating method and droplets are used. Examples thereof include a discharge method and a dipping method, and a coating method is preferable. If the coating method is used, a liquid film can be efficiently formed on the surface of the base material with simple equipment.
  • the coating methods include spray method, roll coat method, spin coat method, gravure coat method, micro gravure coat method, gravure offset method, knife coat method, kiss coat method, bar coat method, die coat method, fountain Mayer bar method, and slot die coat. The law is mentioned.
  • the liquid film is heated at a temperature at which the dispersion medium volatilizes to form a dry film on the surface of the sheet substrate.
  • the heating temperature is preferably + 50 ° C. or lower, the boiling point of the dispersion medium, more preferably 50 ° C. or lower, and further preferably ⁇ 50 ° C. or lower.
  • the drying temperature is preferably 120 ° C to 200 ° C. Air may be blown in the step of removing the dispersion medium.
  • the dispersion medium does not necessarily have to be completely volatilized, and may be volatilized to the extent that the layer shape after holding is stable and the self-supporting film can be maintained.
  • the heating temperature is preferably 380 ° C. or lower, more preferably 350 ° C. or lower.
  • 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.
  • the heating may be performed under normal pressure or reduced pressure.
  • the heating atmosphere may be any of an oxidizing gas atmosphere (oxygen gas, etc.), a reducing gas atmosphere (hydrogen gas, etc.), and an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.). ..
  • the heating time is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes.
  • the thickness of the F layer is preferably 0.1 to 150 ⁇ m. Specifically, when the sheet base material layer is a metal foil, the thickness of the F layer is preferably 1 to 30 ⁇ m. When the sheet base material layer is a heat-resistant resin film, the thickness of the F layer is preferably 1 to 150 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the peel strength between the F layer and the base material layer is preferably 10 N / cm or more, more preferably 15 N / cm or more. The peel strength is preferably 100 N / cm or less.
  • the porosity of the F layer is preferably 30% or less, more preferably 20% or less.
  • the porosity is preferably 0.1% or more, more preferably 1% or more. From this dispersion, it is easy to form an F layer with a low porosity. In particular, even when the porosity of the dry film is 1% or more, it is easy to form an F layer having a low porosity.
  • the void ratio is determined by image processing to determine the void portion of the F layer from the SEM photograph of the cross section of the molded product observed using a scanning electron microscope (SEM), and the area occupied by the void portion is the area occupied by the F layer. It is the ratio (%) divided by the area. The area occupied by the void portion is obtained by approximating the void portion to a circle.
  • the present dispersion may be applied only to one surface of the sheet base material layer, or may be applied to both sides of the sheet base material layer.
  • a laminated body having an F layer on one surface of the sheet base material layer and the sheet base material layer is obtained, and in the latter, the F layer is provided on both the surfaces of the sheet base material layer and the sheet base material layer.
  • a laminate is obtained. Since the latter laminated body is less likely to warp, it is excellent in handleability during its processing.
  • Specific examples of such a laminate include a metal foil, a metal-clad laminate having an F layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having an F 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.
  • As the release layer a metal layer containing nickel or chromium or a multilayer metal layer in which the metal layers are laminated is preferable.
  • the metal leaf with a carrier examples include the trade name "FUTF-5DAF-2" manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd.
  • the ten-point average roughness of the surface of the sheet base material layer is preferably 0.01 to 0.05 ⁇ m. Since the particles are easy to pack densely, a laminated body having excellent peel strength can be formed even if the surface of the sheet base material layer is smooth.
  • the outermost surface of the sheet material may be further surface-treated in order to further improve its low linear expansion property and 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, noble 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.
  • 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 (tow, woven fabric, 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, and examples of the heat-resistant resin include the above-mentioned resins.
  • the laminating method examples 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. Since such a laminate has an F layer having excellent electrical characteristics, it is suitable as a printed circuit board material, and specifically, it can be used as a flexible metal-clad laminate or a rigid metal-clad laminate for manufacturing a printed circuit board, and is particularly flexible. It can be suitably used for manufacturing a flexible printed circuit board as a metal-clad laminate.
  • a printed circuit board is obtained by etching a metal foil of a laminate (metal foil with an F layer) in which the sheet 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 an F layer has a transmission circuit formed from the metal foil and an F layer in this order.
