WO2022092036A1 - Composition including powder particles of tetrafluoroethylene polymer, method for producing same, method for producing dispersion from said composition - Google Patents

Composition including powder particles of tetrafluoroethylene polymer, method for producing same, method for producing dispersion from said composition Download PDF

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WO2022092036A1
WO2022092036A1 PCT/JP2021/039342 JP2021039342W WO2022092036A1 WO 2022092036 A1 WO2022092036 A1 WO 2022092036A1 JP 2021039342 W JP2021039342 W JP 2021039342W WO 2022092036 A1 WO2022092036 A1 WO 2022092036A1
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polymer
composition
liquid medium
powder
particles
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PCT/JP2021/039342
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French (fr)
Japanese (ja)
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創太 結城
敦美 光永
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Ａｇｃ株式会社
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Priority to CN202180072602.6A priority Critical patent/CN116348534A/en
Priority to JP2022559131A priority patent/JPWO2022092036A1/ja
Priority to KR1020237008947A priority patent/KR20230096971A/en
Publication of WO2022092036A1 publication Critical patent/WO2022092036A1/en

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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
    • 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
    • C08J3/124—Treatment for improving the free-flowing characteristics
    • 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
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present invention comprises a high-viscosity composition containing powder particles of a tetrafluoroethylene-based polymer and a liquid medium, a method for producing such a high-viscosity composition, and tetrafluoroethylene-based polymer particles dispersed from the high-viscosity composition.
  • the present invention relates to a method for producing the resulting dispersion.
  • the tetrafluoroethylene polymer is excellent in physical properties such as electrical insulation, water repellency, oil repellency, chemical resistance, and heat resistance. Therefore, the dispersion liquid in which the powder is dispersed in water or an oil-based solvent is useful as a material for forming a resist, an adhesive, an electrically insulating layer, a lubricant, an ink, a paint, and the like.
  • the tetrafluoroethylene polymer has a low surface energy, and the particles constituting the powder (hereinafter, also referred to as “powder particles”) tend to aggregate with each other. Therefore, it is difficult to obtain a low-viscosity dispersion having excellent dispersion stability.
  • Patent Document 1 discloses a non-aqueous dispersion liquid using an additive from the viewpoint of improving the dispersibility of the dispersion liquid and adjusting the physical characteristics of the dispersion liquid.
  • the dispersion liquid described in Patent Document 1 is not yet sufficient in terms of dispersion stability.
  • foaming becomes intense during the preparation of the dispersion, and dispersion stability may decrease due to aggregation.
  • the surface smoothness of the coating film or molded product obtained from such a dispersion liquid may be deteriorated.
  • the present inventors have studied a method for producing such a dispersion in order to obtain a dispersion having excellent dispersion stability of the powder particles from a tetrafluoroethylene polymer powder having a small specific surface area, and have completed the present invention. rice field.
  • the dispersion liquid containing the powder particles of the tetrafluoroethylene-based polymer and further containing other functional materials is a coating film or molded product formed from the dispersion liquid.
  • other functional materials inorganic filler, polymer or resin different from the tetrafluoroethylene-based polymer, etc.
  • the physical properties of other functional materials can be imparted.
  • the affinity between the tetrafluoroethylene polymer and other functional materials is generally low, and the dispersion stability tends to be further lowered in such a dispersion.
  • An object of the present invention is to provide a highly viscous composition such as a paste which is a precursor of a dispersion liquid, which contains powder particles of a tetrafluoroethylene polymer and a liquid medium, and a method for producing the same. Further, the present invention comprises a powder particle of a tetrafluoroethylene polymer, a polar polymer, and a liquid medium having a polarity, and a more highly viscous composition such as a wet powder which is a precursor of a dispersion liquid, and a method for producing the same. The purpose is to provide.
  • an object of the present invention is to provide a dispersion having excellent dispersion stability, which comprises diluting the highly viscous composition with a liquid medium to produce a dispersion in which powder particles of a tetrafluoroethylene polymer are dispersed. do.
  • the present invention has the following aspects.
  • [1] Contains particles and a liquid medium derived from a tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less, a solid content concentration of 40% by mass or more, a temperature of 25 ° C., and a rotation speed.
  • the composition of [1] which further contains a polymer or resin other than the tetrafluoroethylene polymer, which is soluble in the liquid medium.
  • a composition comprising, having a viscosity of 10,000 to 100,000 Pa ⁇ s as measured by a capillograph with a temperature of 25 ° C. and a shear rate of 1 s -1 .
  • the total content of the particles and the content of the polar polymer or its precursor is more than 50% by mass, the content of the liquid medium having the polarity is 40% by mass or less, and the content of the particles is The composition of [3], wherein the ratio of the content of the polar polymer or its precursor to the amount is 0.001 or more and less than 0.5.
  • the composition of [3] or [4], wherein the polar polymer or its precursor is an imide-based polymer, a precursor of an imide-based polymer, a vinyl-based polymer or a polysaccharide.
  • composition according to any one of [1] to [6], wherein the tetrafluoroethylene polymer is a polymer having a carbonyl group-containing group or a hydroxyl group-containing group.
  • the tetrafluoroethylene polymer has a fluorine content of 70% by mass or more.
  • the tetrafluoroethylene polymer has a melting temperature of 180 to 325 ° C.
  • a mixture containing particles derived from a tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less and a liquid medium is kneaded, and degassing during or after kneading and static after kneading are performed.
  • a method for producing a composition wherein the composition according to any one of [1] to [11] is produced by performing at least one of the settings.
  • the production method of [12], wherein both the degassing and the standing still are performed.
  • a method for producing a dispersion liquid wherein the composition according to any one of [1] to [11] is diluted with a second liquid medium to obtain a dispersion liquid.
  • a wet powder comprising a precursor and a liquid medium having at least one polarity selected from the group consisting of amides, ketones and esters.
  • a dispersion liquid containing particles derived from a tetrafluoroethylene polymer powder having a small specific surface area and having excellent dispersion stability can be produced.
  • the dispersion liquid obtained by such a production method the obtained coating film or molded product has an appearance having excellent surface smoothness.
  • the "tetrafluoroethylene-based polymer” is a polymer containing a unit (hereinafter, also referred to as TFE unit) based on tetrafluoroethylene (hereinafter, also referred to as TFE).
  • TFE unit a unit based on tetrafluoroethylene
  • TFE tetrafluoroethylene
  • the "glass transition point (Tg) of the polymer” is a value measured by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method.
  • DMA dynamic viscoelasticity measurement
  • the “polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
  • D50 is the average particle size of the particles constituting the measurement object such as powder or an inorganic filler, and is the volume-based cumulative 50% diameter of the particles constituting the measurement object obtained by the laser diffraction / scattering method. That is, the particle size distribution of the particles constituting the object to be measured is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the object to be measured as 100%, and the cumulative volume is 50% on the cumulative curve. Particle size. “D90” is the cumulative volume particle diameter of the particles constituting the measurement object, and is the volume-based cumulative 90% diameter of the particles obtained in the same manner as in “D50”.
  • Viscosity measured by capillary graph is a viscosity measured by using a capillary having a capillary length of 10 mm and a capillary radius of 1 mm, a furnace body diameter of 9.55 mm, and a load cell capacity of 2 tons.
  • the "viscosity measured by the B-type viscometer” is a value measured by using a B-type viscometer under the condition of a room temperature (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 "tixo ratio" is obtained by measuring the viscosity ⁇ 1 obtained by measuring the viscosity ⁇ 1 at room temperature (25 ° C.) at a rotation speed of 30 rpm using a B-type viscometer under the condition of a rotation speed of 60 rpm. It is a value ( ⁇ 1 / ⁇ 2 ) calculated by dividing by the viscosity ⁇ 2 .
  • a "monomer-based unit" in a polymer is an atomic group formed directly from one molecule of a monomer by polymerization, and an atomic group obtained by processing a part of the atomic group into another structure. Means.
  • the unit based on the monomer a is also simply referred to as “monomer a unit”.
  • the tetrafluoroethylene polymer in the present invention is also referred to as “F polymer”.
  • the powder of F polymer having a specific surface area of 25 m 2 / g or less is also referred to as “this powder”.
  • the liquid medium having polarity is also referred to as “liquid polar medium”.
  • compositions of the present invention contains particles derived from the present powder and a liquid medium, has a solid content concentration of 40% by mass or more, is measured with a B-type viscometer at a temperature of 25 ° C. and a rotation speed of 30 rpm. It is a composition having a viscosity (hereinafter, simply referred to as "viscosity measured by a B-type viscometer") of 8000 to 100,000 mPa ⁇ s.
  • the composition of the present invention is referred to as "the present composition (1)”.
  • the other one of the compositions of the present invention comprises particles derived from the powder, a polar polymer or precursor thereof, and a liquid polar medium and has a viscosity as measured by a capillograph with a shear rate of 1s -1 (hereinafter, simply "". It is a composition having a viscosity (referred to as viscosity measured by capillograph measurement) of 10,000 to 100,000 Pa ⁇ s.
  • the composition of the present invention is referred to as "the present composition (2)”.
  • the present composition (1) and the present composition (2) are collectively referred to as "the present composition”.
  • the present composition is suitable as an intermediate for obtaining a dispersion liquid in which particles derived from the present powder are dispersed in a liquid medium.
  • Such a dispersion can be obtained by diluting the composition with a liquid medium.
  • the liquid medium in the composition is also referred to as a "first liquid medium", if necessary, in order to distinguish it from the second liquid medium used for diluting the composition.
  • first liquid medium the F polymer, the present powder, the liquid medium, the polar polymer and the precursor thereof related to the present composition.
  • the F polymer in the present composition is a polymer containing a unit (hereinafter, also referred to as “TFE unit”) based on tetrafluoroethylene (hereinafter, also referred to as “TFE”).
  • TFE unit a unit based on tetrafluoroethylene
  • the fluorine content of the F polymer is preferably 70% by mass or more.
  • the F polymer having a high fluorine content is excellent in physical properties such as electrical properties of the F polymer, but has a remarkably low affinity with a liquid medium. Therefore, the dispersibility of the particles of the F polymer is further lowered.
  • the present composition even in the dispersion liquid of the particles of the F polymer obtained by using the same composition, the physical characteristics of the entire F polymer are not impaired, and a dispersion liquid having excellent dispersibility can be obtained.
  • the fluorine content of the F polymer is preferably 76% by mass or less.
  • the F polymer may be heat-meltable or non-heat-meltable.
  • the heat-meltable polymer means a polymer having a temperature at which the melting flow rate is 1 to 1000 g / 10 minutes under the condition of a load of 49 N.
  • the non-thermally meltable polymer means a polymer in which there is no temperature at which the melt flow rate is 1 to 1000 g / 10 minutes under the condition of a load of 49 N.
  • the melting temperature of the heat-meltable F polymer is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and even more preferably 260 ° C. or higher.
  • the melting temperature of the F polymer is preferably 325 ° C or lower, more preferably 320 ° C or lower.
  • the melting temperature of the F polymer is particularly preferably 180 to 325 ° C.
  • the glass transition point of the F polymer is preferably 50 ° C. or higher, more preferably 75 ° C. or higher.
  • the glass transition point of the F polymer is preferably 150 ° C. or lower, more preferably 125 ° C. or lower.
  • polytetrafluoroethylene hereinafter, also referred to as “PTFE”
  • PAVE perfluoro (alkyl vinyl ether)
  • PFA unit polymers containing (hereinafter, also referred to as “PFA”) or copolymers containing units based on TFE and hexafluoropropylene (hereinafter, also referred to as “FEP”) are preferable, PFA or FEP is more preferable, and PFA is further preferable.
  • FEP polytetrafluoroethylene
  • FEP hexafluoropropylene
  • CF 2 CFOCF 3
  • CF 2 CFOCF 2 CF 3
  • CF 2 CFOCF 2 CF 3
  • PPVE CFOCF 2 CF 2 CF 3
  • the F polymer preferably has a polar functional group.
  • the F polymer may have two or more polar functional groups.
  • As the polar functional group a carbonyl group-containing group, a hydroxyl group-containing group and a phosphono group-containing group are preferable, and the F polymer has a carbonyl group-containing group or a hydroxyl group-containing group from the viewpoint of easily enhancing physical properties such as dispersibility of the powder. Polymers are more preferred.
  • the polar functional group may be contained in the monomer unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter aspect include an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like.
  • the number of carbonyl group-containing groups in the F polymer is preferably 10 or more and 5000 or less, and 50 or more and 2000 or less per 1 ⁇ 10 6 main chain carbon atoms. More preferred. In this case, the affinity between the F polymer particles and the liquid medium tends to be improved.
  • 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.
  • Examples of the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH 2 ), an acid anhydride residue (-C (O) OC (O)-), and the like.
  • 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.
  • hydroxyl group-containing group an alcoholic hydroxyl group-containing group is preferable, and —CF 2 CH 2 OH, —C (CF 3 ) 2 OH and 1,2-glycol group (—CH (OH) CH 2 OH) are more preferable.
  • Suitable embodiments of the F polymer include a polymer (1) containing TFE and PAVE units and having a carbonyl group-containing group or hydroxyl group, or TFE and PAVE units, with 2 PAVE units for all monomer units.
  • examples thereof include the polymer (2) containing up to 5 mol% and having neither a carbonyl group-containing group nor a hydroxyl group-containing group. Since these polymers form microspherulites in the coating film or molded product, the characteristics of the obtained coating film or molded product can be easily improved.
  • the polymer (1) a polymer containing a TFE unit, a PAVE unit, and a unit based on a monomer having a hydroxyl group-containing group or a carbonyl group-containing group is preferable.
  • the TFE unit is 90 to 99 mol%
  • the PAVE unit is 0.5 to 9.97 mol%
  • the unit based on the monomer is 0.01 to 3 mol%, based on all the units.
  • Polymers containing each are more preferable.
  • examples of the monomer having a hydroxyl group-containing group or a carbonyl group-containing group include itaconic anhydride, citraconic anhydride and 5-norbornen-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter, "NAH”). Note)) is preferable.
  • Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
  • the polymer (2) is preferably composed of only TFE units and PAVE units, and preferably contains 95 to 98 mol% of TFE units and 2 to 5 mol% of PAVE units with respect to all the monomer units.
  • the content of PAVE units in the preferred polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the monomer units.
  • the fact that the polymer (2) has neither a carbonyl group-containing group nor a hydroxyl group-containing group means that the carbonyl group possessed by the polymer per 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. It means that the number of containing groups or hydroxyl group-containing groups is less than 500.
  • the number of carbonyl group-containing groups or hydroxyl group-containing groups is preferably 100 or less, more preferably less than 50.
  • the lower limit of the number of carbonyl group-containing groups or hydroxyl group-containing 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 the polar functional group derived from the polymerization initiator may be used in the polymer chain.
  • a polymer having a polar functional group such as a polymer having a terminal group may be fluorinated to produce the polymer. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314).
  • This powder consists of F polymer particles.
  • the specific surface area of the powder is preferably 8 m 2 / g or less, more preferably 5 m 2 / g or less, and particularly preferably 3 m 2 / g or less.
  • the specific surface area of this powder is preferably 1 m 2 / g or more.
  • the D50 of this powder is preferably 20 ⁇ m or less, more preferably 8 ⁇ m or less.
  • the D50 of this powder is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, still more preferably 1 ⁇ m or more.
  • the D90 of this powder is preferably less than 100 ⁇ m, more preferably 90 ⁇ m or less. If D50 and D90 of the present powder are in such a range, the surface area thereof becomes large, and the dispersibility of the present powder is likely to be further improved.
  • the present powder may be a powder composed of particles composed of a mixture of two or more kinds of F polymers, or may be a powder composed of two or more kinds of particles composed of F polymers.
  • the latter is a powder composed of particles made of one F polymer and particles made of a different F polymer, and is usually a mixture of a certain F polymer powder and a different F polymer powder (that is, a powder mixture).
  • the powder mixture includes a heat-meltable F-polymer powder (such as a heat-meltable F-polymer powder having a carbonyl group-containing group including TFE units and PAVE units) and a non-heat-meltable F-polymer powder (non-heat-melting).
  • a mixture of sex PTFE powder and the like) is preferred.
  • the ratio of the former particles (particles of the heat-meltable F polymer) to the total amount of the present powder is preferably 50% by mass or less, more preferably 25% by mass or less. ..
  • the ratio is preferably 0.1% by mass or more, more preferably 1% by mass or more.
  • the D50 of the former particles is preferably 1 to 4 ⁇ m, and the D50 of the latter particles (particles of the non-heat-meltable F polymer) is preferably 0.1 to 1 ⁇ m.
  • the particles constituting the powder may contain a polymer, resin or inorganic substance different from the F polymer.
  • a polymer, resin or inorganic substance different from the F polymer in this case is insoluble in the liquid medium in the present composition.
  • Specific examples of the polymer or resin different from the F polymer include aromatic elastomers such as aromatic polyimides, aromatic maleimides and styrene elastomers, polymers such as aromatic polyamic acids, and cured products of curable resins.
  • aromatic elastomers such as aromatic polyimides, aromatic maleimides and styrene elastomers
  • polymers such as aromatic polyamic acids
  • inorganic substances include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). Can be mentioned.
  • the powder containing the F polymer and particles containing a polymer or resin or inorganic substance different from the F polymer is composed of, for example, particles composed of a mixture of the F polymer and fine particles of the polymer or resin or inorganic substance different from the F polymer.
  • Examples thereof include the present powder composed of the particles having.
  • Examples of the latter powder include a powder obtained by colliding and aggregating an F polymer powder with a polymer or resin powder different from the F polymer or a powder made of inorganic fine particles and coalescing them.
  • the liquid medium is an inert liquid liquid at 25 ° C. that does not dissolve the F polymer particles (hereinafter, also referred to as “powder particles”) constituting the powder.
  • the liquid medium preferably has an affinity with F polymer particles, for example, a liquid polar medium usually has an affinity with F polymer particles having a carbonyl group-containing group or a hydroxyl group-containing group.
  • the liquid medium in the present composition may be a low-viscosity one or a high-viscosity one. As the liquid medium in this composition, a low-viscosity liquid medium is preferable.
  • the low-viscosity liquid medium means a liquid medium having a viscosity of 10 mPa ⁇ s or less measured by a B-type viscosity meter at 25 ° C.
  • the high-viscosity liquid medium means a liquid medium having a viscosity measured by a B-type viscosity meter at 25 ° C.
  • the boiling point of the low-viscosity liquid medium is preferably 75 ° C. or higher, more preferably 100 ° C. or higher.
  • the boiling point of the low-viscosity liquid medium is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
  • the low-viscosity liquid medium may be a liquid polar medium or a non-polar liquid medium such as a hydrocarbon-based liquid medium.
  • the liquid polar medium is a liquid medium having a polar group, and refers to a liquid medium made of an organic compound having a polar group such as an amide group, a carbonyl group or a carbonyloxy group, and a liquid medium made of an inorganic compound having a polarity such as water. ..
  • the organic compound having the polar group is preferably an amide, a ketone and an ester, and the inorganic compound having the polarity is preferably water.
  • amides which are low-viscosity liquid media, include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropanamide, 3-methoxy-N, Examples thereof include N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N, N-diethylformamide, hexamethylphosphoric triamide and 1,3-dimethyl-2-imidazolidinone.
  • ketones that are low-viscosity liquid media include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone.
  • acetone methyl ethyl ketone
  • methyl isopropyl ketone methyl isobutyl ketone
  • methyl n-pentyl ketone methyl isopentyl ketone
  • 2-heptanone cyclopentanone
  • cyclohexanone cycloheptanone
  • esters that are low-viscosity liquid media include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and 3-ethoxy.
  • examples thereof include ethyl propionate, ⁇ -butyrolactone and ⁇ -valerolactone.
  • the low-viscosity liquid medium water, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, cyclohexanone, and cyclopentanone are preferable.
  • the boiling point of the high-viscosity liquid medium is preferably 100 ° C. or higher.
  • the boiling point of the high-viscosity liquid medium is preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
  • glycols such as ethylene glycol, ditylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, and derivatives such as ethers and esters of such glycols are preferable.
  • glycol monoalkyl ether As the derivative of such glycol ether, glycol monoalkyl ether, glycol monoaryl ether, glycol monoalkyl ether alkyl ester, glycol monoaryl ether alkyl ester, and glycol dialkyl ether are more preferable, and glycol monoalkyl ether is further preferable.
  • the high-viscosity liquid medium include ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, and tripropylene glycol monobutyl ether. , Propylene Glycol Monophenyl Ether, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate.
  • the present composition (1) may contain a polymer or resin other than the F polymer.
  • the fact that the present composition (1) may be contained means that the present powder may be contained in a portion other than the particles constituting the present powder.
  • the polymer or resin other than the F polymer in the present composition (1) may be dissolved in a liquid medium, may be contained as particles similar to the inorganic filler without being dissolved, and may swell including the liquid medium. It may be contained as particles.
  • the present composition (2) contains a polar polymer which is a polymer other than the F polymer or a resin, or a precursor thereof.
  • polymers and resins other than the F polymer that may be contained in the present composition (1) will be described, and then the polar polymer and its precursor contained in the present composition (2) will be described.
  • Polymers and resins other than the F polymer are different from the F polymer, and are reactions such as polymers, precursors thereof (meaning low molecular weight compounds and oligomers that can become the polymers by polymerization, cross-linking, etc.), condensation, and the like. It means a combination of two or more kinds of compounds that can be polymerized by the above, and the like.
  • a resin called a thermoplastic resin is usually a polymer
  • a resin called a curable resin is a combination of a low molecular weight compound, an oligomer, and a low molecular weight compound which are usually reaction-cured to become a polymer.
  • an elastomer or rubber depending on the physical characteristics of the polymer, it may be called an elastomer or rubber.
  • polymers and resins other than F polymer are collectively referred to as "other resins".