  • the configuration of the printed circuit board includes a transmission circuit / F layer / prepreg layer and a transmission circuit / F layer / prepreg layer / F 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 with the present dispersion.
  • the laminate of the F layer and other base materials is useful as antenna parts, printed substrates, aircraft parts, automobile parts, sports equipment, food industry supplies, paints, cosmetics, etc., and specifically, wire coating.
  • Materials aircraft wires, etc.
  • electrical insulating tapes insulating tapes for oil drilling, materials for printed substrates, separation membranes (precision filtration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes) Etc.), electrode binders (for lithium secondary batteries, fuel cells, etc.), copy rolls, furniture, automobile dashboards, covers for home appliances, sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, etc.) , Belt conveyor, food transport belt, etc.), tools (shovel, razor, cut, saw, etc.), boiler, hopper, pipe, oven, baking mold, chute, die, toilet bowl, container covering material.
  • the present dispersion having excellent dispersibility and dispersion stability can be obtained. Further, when the dispersion medium is removed from the present dispersion liquid, composite particles containing F powder and an inorganic filler and having excellent dispersibility and dispersion stability can be obtained. Such composite particles can be effectively used as additives and modifiers for various varnishes (resist, ink, paint, etc.) and can impart physical properties of F polymer.
  • the present invention is not limited to the configuration of the above-described embodiment.
  • this method may additionally have any other step in the configuration of the above embodiment, or may be replaced with any step that produces the same action.
  • the dispersion liquid and the particles may be added to any other configuration or may be replaced with any configuration exhibiting the same function in the configuration of the above embodiment.
  • F powder 1 A polymer having an acid anhydride group containing 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE unit, NAH unit, and PPVE unit in this order (melting temperature 300 ° C., acid anhydride).
  • F powder-2 Particles (average particle diameter 2 ⁇ m, bulk) composed of a functional group-free polymer (melting temperature 305 ° C.) containing 97.5 mol% and 2.5 mol% of TFE units and NAH units in this order.
  • F powder 3 Particles composed of PTFE having a number average molecular weight of 20,000 (average particle diameter 0.3 ⁇ m, bulk density 0.2 g / m 2 )
  • Filler 1 Silica filler (substantially spherical, average particle diameter 0.4 ⁇ m), surface treated with silane coupling agent
  • Filler 2 Silica filler (substantially spherical, average particle diameter 5 ⁇ m), surface treated with silane coupling agent Treated filler 3: Borone nitride filler (scaly, average particle size 8 ⁇ m)
  • Filler 4 Boron nitride filler (scaly, average particle size 4 ⁇ m)
  • Filler 5 Silica filler (substantially spherical, average particle diameter 0.03 ⁇ m), surface-treated with silane coupling agent
  • Filler 6 Silica filler (substantially spherical, average particle diameter 0.4 ⁇ m), silane coupling agent
  • Example 1-1 Production and evaluation of dispersion (1)
  • NMP and varnish 1 were added to a tank equipped with a stirring blade, and the inside of the tank was sufficiently stirred.
  • F powder 1 was added to the tank and stirred for 10 minutes to prepare a liquid composition (F powder content: 33% by mass) in which F powder 1 was dispersed.
  • the filler 1 is added, the inside of the tank is stirred at 800 rpm for 15 minutes, and the shearing treatment is performed in a state where an ascending flow is formed.
  • a dispersion 1 containing (1 part by mass as PI1) and NMP (59 parts by mass) was obtained.
  • the viscosity of the obtained dispersion liquid 1 was 400 mPa ⁇ s, and the viscosity did not increase even when stirred at 500 rpm for 72 hours with a ball mill, and the component sedimentation rate was evaluated according to the following, and the result was “ ⁇ ”. .. ⁇ Evaluation criteria for component sedimentation rate> ⁇ : The erythrocyte sedimentation rate is 60% or more. ⁇ : The erythrocyte sedimentation rate is more than 40% and 60% or less. X: The erythrocyte sedimentation rate is 40% or less.
  • the erythrocyte sedimentation rate of the composite particles 1 was " ⁇ " as a result of preparing a liquid composition containing the composite particles 1 (40 parts by mass) and NMP (60 parts by mass) and evaluating the same as the above component sedimentation rate. rice field.
  • Example 1-2 to Example 1-8 Dispersions 2 to 8 and composite particles 2 to 8 were obtained in the same manner as in Example 1-1, except that the type and amount of each component were changed as shown in Table 1 below.
  • Example 1-7 the stirring speed in the shearing treatment was increased to adjust the viscosity of the obtained dispersion.
  • Example 1-8 in addition to NMP and varnish 1, the filler 5 was also stirred in a tank in advance, and F powder 1 was added thereto to produce a dispersion liquid.
  • Table 1 shows the evaluation results of the obtained dispersion liquid and composite particles.
  • Example 2-1 The dispersion liquid 1 was applied to the surface of a long copper foil (thickness 18 ⁇ m) using a bar coater to form a wet film. Next, the metal foil on which the wet film was formed was passed through a drying oven at 110 ° C. for 5 minutes and dried by heating to obtain a dry film. Then, the dry membrane was heated at 380 ° C. for 3 minutes in a nitrogen oven. As a result, a laminate 1 having a metal foil and a polymer layer (thickness 20 ⁇ m) as a molded product containing a melt-fired product of F powder 1 and filler 1 and PI1 on the surface thereof was produced.
  • the cross section of the laminated body 1 was observed using a scanning electron microscope (SEM), and the porosity was evaluated according to the following criteria.
  • ⁇ Electrical characteristics> A rectangular test piece having a length of 100 mm and a width of 50 mm was cut out from the laminate 1 and etched with an aqueous ferric chloride solution to remove the copper foil to obtain a single polymer layer. After holding the polymer layer alone in an atmosphere of 85 ° C. and 85% relative humidity for 72 hours, the dielectric loss tangent (measurement frequency: 10 GHz) of the polymer layer was measured by the SPDR (split post dielectric resonance) method. It was evaluated according to the criteria of. [Evaluation criteria for electrical characteristics after water absorption] ⁇ : The dielectric loss tangent is less than 0.0020. ⁇ : The dielectric loss tangent is 0.0020 or more and 0.0040 or less. X: The dielectric loss tangent is more than 0.0040.
  • ⁇ Linear expansion coefficient> The copper foil of the laminate 1 was removed by etching with an aqueous solution of ferric chloride to prepare a single polymer layer. A 180 mm square test piece is cut out from the prepared polymer layer, and the linear expansion coefficient of the test piece is measured in the range of 25 ° C. or higher and 260 ° C. or lower according to the measurement method specified in JIS C 6471: 1995, and the following criteria are used. Evaluated according to. [Evaluation criteria for coefficient of linear expansion] ⁇ : 50 ppm / ° C or less. ⁇ : More than 50 ppm / ° C. and 75 ppm / ° C. or less. X: Over 75 ppm / ° C.
  • Laminates 2 to 7 were obtained in the same manner as in Example 2-1 except that the dispersions 2 to 7 were used respectively. Table 2 shows the evaluation results for each laminated body.
  • a liquid composition containing the obtained F powder 1 (35 parts by mass), filler 1 (40 parts by mass), varnish 1 (1 part by mass as PI1) and NMP (remaining portion) was prepared, and further NMP was added to the dispersion liquid. 31 (viscosity: 300 mPa ⁇ s) was obtained. A few drops of the dispersion liquid 31 were dropped onto a glass substrate and air-dried at 120 ° C. for 5 minutes to obtain composite particles 31 (D50: 8 ⁇ m) having F powder 1 as a core and filler 1 as a shell.
  • Example 3-2 A dispersion liquid 32 was obtained in the same manner as in Example 3-1 except that the agent 1 was further added so as to be 1% by mass with respect to the content of the F powder 1. Further, composite particles 32 (D50: 8 ⁇ m) were obtained in the same manner as in Example 3-1 except that the dispersion liquid 31 was changed to the dispersion liquid 32.
  • Example 3-3 Dispersion is performed in the same manner as in Example 3-1 except that the increase in the liquid temperature in the tank due to the shearing treatment of Example 3-1 is not controlled and the liquid temperature in the tank during the shearing treatment temporarily exceeds 50 ° C. Liquid 33 was obtained.
  • the composite particles 33 were obtained in the same manner as in Example 3-1 except that the dispersion liquid 31 was changed to the dispersion liquid 33.