  • Other resins include aromatic polyesters, aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, precursors of aromatic polyamideimides, epoxy resins, maleimide resins, urethane resins, thermoplastic elastomers, polyamideimides, polyphenylene ethers, etc.
  • Fluoropolymers other than polyphenylene oxide, liquid crystal polyester, polysaccharides, nylon, acrylic resin, methacrylic resin, butyral, cyanate resin, ABR rubber, cellulose, PVA acrylic methacryl, polyalkylene ether, polyoxyethylene alkyl ether, and F polymer Can be mentioned.
  • aromatic polyester aromatic polyimide
  • aromatic polyamic acid aromatic polyamideimide
  • aromatic polyamideimide precursor of aromatic polyamideimide
  • polyphenylene ether epoxy resin
  • maleimide resin thermoplastic elastomer
  • the aromatic polyimide may be thermoplastic or thermosetting.
  • aromatic polyimides include “Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria (registered trademark)” series (manufactured by Somar), and “Q-PILON (registered trademark)” series ( PI Technology Research Institute), “WINGO” series (Wingo Technology), “Toamide (registered trademark)” series (T & K TOKA), “KPI-MX” series (Kawamura Sangyo), “Yupia (" Registered trademark) -AT “series (manufactured by Ube Kosan Co., Ltd.) can be mentioned.
  • Specific examples of the aromatic polyamide-imide and the precursor of the aromatic polyamide-imide include “HPC-1000” and “HPC-2100D” (both manufactured by Showa Denko Materials Co., Ltd.).
  • styrene elastomer examples include styrene-butadiene copolymer, hydrogenated-styrene-butadiene copolymer, hydrogenated-styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene block copolymer.
  • examples thereof include hydrogenated products of styrene-butadiene-styrene block copolymers, and hydrogenated products of styrene-isoprene-styrene block copolymers.
  • the urethane resin may be, for example, urethane fine particles containing an acrylic component, or a homopolymer or a copolymer. Specific examples thereof include commercially available dimic beads CM (manufactured by Dainichiseika Kogyo Co., Ltd.), Art Pearl (manufactured by Negami Kogyo Co., Ltd.), and Grand Pearl (manufactured by Aica Kogyo Co., Ltd.).
  • CM commercially available dimic beads CM (manufactured by Dainichiseika Kogyo Co., Ltd.), Art Pearl (manufactured by Negami Kogyo Co., Ltd.), and Grand Pearl (manufactured by Aica Kogyo Co., Ltd.).
  • Polysaccharides include glycogen, amylose, agarose, amyropectin, cellulose, dextrin, glucan, fructan, xanthan gum, guar gum, casein, arabic gum, gelatin, agaropectin, arabinan, curdlan, carose, carboxymethyl starch, chitin, chitosan, quince.
  • Seeds glucomannan, gellan gum, tamarin seed gum, dextrin, nigeran, hyaluronic acid, pustulose, funoran, pectin, porphyran, laminaran, likenan, curdlanan, alginic acid, tragacanth gum, alkathy gum, locust bean gum.
  • Acrylic resins and methacrylic resins include polyacrylates, polymethacrylates, ethylene-methylmethacrylate copolymers, ethylene-methylacrylate copolymers, ethylene-ethylacrylate copolymers, ethylene-butylacrylate copolymers, and ethylene-vinyl acetates. Examples include copolymers. Examples of the acrylic resin and the methacrylic resin include the Neocryl series manufactured by Kusumoto Kasei Co., Ltd. as a commercially available product.
  • nylon examples include nylon 6, nylon 11, and nylon 12.
  • examples of commercially available butyral resins include Sekisui Chemical's Eslek (registered trademark) B series, K (KS) series, SV series, and Kuraray's Mobital (registered trademark) series.
  • examples of the bisphenol ester resin include bisphenol A type cyanic acid, bisphenol F type cyanate ester resin, 6F bisphenol A dicyan acid ester resin, bisphenol E type dicyan acid ester resin, tetramethyl bisphenol F dicyan acid ester resin, and bisphenol M dicyan acid. Examples thereof include ester resins, dicyclopentadienbisphenol disyanic acid ester resins, and novolak cyanate resins.
  • epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, and glycidylamine type epoxy resin.
  • Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogen Epoxy resin can be mentioned.
  • thermoplastic elastomers include TR series (styrene / butadiene thermoplastic elastomer, manufactured by JSR Co., Ltd.), RB series (polybutadiene-based thermoplastic elastomer, manufactured by JSR Co., Ltd.), and JSR EXELINK (olefin-based thermoplastic elastomer, JSR).
  • DYNARON (registered trademark) series hydrogenated thermoplastic elastomer, manufactured by JSR Co., Ltd.), Thermolan (registered trademark) (olefin-based thermoplastic elastomer, manufactured by Mitsubishi Chemical Corporation), Epox TPE series (olefin-based heat) Plastic Elastomer, Sumitomo Chemical Co., Ltd.), Septon (Registered Trademark) Series (Hydrogenized styrene Thermoplastic Elastomer, Claret Co., Ltd.), Tough Tech (Registered Trademark) (Hydrogenized Styrene Thermoplastic Elastomer, Asahi Kasei Co., Ltd.) Can be mentioned.
  • the fluoropolymer other than the F polymer include polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene and the like.
  • the composition (2) contains a polar polymer or a precursor thereof as the other resin.
  • the polar polymer in the present composition (2) is a polymer having a polar functional group in the main chain or side chain of the polymer, and the precursor of the polar polymer is a precursor that can be polymerized by heating or the like to become a polar polymer.
  • Polar functional groups are usually heteroatoms or atomic groups containing heteroatoms. Heteroatoms include, for example, halogen atoms other than oxygen, sulfur, nitrogen and fluorine.
  • a precursor of a polar polymer is such a polar functional group or a precursor having a group that can become such a polar functional group by polymerization.
  • Examples of the polymer having a polar functional group in the main chain of the polymer include a polymer having an ether bond, an ester bond, an amide bond, an imide bond, a thioether bond, a sulfide bond or a disulfide bond in the main chain.
  • Examples of the polar functional group in the polymer having a polar functional group on the side chain of the polymer include the carbonyl group-containing group, the hydroxyl group-containing group, the thiol group, the sulfide group, the sulfonyl group, the sulfoxyl group, the amino group and the amide group. , A carbonyl group-containing group and a hydroxyl group-containing group are preferable. In this case, the interaction between the F polymer and the polar polymer (or its predecessor) and the liquid medium is likely to be improved, and the above-mentioned mechanism of action is likely to be remarkably developed.
  • the molecular weight of the polar polymer and its precursor is preferably 3000 or more, more preferably 5000 or more, and even more preferably 10,000 or more.
  • the molecular weight of the polar polymer and its precursor is preferably 50,000 or less, more preferably 30,000 or less.
  • the polar polymer and its precursor easily interact with the F polymer and the liquid polar medium, and the present composition (2) tends to have excellent physical properties such as dispersion stability.
  • the polar polymer and its precursor are preferably those that are soluble in a liquid polar medium.
  • polar polymer examples include ether polymers such as polyacetal, polyalkylene glycol, polyether ketone, polyether ether ketone, and polyether sulfone, ester polymers such as polyalkylene terephthalate and polyalkylene naphthalate, and amide polymers such as nylon and aramid.
  • ether polymers such as polyacetal, polyalkylene glycol, polyether ketone, polyether ether ketone, and polyether sulfone
  • ester polymers such as polyalkylene terephthalate and polyalkylene naphthalate
  • amide polymers such as nylon and aramid.
  • Polymers such as polyimide and polyamideimide, sulfide-based polymers such as polythiol, polysulfide, and polydisulfide, sulfonate-based polymers such as polyether sulfone and polyphenyl sulfone, polyvinyl alcohol, polyacrylate, polymethacrylate, polyvinylpyrrolidone, and poly.
  • examples thereof include vinyl acetate, carboxyvinyl polymers, polyhalogenated vinyls other than F polymers, vinyl-based polymers such as polyhalogenated vinylidene, polysaccharides and precursors thereof.
  • polar polymer a polymer in which the polar functional group is introduced into polyolefin can also be mentioned.
  • the polysaccharide include the polysaccharides mentioned as the other resins.
  • These polar polymers may be copolymers composed of a plurality of types of monomers.
  • an imide-based polymer As the polar polymer and its precursor, an imide-based polymer, a precursor of the imide-based polymer, a vinyl-based polymer and a polysaccharide are preferable.
  • Preferred imide-based polymers and precursors thereof include polyimide, polyamide-imide, polyamic acid, and polyamide-imide precursors, with aromatic polyimides, aromatic polyamideimides, aromatic polyamic acids, and aromatic polyamide-imide precursors being more preferred. ..
  • imide-based polymers include "Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria (registered trademark)” series (manufactured by Somar), and “Q-PILON (registered trademark)” series ( PI Technology Research Institute), “WINGO” series (Wingo Technology), “Tombide (registered trademark)” series (T & K TOKA), “KPI-MX” series (Kawamura Sangyo), “Yupia (“ Examples include the “AT” series (manufactured by Ube Kosan Co., Ltd.), “HPC-1000", and “HPC-2100D” (manufactured by Showa Denko Materials Co., Ltd.).
  • Preferred vinyl-based polymers include vinyl alcohol-based polymers such as polyvinyl alcohol, vinylpyrrolidone-based polymers such as polyvinylpyrrolidone, acrylic acid-based polymers such as polyacrylic acid, and carboxyvinyl-based polymers such as carboxyvinyl polymer.
  • the based polymer is more preferable.
  • the vinyl alcohol-based polymer polyvinyl alcohol, polyvinyl acetate, a partially acetylated product of polyvinyl alcohol, a partially acetal product of polyvinyl alcohol, and a copolymer of vinyl alcohol, vinyl butyral, and vinyl acetate are preferable.
  • vinyl alcohol polymers include “Eslek (registered trademark) B” series, “Eslek (registered trademark) K (KS)” series, and “Eslek (registered trademark) SV” series (all manufactured by Sekisui Chemical Co., Ltd.). , “Mobital (registered trademark)” series (manufactured by Kuraray).
  • acrylic acid-based polymer examples include polyacrylates such as polyacrylic acid, methyl polyacrylate and ethyl polyacrylate, poly- ⁇ -haloacrylate, poly- ⁇ -cyanoacrylate, polyacrylamide, and sodium polyacrylate.
  • Preferred polysaccharides include glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, and chitin among the polysaccharides.
  • Carboxymethyl cellulose is preferable as the cellulose.
  • the carboxymethyl cellulose may be a carboxymethyl cellulose salt such as sodium carboxymethyl cellulose or ammonium carboxymethyl cellulose.
  • the other resins in the present composition are preferably dissolved in a liquid medium or swollen by a liquid medium, particularly polar polymers and
  • the precursor is preferably dissolved in a liquid medium.
  • the other resin that does not dissolve in the liquid medium is contained in the present composition as particles similar to the particles of the following inorganic filler.
  • the particles similar to the particles of the inorganic filler particles made of a cured product of a curable resin are preferable.
  • the composition may contain particles of the inorganic filler.
  • the inorganic filler is used to improve the physical properties of the coating film or the molded product obtained when the composition or the dispersion obtained by diluting the composition is used for forming various coating films or molded products.
  • the type is appropriately selected according to the purpose of the coating film or the molded product.
  • the perovskite-type ferroelectric filler and the bismuth layered perovskite-type ferroelectric filler are preferable as the inorganic filler.
  • perovskite-type ferroelectric substance examples include barium titanate, lead zirconate titanate, lead titanate, zirconium oxide, and titanium oxide.
  • examples of the bismuth layered perovskite type ferroelectric substance include bismuth strontium tantalate, bismuth strontium niobate, and bismuth titanate.
  • a low dielectric constant, low dielectric loss tangent or low linear expansion rate inorganic filler is used as the inorganic filler.
  • a boron nitride filler a beryllium oxide filler (berilia filler), a silicon oxide filler (silica filler), a wollastonite filler, and a magnesium metasilicate filler (steatite filler) are preferable.
  • a metal oxide filler is used as the inorganic filler.
  • the metal oxide aluminum oxide, lead oxide, iron oxide, tin oxide, magnesium oxide, titanium oxide, zinc oxide, antimony pentoxide, zirconium oxide, lanthanum oxide, neodium oxide, cerium oxide and niobium oxide are preferable, and aluminum oxide is preferable. Is more preferable.
  • a glass fiber filler or a carbon filler may be used as the inorganic filler other than these.
  • the carbon filler include carbon fiber (carbon fiber), carbon black, graphene, graphene oxide, fullerene, graphite and graphite oxide.
  • carbon fibers include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, vapor-phase-grown carbon fibers, and carbon nanotubes (single-wall, double-wall, multi-wall, cup-laminated type, etc.).
  • the inorganic filler a boron nitride filler, a silica filler and a magnesium metasilicate filler are preferable, and a silica filler is more preferable.
  • These fillers may be fired ceramic fillers.
  • the shape of the inorganic filler particles (that is, the particles constituting the inorganic filler) is appropriately selected depending on the intended purpose, and may be agglomerate particles or fibrous particles. If a filler composed of agglomerated particles is used, the surface flatness of the coating film or the molded product is improved, the slidability of the surface is improved, and the scratch resistance is likely to be improved. On the other hand, if an inorganic filler composed of fibrous particles is used, a part of the filler particles is exposed on the surface of the coating film or the molded product, and it is easy to improve the wear resistance and scratch resistance of the product surface, for example.
  • the average particle size (D50) is preferably 0.02 to 200 ⁇ m.
  • the average fiber length thereof is preferably 0.05 to 300 ⁇ m.
  • the average fiber diameter of the fibrous inorganic filler is preferably 0.01 to 15 ⁇ m.
  • the particles constituting the inorganic filler may have various shapes such as a plate shape, a hollow shape, and a honeycomb shape.
  • the inorganic filler is preferably composed of inorganic filler particles surface-treated with a silane coupling agent.
  • a silane coupling agent include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-. Ixylpropyltriethoxysilane is preferred.
  • Suitable specific examples of the inorganic filler are zinc oxide fillers surface-treated with esters such as silica fillers (“Admafine (registered trademark)” series manufactured by Admatex) and propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.).
  • esters such as silica fillers (“Admafine (registered trademark)” series manufactured by Admatex) and propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.).
  • the composition may contain components other than the powder particles, the liquid medium, other resins and the inorganic filler.
  • other components include surfactants from the viewpoint of improving dispersion stability and handleability.
  • the surfactant is preferably a nonionic surfactant.
  • the hydrophilic moiety of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
  • the oxyalkylene group may be composed of one kind or two or more kinds. In the latter case, the different types of oxyalkylene groups may be randomly arranged or may be arranged in a block shape. As the oxyalkylene group, an oxyethylene group is preferable.
  • the hydrophobic moiety of the surfactant preferably has an acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group.
  • the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
  • a fluorine-based surfactant a fluorine-based surfactant having a hydroxyl group, particularly an alcoholic hydroxyl group or an oxyalkylene group, and a perfluoroalkyl group or a perfluoroalkenyl group is preferable.
  • surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafuck” series (manufactured by DIC), and “Unidyne” series (Daikin Industries).
  • the present composition contains a surfactant (however, when the inorganic filler is an inorganic filler previously treated with a surfactant, the surfactant attached to the inorganic filler is excluded), the amount thereof is determined by the present composition.
  • the content in the present dispersion is preferably 1 to 15% by mass. In this case, the affinity between the components is increased, and the dispersion stability of the present dispersion is more likely to be improved.
  • the present composition also contains a tyxicity-imparting 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. It may further contain additives such as agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, and various fillers.
  • the composition (1) contains particles derived from F polymer powder and a liquid medium, has a solid content concentration of 40% by mass or more, and has a viscosity measured by a B-type viscometer of 8000 to 100,000 mPa ⁇ s.
  • the present composition (1) is a slurry-like, paste-like or gel-like composition, and is preferably a high-viscosity composition called a paste.
  • the solid content concentration of the composition (1) is preferably 50% by mass or more.
  • the solid content concentration of the composition (1) is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the viscosity measured by the B-type viscometer of the present composition (1) is preferably 10,000 mPa ⁇ s or more.
  • the viscosity is preferably 80,000 mPa ⁇ s or less, more preferably 40,000 mPa ⁇ s or less, and even more preferably 20,000 mPa ⁇ s or less.
  • the liquid medium in the present composition (1) is preferably a low-viscosity liquid medium, and the present composition (1) may contain two or more kinds of liquid media.
  • the present composition (1) may contain other components such as the other resin and the inorganic filler.
  • the other resin is a resin other than the polar polymer or its precursor
  • the other resin is preferably dissolved in a liquid medium, and in that case, the liquid medium in which the other resin is dissolved is other than the liquid polar medium. It may be a liquid medium of.
  • the composition (1) preferably has a foam volume ratio of 10% or less.
  • the foam volume ratio was measured by measuring the volume ( VN ) of the present composition (1) at standard atmospheric pressure and 20 ° C. and the combined volume ( VV ) of the foam when the pressure was reduced to 0.003 MPa. It is a value obtained by the following formula.
  • Foam volume ratio [%] 100 x ( VV - VN) / VN
  • the present composition (1) is obtained, for example, by kneading a mixture containing an F polymer powder and a liquid medium, and at least either degassing during or after the kneading or allowing the mixture to stand after the kneading. be able to. If the present composition (1) is prepared by such a method, the foam volume ratio can be within the above range.
  • the content of the liquid medium in the composition (1) is preferably 10% by mass or more.
  • the content of the liquid medium is preferably 60% by mass or less, more preferably 25% by mass or less.
  • the solid content concentration of the present composition (1) can be set within the above range by appropriately setting the amounts of the F polymer and the liquid medium. Even when other resins or inorganic fillers are contained, the solid content concentration in the composition (1) can be set within the above range by appropriately setting the same. Further, by selecting the viscosity of the liquid medium, the viscosity of the present composition (1) can be within the above range.
  • the mass ratio of the powder particles to the other resin is such that the mass of the powder particles is 1 and the mass of the other resin is 0.01 to 0.5.
  • the ratio is preferable, and the ratio of 0.1 to 0.3 is more preferable.
  • the content of the inorganic filler in the solid content is preferably 25% by mass or more, more preferably 50% by mass or more.
  • the inorganic filler is preferably 75% by mass or less, more preferably 60% by mass or less.
  • the foam volume ratio of the dispersion obtained by diluting the present composition (1) with a second liquid medium can be easily set to the same range as the foam volume ratio of the present composition (1). Therefore, it is possible to reduce the uniformity of the component distribution of the coating film or the molded product obtained from the dispersion liquid and suppress the voids.
  • the present composition (2) is a composition containing particles derived from F polymer powder, a polar polymer or a precursor thereof, and a liquid polar medium, and having a viscosity as measured by capillograph of 10,000 to 100,000 Pa ⁇ s.
  • the composition (2) is preferably a highly viscous composition, also called a wet powder.
  • the composition (2) may further contain other components such as an inorganic filler and a surfactant.
  • the ratio of the total mass of the powder particles to the polar polymer in the composition (2) is preferably more than 50% by mass, more preferably 60% by mass or more, with the total mass of the composition (2) being 100% by mass. , 80% by mass or more is more preferable.
  • the ratio of the total mass is preferably 99% by mass or less, more preferably 90% by mass or less.
  • the mass ratio of the liquid polar medium in the composition (2) is preferably 40% by mass or less, more preferably 20% by mass or less, with the total mass of the composition (2) being 100% by mass.
  • the mass ratio is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the ratio of the content of the polar polymer to the content of the powder particles in the composition (2) is preferably 0.001 or more and less than 0.5, where the content of the powder particles is 1.
  • the ratio is more preferably 0.005 or more, still more preferably 0.01 or more.
  • the ratio is more preferably 0.25 or less, still more preferably less than 0.1.
  • the viscosity of the composition (2) measured by capillograph is more preferably 15,000 Pa ⁇ s or more.
  • the viscosity of the composition (2) is more preferably 50,000 Pa ⁇ s or less, and even more preferably 30,000 Pa ⁇ s or less.
  • the state of the present composition (2) having a viscosity as measured by capillograph in such a range is a composition containing the present powder particles wet with a liquid polar medium in which a polar polymer (or a precursor thereof) is sufficiently dissolved, and is in the form of a lump.
  • the clay-like composition is also called a wet powder.
  • the present powder particles in the present composition (2) are in a state of being dispersed in a small amount of a liquid polar medium in which a polar polymer (or a precursor thereof) is dissolved, or are in a state of being dispersed. It is considered that the powder particles in the composition (2) are in contact with each other and a liquid polar medium in which the polar polymer (or its precursor) is dissolved is present in the particle gaps thereof.
  • the composition (2) preferably contains a surfactant.
  • particles derived from the powder of the F polymer having a carbonyl group-containing group or a hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, and a carbonyl group-containing group particles derived from the powder of the F polymer having a carbonyl group-containing group or a hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, and a carbonyl group-containing group.
  • a wet powder containing a polar polymer having a hydroxyl group or a precursor thereof and at least one liquid polar medium selected from the group consisting of amides, ketones and esters can be mentioned.
  • the solid content concentration of the composition (2) is preferably more than 50% by mass, more preferably 60% by mass or more.
  • the solid content concentration is preferably 99% by mass or less, more preferably 95% by mass or less.
  • the composition (2) is excellent in dispersibility with respect to the second liquid medium, and the obtained dispersion is excellent in dispersion stability.
  • the solid content in the present composition (2) means the total amount of substances forming the solid content in the coating film or the molded product formed from the present composition (2) or the obtained dispersion liquid.
  • the composition (2) contains an F polymer, a polar polymer, and an inorganic filler
  • the total content of these components is the solid content in the composition (2).
  • the mass ratio of the inorganic filler to the powder particles is preferably 0.5 to 2, more preferably 0.6 to 1.5, and further preferably 0.7 to 1. preferable.