  • the dispersion liquid 34 was obtained in the same manner as in Example 3-1 except that the stirring in the shearing treatment was strengthened and the viscosity of the liquid in the tank during the shearing treatment exceeded 10,000 mPa ⁇ s. Further, the composite particles 34 were obtained in the same manner as in Example 3-1 except that the dispersion liquid 31 was changed to the dispersion liquid 34.
  • the dispersion liquid 35 was obtained in the same manner as in Example 3-1 except that the filler 1 was changed to the filler 6. Further, the composite particles 35 were obtained in the same manner as in Example 3-1 except that the dispersion liquid 31 was changed to the dispersion liquid 35.
  • Example 1-1 For each of the obtained dispersions 31 to 35, the dispersion stability and the erythrocyte sedimentation rate were evaluated in the same manner as in “Example 1-1". With respect to the composite particles 31 and the composite particles 32, the erythrocyte sedimentation rate was evaluated in the same manner as in “Example 1-1". The results are shown in Table 3.
  • Part 2 Manufacture and evaluation of laminate (Part 2)
  • the laminated body 31 and the laminated body 32 were obtained in the same manner as in Example 2-1 except that the dispersion liquid 1 was changed to the dispersion liquid 31 and the dispersion liquid 32, respectively.
  • the laminated body 32 as compared with the laminated body 31, powder falling of the inorganic filler was suppressed at the end portion and the curved surface portion of the polymer layer.
  • the dispersion liquid produced by the method of the present invention has excellent dispersion stability and can be easily processed into a film, a fiber reinforced film, a prepreg, and a metal laminated plate (metal foil with resin).
  • the obtained processed article can be used as a material for antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry goods, sliding bearings and the like.
  • the composite particles obtained from the dispersion liquid can be effectively used as additives and modifiers for various varnishes (resist, ink, paint, etc.).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir : un procédé de production d'une dispersion contenant des particules d'un polymère à base de tétrafluoroéthylène, ayant une excellente stabilité de dispersion ; et un procédé de production de particules composites obtenues à partir de ladite dispersion. La solution selon l'invention consiste en un procédé de production d'une dispersion impliquant la mise en oeuvre d'un traitement de cisaillement sur une composition liquide contenant des particules d'un polymère à base de tétrafluoroéthylène thermofusible, une charge d'un composé inorganique, et un milieu de dispersion polaire liquide, pour obtenir une dispersion contenant le polymère à base de tétrafluoroéthylène, la charge du composé inorganique et le milieu de dispersion liquide.
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WO2023234377A1 (fr) * 2022-06-03 2023-12-07 Ａｇｃ株式会社 Substrat stratifié allongé, rouleau de feuille allongé, et procédés de fabrication associés
WO2024053554A1 (fr) * 2022-09-09 2024-03-14 Ａｇｃ株式会社 Composition liquide et procédé de production d'un stratifié utilisant la composition liquide

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WO2018016644A1 (fr) * 2016-07-22 2018-01-25 旭硝子株式会社 Composition liquide, procédé de fabrication de film et corps stratifié utilisant ladite composition liquide
WO2020071381A1 (fr) * 2018-10-03 2020-04-09 Ａｇｃ株式会社 Dispersion
WO2020090607A1 (fr) * 2018-10-30 2020-05-07 Ａｇｃ株式会社 Dispersion

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JP2020037662A (ja) * 2018-09-05 2020-03-12 Ａｇｃ株式会社 フッ素樹脂膜、分散液の製造方法およびフッ素樹脂膜付基材の製造方法

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WO2018016644A1 (fr) * 2016-07-22 2018-01-25 旭硝子株式会社 Composition liquide, procédé de fabrication de film et corps stratifié utilisant ladite composition liquide
WO2020071381A1 (fr) * 2018-10-03 2020-04-09 Ａｇｃ株式会社 Dispersion
WO2020090607A1 (fr) * 2018-10-30 2020-05-07 Ａｇｃ株式会社 Dispersion

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023234377A1 (fr) * 2022-06-03 2023-12-07 Ａｇｃ株式会社 Substrat stratifié allongé, rouleau de feuille allongé, et procédés de fabrication associés
WO2024053554A1 (fr) * 2022-09-09 2024-03-14 Ａｇｃ株式会社 Composition liquide et procédé de production d'un stratifié utilisant la composition liquide

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