  • the content of the powder particles in the solid content is preferably 25% by mass or more, more preferably 30% by mass or more.
  • the content of the powder particles is preferably 60% by mass or less, more preferably 50% by mass or less.
  • the content of the inorganic filler in the solid content is preferably 10% by mass or more, more preferably 25% by mass or more.
  • the content of the inorganic filler is preferably 75% by mass or less, more preferably 60% by mass or less.
  • the F polymer is a polymer having low surface tension and rigidity
  • the F polymer particles tend to aggregate with each other in a dispersion liquid in which the powder is dispersed in a liquid dispersion medium. Therefore, it has been difficult to obtain a dispersion liquid having excellent processability and dispersion stability.
  • foaming becomes intense during the preparation of the dispersion liquid, and the dispersion stability decreases due to aggregation. There was a case. Further, due to the characteristics of this F polymer, it is difficult for this powder to interact with other components in a dispersion liquid containing the powder particles and other components.
  • the interaction between the components does not necessarily increase, and agglomeration of F polymer particles occurs, making it difficult to form a dense and uniform dispersion. This tendency was particularly remarkable when the F polymer was mixed with the polar polymer to obtain a uniform dispersion liquid.
  • the present composition by using the present composition, wetting of the present powder and interaction between the components can be promoted, and a dispersion liquid without the above-mentioned problems can be obtained.
  • the polar polymer interacts with a liquid polar medium having the same polarity, and at least a part thereof is dissolved.
  • the degree of freedom of the molecular motion of the polar polymer is increased and the interaction between the polar polymer and the powder particles is promoted. It is considered that this also promotes the interaction between the liquid polar medium in which the polar polymer is dissolved and the powder particles, and makes the powder particles easy to get wet.
  • the present composition (2) which is a composition in which the three components are densely and uniformly mixed in a predetermined viscosity range, is formed.
  • the dispersion obtained by diluting the composition (2) with a second polar solvent can also be used. It is considered that the dispersion stability has improved.
  • the present composition (2) is preferably kneaded with a mixture containing the powder of the F polymer and the liquid polar medium, and is degassed during or after such kneading, as in the present composition (1). It is preferably obtained by performing at least one of standing after kneading.
  • the present invention is also a method for producing the present composition, in which a mixture containing the present powder and a liquid medium (hereinafter, also referred to as “the present mixture”) is kneaded, and deaeration and kneading during or after such kneading are performed. It is a method of producing the present composition by performing at least one of the subsequent standing.
  • the composition (2) can be produced by this method by using a polar polymer together with the powder and using a liquid polar medium as the liquid medium. Deaeration of the kneaded product during or after kneading promotes efficient removal of gas such as air existing in the particle gaps of the powder and atmospheric gas brought in during the preparation of the composition, and wets the powder particles. Improve sex. Further, the standing of the kneaded product after kneading promotes the penetration of the liquid medium between the powder particles and promotes the wetting of the powder particles. It is preferable to perform both degassing and standing
  • each component or a part of the mixture is mixed in the kneader. It may be introduced into the kneader to make the present mixture in a kneader. Further, a part of each component may be introduced into the kneader during the kneading of each component. For example, a liquid medium may be further added to the kneaded product (including the liquid medium) being kneaded. Further, as the polar polymer, it is preferable to use a solution dissolved in a liquid polar medium for forming the present mixture. Further, it is also preferable that the liquid component such as a liquid medium is degassed and used before the formation of the present mixture.
  • kneading the present mixture it is preferable to knead the mixture so that the mass of the present mixture does not substantially change, and it is preferable to knead the mixture in a closed system. In other words, it is preferable to knead the mixture so that the liquid components of the present mixture do not evaporate during kneading.
  • a kneader equipped with a stirring tank and uniaxial or multiaxial stirring blades. The number of stirring blades is preferably two or more in order to obtain a high kneading action.
  • the kneading method may be either a batch method or a continuous method.
  • the planetary mixer has a biaxial stirring blade that rotates and revolves with each other, and has a structure in which the kneaded material in the stirring tank is stirred and kneaded. Therefore, there is little dead space in the stirring tank where the stirring blades do not reach.
  • the shape of the blade is thick and a high load can be applied, but it can also be used like a normal stirrer in which the stirring blade is rotated in a stirring tank. Therefore, there is little dead space in the stirring tank where the stirring blades do not reach, the load on the blades can be reduced, and the present mixture can be highly kneaded.
  • the kneading of the present mixture is preferably carried out while cooling.
  • the vaporization of the liquid medium is suppressed, the mixture becomes sticky, and a load is applied to the stirring blades of the kneader, and as a result, the shearing force on the mixture increases.
  • a shearing force is likely to be applied to the material between the stirring blades or between the stirring blades and the stirring tank.
  • the temperature in the kneading is preferably not less than the boiling point of the liquid medium, and more preferably 30 ° C. or less.
  • the temperature in kneading is preferably 0 ° C. or higher, more preferably 10 ° C. or higher.
  • the kneading for obtaining the present composition (2) is preferably carried out until the fluctuation range of the viscosity of the kneaded product becomes ⁇ 5% or less when the capillograph is measured at a temperature of 25 ° C. and a shear rate of 1s -1 . ..
  • the fluctuation range is more preferably ⁇ 3% or less.
  • the fluctuation range of the viscosity can be confirmed by sampling the kneaded product from the kneader every 10 minutes while kneading and measuring the viscosity by capillograph measurement at the upper limit.
  • the end point of kneading can be determined by monitoring the current consumption because the load applied to the stirring blade becomes smaller and the current consumption of the kneader decreases as the kneading progresses. Further, the kneading may be controlled by using the value obtained by dividing the load current of the kneader by the shear rate of the kneader as the force and energy given to the kneaded product. Specifically, it is preferable to increase the load current from the start of kneading and gradually decrease it.
  • the continuous kneader examples include a twin-screw extrusion kneader and a stone mill type kneader.
  • the twin-screw extrusion kneader is, for example, a twin-screw-type continuous kneading device that kneads an object to be kneaded by a shear force between two screws arranged in parallel in close proximity to each other.
  • the stone mill type kneader is, for example, a tubular fixed portion having an internal space through which the kneaded material can pass, and a kneaded material which is arranged in the internal space of the fixed portion and passes through the internal space by rotating. It is a kneading machine having a rotating portion that conveys in the direction of the rotation axis while kneading.
  • Degassing may be performed during the kneading, after the kneading, or alternately with the kneading a plurality of times. Degassing may be performed continuously or intermittently. Degassing is preferably performed so that the mass of the present mixture does not change substantially.
  • the degassing method includes, for example, a method of depressurizing the liquid composition, a method of heating the liquid composition, a method of freezing the liquid composition, a method of irradiating the mixture with ultrasonic waves, and these methods. The combined method can be mentioned.
  • a method of putting the present mixture in a depressurized state or a method of putting the present mixture in a heated state is preferable from the viewpoint of simplicity of operation, and a method in which both are combined is more preferable from the viewpoint of degassing efficiency. Further, as described above, it is particularly preferable to carry out the process while cooling.
  • the temperature and pressure at the time of degassing are appropriately set according to the present mixture in the liquid composition, and the pressure and temperature at which the present mixture does not boil are selected.
  • the pressure is preferably about 0 Pa to 0.01 MPa
  • the temperature is preferably 100 ° C. to 250 ° C. lower than the boiling point of the liquid medium in the present mixture.
  • the degassing time is not particularly limited, but it is usually 10 minutes to 6 hours because the degassing effect does not change significantly even if the degassing time is too long.
  • an operation such as stirring may be performed to prevent bumping.
  • the kneaded product is usually allowed to stand after the kneading.
  • the kneaded product after kneading is allowed to stand in a container for a certain period of time. It is preferable to allow the kneaded product to stand so that the mass of the kneaded product does not substantially change, and it is preferable to allow the kneaded product to stand in a closed system such as in a closed container.
  • the temperature and pressure of the atmosphere in which the kneaded material is allowed to stand are usually about 10 to 30 ° C. and 1 atm, preferably under constant temperature and humidity.
  • the powder particles in the kneaded product may be agitated to the extent that they do not coagulate and settle during standing.
  • the standing time is preferably 24 hours or more, more preferably 48 hours or more.
  • the standing time is preferably 168 hours or less because the effect obtained does not change significantly even if the standing time is too long.
  • the viscosity of the kneaded product at the time of standing to obtain the present composition (1) is preferably 40,000 mPa ⁇ s or less, and more preferably 20,000 mPa ⁇ s or less.
  • the viscosity is preferably 8000 mPa ⁇ s or more. In this case, the permeation of the liquid medium between the powder particles is further promoted, and the above-mentioned mechanism of action is likely to be enhanced.
  • the viscosity of the kneaded product at the time of standing may be adjusted by the temperature thereof or by adding a liquid medium such as a liquid polar medium to the kneaded product.
  • either degassing or standing may be performed, but it is preferable to perform both from the viewpoint of the dispersion stability of the dispersion obtained by diluting the composition.
  • Examples of performing both are a mode in which the mixture is kneaded, then degassing is continuously or intermittently performed, and then the mixture is allowed to stand without degassing, and the mixture is continuously or intermittently degassed. Kneading while kneading and allowing the obtained kneaded product to stand still, kneading the mixture while continuously or intermittently degassing, and then allowing the obtained kneaded product to stand still, and then further degassing.
  • the present mixture is kneaded, and after kneading, the mixture is allowed to stand while being degassed, and then the mixture is allowed to stand without being degassed.
  • a mode of degassing continuously or intermittently is mentioned.
  • the agglomeration of the powder particles is suppressed, and when the composition and the second liquid medium are mixed. Foaming is suppressed. As a result, the surface smoothness of the obtained coating film or molded product is excellent.
  • the present composition is diluted with a second liquid medium and used as a dispersion having a lower viscosity than the present composition.
  • the composition can also be used for other purposes.
  • the dispersion obtained by diluting the composition with a second liquid medium (hereinafter, also referred to as “the dispersion”) is suitable for applications such as coating agents and paints.
  • the second liquid medium is a liquid medium compatible with the first liquid medium, and may be the same liquid medium as the first liquid medium.
  • the second liquid medium is a liquid medium that does not dissolve insoluble components such as powder particles and inorganic fillers in the composition by diluting the composition, and is dissolved in the first liquid medium. It is preferably a liquid medium that does not precipitate components.
  • the polar polymer swells in the present composition (2).
  • a second liquid medium is particularly preferably the same liquid medium as the first liquid medium in the diluted composition.
  • the second liquid medium include liquid media that may be used as the first liquid medium, and among them, a liquid medium having a low viscosity is preferable.
  • the mixing of the present composition for diluting with the second liquid medium and the second liquid medium is preferably mixed using, for example, a disperser from the viewpoint of the dispersibility and dispersion stability of the obtained dispersion liquid.
  • a disperser from the viewpoint of the dispersibility and dispersion stability of the obtained dispersion liquid.
  • the disperser using media include an ultrasonic homogenized baint shaker, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, and an agitator mill.
  • Examples of those that do not use media include an ultrasonic homogenizer, a nanomizer, a resolver, a disper, a high-speed impeller disperser, a rotation / revolution agitator, and a thin-film swirling high-speed mixer.
  • a disperser using media is preferable because it has a high dispersive capacity.
  • the collision type disperser is a disperser that collides with a liquid medium once pressurized by a high-pressure pump and disperses by the impact force or the like at this time.
  • the collision type disperser can be roughly divided into two types depending on the object to be collided. There are a method in which liquid media collide with each other and a method in which the liquid medium collides with an object to collide. Examples of the method of colliding liquid media with each other include nanomizer, Genus PY, ultimateizer, Aqua, microfluidizer and the like. An example of a method of colliding a liquid medium with a collision object is a homogenizer or the like.
  • the present composition and the second liquid medium are mixed in the kneader having the stirring tank and the stirring blade used for the kneading.
  • the kneader having the stirring tank and the stirring blade used for the kneading.
  • examples thereof include a method of mixing the liquid medium of the above, a method of mixing the present composition with the second liquid medium by a different kneading machine, and the like.
  • the kneader are the same as those of the batch type and continuous type kneaders.
  • this dispersion other resins, inorganic fillers, surfactants and the like may be added as needed.
  • the other resin and the inorganic filler may be added separately or together, or a masterbatch in which the other resin and the inorganic filler are mixed in advance. May be prepared and this masterbatch may be added.
  • the solid content concentration in the dispersion is preferably 40% by mass or more, more preferably 50% by mass or more. Further, from the viewpoint of dispersibility of the present dispersion, the solid content concentration is preferably 90% by mass or less, more preferably 75% by mass or less.
  • the solid content of the present dispersion means the components obtained by removing all the liquid media from the present dispersion, and means the total amount of substances forming the solid components in the coating film or the molded product normally formed from the present dispersion. do.
  • the content of the powder particles with respect to the solid content in the dispersion is preferably 20% by mass or more, more preferably 30% by mass or more.
  • the content of the powder particles is preferably 70% by mass or less, more preferably 50% by mass or less.
  • the viscosity of this dispersion measured by a B-type viscometer is preferably 50 mPa ⁇ s or more, more preferably 75 mPa ⁇ s or more, and even more preferably 100 mPa ⁇ s or more.
  • the viscosity is preferably less than 8000 mPa ⁇ s, more preferably 5000 mPa ⁇ s or less, and even more preferably 1000 mPa ⁇ s or less.
  • the dispersion having such a viscosity is excellent in coatability.
  • the thixotropic ratio of this dispersion is preferably 1 to 10.
  • the foam volume ratio in the dispersion is preferably less than 10%, more preferably less than 5%.
  • the foam volume ratio is preferably 0% or more. According to this method, a dispersion having excellent physical characteristics can be easily obtained by the above-mentioned mechanism of action.
  • a laminate having the base material and the F layer can be produced. ..
  • the dispersion may be further allowed to stand before its use.
  • Preferable embodiments of the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof.
  • the metal foil in the metal-clad laminate is preferably a copper foil.
  • Such a metal-clad laminate is particularly useful as a printed circuit board material.
  • the resin film in the multilayer film is preferably a polyimide film. Such a multilayer film is useful as an electric wire coating material and a printed circuit board material.
  • the F layer may be formed on at least one side of the surface of the base material, the F layer may be formed on only one side of the base material, and the F layer is formed on both sides of the base material. You may.
  • the surface of the base material may be surface-treated with a silane coupling agent or the like.
  • the 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. , Slot die coat method, dip coat method can be used.
  • the F layer is preferably formed by removing the liquid medium from the dispersion by heating and then firing the polymer by further heating.
  • the temperature for removing the liquid medium is preferably as low as possible, preferably 50 to 150 ° C. lower than the boiling point of the liquid medium.
  • N-methyl-2-pyrrolidone having a boiling point of about 200 ° C. it is preferable to heat it at 180 ° C. or lower, preferably 100 to 150 ° C. It is preferable to blow air in the step of removing the liquid medium.
  • the F layer preferably contains a fired product of the F polymer.
  • the F layer is formed through the steps of applying, drying, and firing the present dispersion as described above. These steps may be performed once or twice or more.
  • the step of applying the present dispersion liquid to the surface of the base material, removing the liquid medium by heating to form a film is repeated twice, and the film having an increased thickness is heated to form an F polymer. It may be formed by firing. From the viewpoint of easily obtaining a thick F layer having excellent smoothness, the steps of applying and drying the dispersion may be performed twice or more.
  • the thickness of the F layer is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more.
  • the upper limit of the thickness is 100 ⁇ m. In this range, the F layer having excellent crack resistance can be easily formed.
  • 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. By using this dispersion, such a laminate can be easily formed without impairing the physical properties of the F polymer in the F layer.
  • the porosity of the F layer is preferably 5% or less, more preferably 4% or less.
  • the porosity is preferably 0.01% or more, more preferably 0.1% or more.
  • the porosity is the ratio (%) of the area of the void portion in the cross section of the coating film or the molded product observed using a scanning electron microscope (SEM).
  • Materials for the base material include metal substrates (copper, nickel, aluminum, titanium, metal foils such as alloys thereof, etc.), resin films (polyimide, polyarylate, polysulfone, polyallyl sulfone, polyamide, polyetheramide, polyphenylene sulfide, etc.). , Polyallyl ether ketone, polyamideimide, liquid crystal polyester, liquid crystal polyester amide and other films), prepreg (precursor of fiber reinforced resin substrate), ceramics substrate, glass substrate and the like.
  • Examples of the shape of the base material include a planar shape, a curved surface shape, and an uneven shape, and may be any of a foil shape, a plate shape, a film shape, and a fibrous shape.
  • the ten-point average roughness of the surface of the base material is preferably 0.01 to 0.05 ⁇ m.
  • the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof.
  • the metal foil in the metal-clad laminate is preferably a copper foil.
  • Such a metal-clad laminate is particularly useful as a printed circuit board material.
  • the resin film in the multilayer film is preferably a polyimide film. Such a multilayer film is useful as an electric wire coating material and a printed circuit board material.
  • the printed circuit board includes a flexible printed circuit board and a rigid printed circuit board.
  • Another substrate may be laminated on the opposite side of the F layer to the substrate to form a multilayer laminate.
  • Lamination can be performed, for example, by thermocompression bonding.
  • the structure of the multilayer laminate includes a base material / F layer / another base material / F layer / base material, a metal substrate layer / another base material layer / F layer / another base material layer / metal substrate layer, and the like. Can be mentioned.
  • Each layer may further contain a glass cloth or filler.
  • Such a laminate 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.
  • Insulating tape Insulating tape, insulating tape for oil drilling, material for printed substrate, precision filtration membrane, ultrafiltration membrane, reverse osmosis membrane, ion exchange membrane, dialysis membrane, separation membrane such as gas separation membrane, lithium secondary battery, fuel Electrode binders for batteries, copy rolls, furniture, automobile dash boats, covers for home appliances, load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, sliding members such as food transport belts, shovels. It is useful as tools for shavings, cuttings, saws, boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container covering materials, and mold release films.
  • an impregnated woven fabric in which the F polymer is impregnated in the woven fabric can be obtained.
  • the impregnated woven fabric can also be said to be a coated woven fabric in which the woven fabric is covered with an F layer.
  • the woven fabric is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric, and more preferably a glass fiber woven fabric or a carbon fiber woven fabric.
  • the woven fabric may be treated with a silane coupling agent from the viewpoint of enhancing the adhesiveness with the F layer.
  • the content of the F polymer in the impregnated woven fabric is preferably 30 to 80% by mass.
  • Examples of the method of impregnating the woven fabric with the dispersion liquid include a method of immersing the woven fabric in the dispersion liquid and a method of applying the dispersion liquid to the woven fabric.
  • the F polymer may be fired.
  • the method of firing the F polymer include a method of passing the woven fabric through a ventilation drying oven in an atmosphere of 300 to 400 ° C.
  • the drying of the woven fabric and the firing of the polymer may be carried out in one step.
  • the woven fabric thus obtained is excellent in characteristics such as high adhesion or adhesiveness between the F layer and the woven fabric, high surface smoothness, and little distortion.
  • thermocompression bonding the woven fabric and the metal foil a metal-clad laminate having high peel strength and resistance to warping can be obtained, which can be suitably used as a printed circuit board material.
  • the woven fabric impregnated with the dispersion liquid is placed on the surface of the base material by sticking or the like, heated and dried to form an impregnated woven fabric layer containing the F polymer and the woven fabric. May be formed to produce a laminated body in which the base material and the impregnated woven fabric layer are laminated in this order.
  • the embodiment is also not particularly limited, and for example, if a woven fabric impregnated with the present dispersion is placed on a part or all of the inner wall surface of a member such as a tank, a pipe, or a container, and the member is heated while rotating.
  • An impregnated woven fabric layer can be formed on a part or all of the inner wall surface of the member. This manufacturing method is also useful as a method for lining the inner wall surface of members such as tanks, pipes, and containers.
  • this dispersion has excellent dispersion stability and can be efficiently impregnated into a porous or fibrous material.
  • porous or fibrous materials include materials other than the above-mentioned woven fabrics, specifically, plate-shaped, columnar or fibrous materials. These materials may be pretreated with a curable resin, a silane coupling agent, or the like, or may be further filled with an inorganic filler, another resin, or the like. In addition, these materials may be twisted together to form a thread, a cable, or a wire. At the time of twisting, an intervening layer made of another polymer such as polyethylene may be arranged.
  • the fibrous material examples include high-strength and low-elongation fibers such as carbon fiber, aramid fiber, and silicon carbide fiber.
  • a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, or a polyurethane resin is preferable.
  • Specific examples of such an embodiment include a composite cable formed by impregnating a cable made by twisting carbon fibers carrying a thermosetting resin with a dispersion liquid and further heating the cable to bake an F polymer.
  • Such a composite cable is useful as a cable for large structures, ground anchors, oil excavation, cranes, cableways, elevators, agriculture, forestry and fisheries, and slinging cables.
  • the present dispersion having excellent dispersibility and dispersion stability can be obtained.
  • aggregation of F polymer particles is suppressed, and foaming during production and use of this dispersion is suppressed.
  • the surface smoothness of the obtained coating film or molded product is excellent.
  • the present invention is not limited to the configuration of the above-described embodiment.
  • the method for producing the present composition and the present dispersion 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 present composition and the present dispersion may be added to any other composition in the configuration of the above embodiment, or may be replaced with an arbitrary composition exhibiting the same function.
  • Powder 12 A powder consisting of a polymer (fluorine content: 76% by mass) having 40 carbonyl group-containing groups per 1 ⁇ 10 6 main chain carbon atoms (D50: 2.4 ⁇ m, consisting of TFE units and PPVE units).
  • Varnish 1 Varnish in which thermoplastic aromatic polyimide (PI1) is dissolved in NMP [surfactant]
  • Nonionic polymer that is a copolymer and has a fluorine content of 35% by mass [Liquid medium]
  • NMP N-methyl-2-pyrrolidone [viscosity]
  • the viscosity in Example 1 below refers to the viscosity measured by a B-type viscometer at a temperature of 25 ° C. and a rotation speed of 30 rpm.
  • Example 1-1 Production Example of Dispersion Liquid [Example 1-1] Powder 11 (70 parts by mass), PI1 (1.8 parts by mass), and surfactant 1 (3.5 by mass) obtained by mixing powder 11, varnish 1, surfactant 1, and NMP in a planetary mixer. A liquid composition containing (parts by mass) and NMP (30 parts by mass) was added, the liquid composition was kneaded while holding the inside of the planetary mixer under reduced pressure and degassed, and NMP was added to bring the viscosity to 10,000 mPa ⁇ s. A viscosity-adjusted paste-like composition 1 was obtained. After allowing the composition 1 to stand at 25 ° C.
  • the NMP is added to the composition 1 in a plurality of times so that the NMP becomes 70 parts by mass as a whole, and the mixture is stirred and mixed. Then, a dispersion liquid 11 having a viscosity of 1000 mPa ⁇ s was obtained.
  • Examples 1-2 to 1-6 Except for changing the type of powder, the presence or absence of degassing or standing, and the viscosity adjustment during standing, that is, the presence or absence of additional addition of NMP when producing a paste-like composition, as shown in Table 1.
  • the same procedure as in Example 1-1 was carried out to obtain paste-like compositions 2 to 6.
  • dispersion liquids 12 to 16 were obtained in the same manner as in Example 1-1.
  • the numerical value in parentheses in the "static" column in Table 1 indicates the static time (unit: hr).
  • the foam volume ratio of the composition 1, the composition 3, the dispersion liquid 11, and the dispersion liquid 13 is 0% or more and less than 5%, and the composition 2, the composition 4, the composition 6, the dispersion liquid 12, and the dispersion liquid 14
  • the foam volume ratio of the dispersion liquid 16 was more than 5% and less than 10%.
  • the foam volume ratio of the composition 5 and the dispersion liquid 15 was 10% or more.
  • laminated body 1 The dispersion liquid 11 was applied to the surface of a long copper foil having a thickness of 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 11 having a metal foil and a polymer layer having a thickness of 20 ⁇ m as a molded product containing a melt-fired product of powder 11 and PI1 on the surface thereof was produced.
  • Dielectric Dissipation Factor of Laminates For each laminate, the copper foil of the laminate is removed by etching with an aqueous ferric chloride solution to prepare a single polymer layer, and SPDR (split post dielectric) is prepared. By the resonance) method, the dielectric loss tangent of the polymer layer was measured at a measurement frequency of 10 GHz and evaluated according to the following criteria.
  • Powder 21 Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order, and has 1000 carbonyl groups per 1 ⁇ 10 6 main chain carbon atoms.
  • Polar Polymer 1 Aromatic Polyimide (manufactured by Ube Kosan Co., Ltd., "U-Varnish”)
  • Polar Polymer 2 Carboxymethyl Cellulose (Nippon Paper Industries, Ltd., "Sunrose MAC Series 200HC”)
  • Polar polymer 3 Polyvinyl alcohol (manufactured by Sekisui Chemical Co., Ltd., "Eslek BL-1”)
  • Inorganic filler 1 Silica filler surface-treated with an aminosilane coupling agent (D50: 0.2 ⁇ m)
  • the viscosity of the composition in Example 2 below refers to the viscosity measured by capillograph at a temperature of 25 ° C. and a shear rate of 1s -1 , and the viscosity of the dispersion liquid is a B-type viscosity at a temperature of 25 ° C. and a rotation speed of 30 rpm. Viscosity measured by a meter.
  • Example 2-1 Production Example of Composition
  • the varnish (solvent: NMP) of polar polymer 1 and NMP were put into a pot and mixed. Further, a powder mixture of the powder 21 and the inorganic filler 1 was put into a pot and mixed to prepare a mixture. This mixture is kneaded in a planetary mixer and then taken out, and has a composition containing powder 21 (50 parts by mass), inorganic filler 1 (40 parts by mass) and polar polymer 1 (10 parts by mass), and NMP (30 parts by mass). I got the thing 21.
  • the composition 21 was lumpy, clay-like, and wet powder. When the capillograph was measured at a temperature of 25 ° C.
  • the viscosity of the composition 21 was 18,000 Pa ⁇ s, and even if the composition 21 was further kneaded, the fluctuation range of the viscosity was ⁇ 3%. It was within. NMP was added to the composition 21 in a plurality of times, and the mixture was stirred while degassing at 2000 rpm with a rotating revolution stirrer. Further, NMP was added in a plurality of times and stirred, and 80 parts by mass of NMP as a whole was added to the composition 21 to prepare a dispersion liquid, and a dispersion liquid 21 was obtained. The viscosity of the dispersion 21 was 300 mPa ⁇ s.
  • Example 2-2 The composition 22 and the dispersion liquid 22 were obtained in the same manner as in Example 2-1 except that the polar polymer 1 was changed to the polar polymer 2.
  • the viscosity of the composition 22 was 20000 Pa ⁇ s, and even when the composition 22 was further kneaded, the fluctuation range of the viscosity was within ⁇ 3%.
  • the viscosity of the dispersion 22 was 400 mPa ⁇ s.
  • Example 2-3 The composition 23 and the dispersion liquid 23 were obtained in the same manner as in Example 2-1 except that the polar polymer 1 was changed to the polar polymer 3.
  • the viscosity of the composition 23 was 21000 Pa ⁇ s, and even when the composition 23 was further kneaded, the fluctuation range of the viscosity was within ⁇ 3%.
  • the viscosity of the dispersion liquid 23 was 400 mPa ⁇ s.
  • Example 2-4 The composition 24 and the dispersion liquid 24 were obtained in the same manner as in Example 2-1 except that the kneading time was halved.
  • the viscosity of the composition 24 was 60,000 Pa ⁇ s, and when the composition 24 was further kneaded, the viscosity fluctuated by more than ⁇ 5%.
  • the viscosity of the dispersion liquid 24 was 800 mPa ⁇ s.
  • Example 2-5 The composition 25 and the dispersion liquid 25 were obtained in the same manner as in Example 2-1 except that the amount of the powder 21 was changed to 25 parts by mass and the amount of the polar polymer 1 was changed to 5 parts by mass.
  • the viscosity of the composition 25 was 8000 Pa ⁇ s.
  • the viscosity of the dispersion liquid 25 was 400 mPa ⁇ s.
  • Example 2-6 The composition 26 and the dispersion liquid 26 were obtained in the same manner as in Example 2-1 except that the NMP was changed to n-decane.
  • the viscosity of the composition 26 was 80,000 Pa ⁇ s, and even when the composition 26 was further kneaded, the fluctuation range of the viscosity was within ⁇ 3%.
  • the viscosity of the dispersion liquid 26 was 3000 mPa ⁇ s.
  • the dispersion prepared by this method is excellent in dispersibility, dispersion stability, and thixotropic stability, and therefore, the laminate using the dispersion obtained by this method has a uniform component distribution. It was excellent in properties and various physical properties.

Abstract

Provided are a high-viscosity composition containing powder particles of a tetrafluoroethylene polymer and a liquid medium, a method for producing the composition, and a method for producing a dispersion having excellent dispersion stability from the composition.　A composition including particles derived from a powder of a tetrafluoroethylene polymer having a specific surface area of 25 m2/g or less, a liquid medium, and optionally other polymers dissolved in the liquid medium, wherein the composition has a viscosity measured by B-type viscometer at a temperature of 25°C and rotary speed of 30 rpm of 8,000-100,000 mPa∙s or a viscosity measured by capillograph at a temperature of 25°C and shear rate of 1 s-1 of 10,000-100,000 Pa∙s. Also, a method for producing the composition that kneads a mixture of the components of the composition and carries out at least one of degassing during or after the kneading and standing after kneading, and a method for producing a dispersion in which particles derived from the powder are dispersed in a liquid medium that dilutes the composition by a liquid medium.

Description

テトラフルオロエチレン系ポリマーのパウダー粒子を含む組成物、その製造方法、その組成物からの分散液の製造方法A composition containing powder particles of a tetrafluoroethylene polymer, a method for producing the same, and a method for producing a dispersion liquid from the composition.
　本発明は、テトラフルオロエチレン系ポリマーのパウダー粒子と液状媒体を含む高粘度の組成物、かかる高粘度の組成物の製造方法、および、かかる高粘度の組成物からテトラフルオロエチレン系ポリマー粒子が分散した分散液を製造する方法に関する。 The present invention comprises a high-viscosity composition containing powder particles of a tetrafluoroethylene-based polymer and a liquid medium, a method for producing such a high-viscosity composition, and tetrafluoroethylene-based polymer particles dispersed from the high-viscosity composition. The present invention relates to a method for producing the resulting dispersion.
　テトラフルオロエチレン系ポリマーは、電気絶縁性、撥水撥油性、耐薬品性、耐熱性等の物性に優れている。このため、そのパウダーを水や油性溶剤中に分散させた分散液は、レジスト、接着剤、電気絶縁層、潤滑剤、インク、塗料等を形成するための材料として有用である。しかし、テトラフルオロエチレン系ポリマーは、表面エネルギーが低く、そのパウダーを構成している粒子（以下、「パウダー粒子」ともいう。）同士は、凝集しやすい。このため、分散安定性に優れた、低粘性の分散液を得ることはむずかしい。
　例えば、特許文献１には、分散液の分散性を向上させ、その液物性を調整する観点から、添加剤を使用した非水系分散液が開示されている。 The tetrafluoroethylene polymer is excellent in physical properties such as electrical insulation, water repellency, oil repellency, chemical resistance, and heat resistance. Therefore, the dispersion liquid in which the powder is dispersed in water or an oil-based solvent is useful as a material for forming a resist, an adhesive, an electrically insulating layer, a lubricant, an ink, a paint, and the like. However, the tetrafluoroethylene polymer has a low surface energy, and the particles constituting the powder (hereinafter, also referred to as “powder particles”) tend to aggregate with each other. Therefore, it is difficult to obtain a low-viscosity dispersion having excellent dispersion stability.
For example, Patent Document 1 discloses a non-aqueous dispersion liquid using an additive from the viewpoint of improving the dispersibility of the dispersion liquid and adjusting the physical characteristics of the dispersion liquid.
国際公開２０１６／１５９１０２号International Publication 2016/159102
　しかしながら特許文献１に記載の分散液も分散安定性という点では未だ充分ではない。
　特にフッ素含有量が高く比表面積の小さいテトラフルオロエチレン系ポリマーのパウダーの場合、その分散液の調製の際に泡立ちが激しくなり、凝集により分散安定性が低下する場合があった。またそのような分散液から得られる塗膜や成形物は、その表面平滑性が低下する場合があった。 However, the dispersion liquid described in Patent Document 1 is not yet sufficient in terms of dispersion stability.
In particular, in the case of a tetrafluoroethylene polymer powder having a high fluorine content and a small specific surface area, foaming becomes intense during the preparation of the dispersion, and dispersion stability may decrease due to aggregation. Further, the surface smoothness of the coating film or molded product obtained from such a dispersion liquid may be deteriorated.
　本発明者らは、比表面積が小さいテトラフルオロエチレン系ポリマーのパウダーからそのパウダー粒子の分散安定性に優れた分散液を得るべく、かかる分散液の製造方法を検討し、本発明の完成に至った。 The present inventors have studied a method for producing such a dispersion in order to obtain a dispersion having excellent dispersion stability of the powder particles from a tetrafluoroethylene polymer powder having a small specific surface area, and have completed the present invention. rice field.
　また、テトラフルオロエチレン系ポリマーのパウダー粒子を含み、さらに他の機能性材料（無機フィラー、テトラフルオロエチレン系ポリマーとは異なるポリマーや樹脂等）を含む分散液は、それから形成する塗膜や成形物において、他の機能性材料の物性も付与できる可能性がある。
　しかしながら、テトラフルオロエチレン系ポリマーと他の機能性材料との親和性は、総じて低く、かかる分散液においては、その分散安定性がさらに低下する傾向にある。
　他の機能性材料を添加する際に、高せん断を加えてテトラフルオロエチレン系ポリマーのパウダーを分散させようとすると、空気の巻き込み、テトラフルオロエチレン系ポリマーの変質等により、発泡や凝集が生じやすい。
　その結果、上記分散液から得られる塗膜や成形物における、成分分布の均一性の低下や空隙の発生による耐水性の低下が生じやすい。 Further, the dispersion liquid containing the powder particles of the tetrafluoroethylene-based polymer and further containing other functional materials (inorganic filler, polymer or resin different from the tetrafluoroethylene-based polymer, etc.) is a coating film or molded product formed from the dispersion liquid. In, there is a possibility that the physical properties of other functional materials can be imparted.
However, the affinity between the tetrafluoroethylene polymer and other functional materials is generally low, and the dispersion stability tends to be further lowered in such a dispersion.
When high shear is applied to disperse the tetrafluoroethylene polymer powder when other functional materials are added, foaming and aggregation are likely to occur due to air entrainment, alteration of the tetrafluoroethylene polymer, and the like. ..
As a result, in the coating film or the molded product obtained from the dispersion liquid, the uniformity of the component distribution is likely to be lowered and the water resistance is likely to be lowered due to the generation of voids.
　本発明は、テトラフルオロエチレン系ポリマーのパウダー粒子と液状媒体とを含有する、分散液の前駆体となるペースト状等の高粘性の組成物、およびその製造方法の提供を目的とする。
　また本発明は、テトラフルオロエチレン系ポリマーのパウダー粒子と極性ポリマーと、極性を有する液状媒体を含有する、分散液の前駆体となるウェットパウダー状等のさらに高粘性の組成物、およびその製造方法の提供を目的とする。
　さらに本発明は、上記高粘度の組成物を液状媒体で希釈することにより、テトラフルオロエチレン系ポリマーのパウダー粒子が分散した分散液を製造する、分散安定性に優れた分散液の提供を目的とする。 An object of the present invention is to provide a highly viscous composition such as a paste which is a precursor of a dispersion liquid, which contains powder particles of a tetrafluoroethylene polymer and a liquid medium, and a method for producing the same.
Further, the present invention comprises a powder particle of a tetrafluoroethylene polymer, a polar polymer, and a liquid medium having a polarity, and a more highly viscous composition such as a wet powder which is a precursor of a dispersion liquid, and a method for producing the same. The purpose is to provide.
Further, an object of the present invention is to provide a dispersion having excellent dispersion stability, which comprises diluting the highly viscous composition with a liquid medium to produce a dispersion in which powder particles of a tetrafluoroethylene polymer are dispersed. do.
　本発明は、下記の態様を有する。
［１］　比表面積が２５ｍ２／ｇ以下であるテトラフルオロエチレン系ポリマーのパウダーに由来する粒子と液状媒体を含有し、固形分濃度が４０質量％以上であり、温度を２５℃、回転数を３０ｒｐｍとしてＢ型粘度計で測定される粘度が８０００～１０００００ｍＰａ・ｓである、組成物。
［２］　さらに前記液状媒体に溶解性の、前記テトラフルオロエチレン系ポリマー以外のポリマーまたは樹脂を含む、［１］の組成物。
［３］　比表面積が２５ｍ２／ｇ以下であるテトラフルオロエチレン系ポリマーのパウダーに由来する粒子、極性ポリマーまたはその前駆体、およびかかる極性ポリマーまたはその前駆体を溶解しうる極性を有する液状媒体を含み、温度を２５℃、剪断速度を１ｓ－１とするキャピログラフ測定による粘度が１００００～１０００００Ｐａ・ｓである、組成物。
［４］　前記粒子の含有量と前記極性ポリマーまたはその前駆体の含有量の合計が５０質量％超であり、前記極性を有する液状媒体の含有量が４０質量％以下であり、前記粒子の含有量に対する前記極性ポリマーまたはその前駆体の含有量の比が０．００１以上０．５未満である、［３］の組成物。
［５］　前記極性ポリマーまたはその前駆体が、イミド系ポリマー、イミド系ポリマーの前駆体、ビニル系ポリマーまたは多糖類である、［３］または［４］の組成物。
［６］　前記極性を有する液状媒体が、水、アミド、ケトンおよびエステルからなる群から選ばれる液状媒体である、［３］～［５］のいずれかの組成物。 The present invention has the following aspects.
[1] Contains particles and a liquid medium derived from a tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less, a solid content concentration of 40% by mass or more, a temperature of 25 ° C., and a rotation speed. A composition having a viscosity measured by a B-type viscometer at 30 rpm of 8000 to 100,000 mPa · s.
[2] The composition of [1], which further contains a polymer or resin other than the tetrafluoroethylene polymer, which is soluble in the liquid medium.
[3] Particles derived from a powder of a tetrafluoroethylene-based polymer having a specific surface area of 25 m 2 / g or less, a polar polymer or a precursor thereof, and a liquid medium having a polarity capable of dissolving such a polar polymer or a precursor thereof. A composition comprising, having a viscosity of 10,000 to 100,000 Pa · s as measured by a capillograph with a temperature of 25 ° C. and a shear rate of 1 s -1 .
[4] The total content of the particles and the content of the polar polymer or its precursor is more than 50% by mass, the content of the liquid medium having the polarity is 40% by mass or less, and the content of the particles is The composition of [3], wherein the ratio of the content of the polar polymer or its precursor to the amount is 0.001 or more and less than 0.5.
[5] The composition of [3] or [4], wherein the polar polymer or its precursor is an imide-based polymer, a precursor of an imide-based polymer, a vinyl-based polymer or a polysaccharide.
[6] The composition according to any one of [3] to [5], wherein the liquid medium having the polarity is a liquid medium selected from the group consisting of water, amides, ketones and esters.
［７］　前記テトラフルオロエチレン系ポリマーがカルボニル基含有基または水酸基含有基を有するポリマーである、［１］～［６］のいずれかの組成物。
［８］　前記テトラフルオロエチレン系ポリマーのフッ素含有量が７０質量％以上である、［１］～［７］のいずれかの組成物。
［９］　前記テトラフルオロエチレン系ポリマーの溶融温度が１８０～３２５℃である、［１］～［８］のいずれかの組成物。
［１０］　前記テトラフルオロエチレン系ポリマーのパウダーを構成する粒子の平均粒子径が０.１～２０μｍである、［１］～［９］のいずれかの組成物。
［１１］　さらに無機フィラーを含む、［１］～［１０］のいずれかの組成物。 [7] The composition according to any one of [1] to [6], wherein the tetrafluoroethylene polymer is a polymer having a carbonyl group-containing group or a hydroxyl group-containing group.
[8] The composition according to any one of [1] to [7], wherein the tetrafluoroethylene polymer has a fluorine content of 70% by mass or more.
[9] The composition according to any one of [1] to [8], wherein the tetrafluoroethylene polymer has a melting temperature of 180 to 325 ° C.
[10] The composition according to any one of [1] to [9], wherein the particles constituting the tetrafluoroethylene polymer powder have an average particle size of 0.1 to 20 μm.
[11] The composition according to any one of [1] to [10], further comprising an inorganic filler.
［１２］　比表面積が２５ｍ２／ｇ以下であるテトラフルオロエチレン系ポリマーのパウダーに由来する粒子と液状媒体とを含む混合物を混練するとともに、かかる混練中もしくは混練後の脱気および混練後の静置の少なくともいずれかを行うことにより［１］～［１１］のいずれかの組成物を製造する、組成物の製造方法。
［１３］　前記脱気および前記静置の両方を行う、［１２］の製造方法。
［１４］　［１］～［１１］のいずれかの組成物を第２の液状媒体で希釈して分散液を得る、分散液の製造方法。
［１５］　比表面積が２５ｍ２／ｇ以下であるカルボニル基含有基または水酸基含有基を有するテトラフルオロエチレン系ポリマーのパウダーに由来する粒子と、カルボニル基含有基または水酸基含有基を有する極性ポリマーまたはその前駆体と、アミド、ケトンおよびエステルからなる群から選ばれる少なくとも１種の極性を有する液状媒体とを含む、ウェットパウダー。 [12] A mixture containing particles derived from a tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less and a liquid medium is kneaded, and degassing during or after kneading and static after kneading are performed. A method for producing a composition, wherein the composition according to any one of [1] to [11] is produced by performing at least one of the settings.
[13] The production method of [12], wherein both the degassing and the standing still are performed.
[14] A method for producing a dispersion liquid, wherein the composition according to any one of [1] to [11] is diluted with a second liquid medium to obtain a dispersion liquid.
[15] Particles derived from a powder of a tetrafluoroethylene-based polymer having a carbonyl group-containing group or a hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, and a polar polymer having a carbonyl group-containing group or a hydroxyl group-containing group or a polar polymer thereof. A wet powder comprising a precursor and a liquid medium having at least one polarity selected from the group consisting of amides, ketones and esters.
　本発明の高粘度の組成物を用いることにより、比表面積の小さいテトラフルオロエチレン系ポリマーのパウダーに由来する粒子を含有する分散安定性に優れた分散液が製造できる。かかる製造方法により得られる分散液を用いることで、得られる塗膜や成形物は、その表面平滑性に優れた外観となる。 By using the high-viscosity composition of the present invention, a dispersion liquid containing particles derived from a tetrafluoroethylene polymer powder having a small specific surface area and having excellent dispersion stability can be produced. By using the dispersion liquid obtained by such a production method, the obtained coating film or molded product has an appearance having excellent surface smoothness.
　以下の用語は、以下の意味を有する。
　「テトラフルオロエチレン系ポリマー」とは、テトラフルオロエチレン（以下、ＴＦＥとも記す）に基づく単位（以下、ＴＦＥ単位とも記す）を含有するポリマーである。
　「ポリマーのガラス転移点（Ｔｇ）」は、動的粘弾性測定（ＤＭＡ）法でポリマーを分析して測定される値である。
　「ポリマーの溶融温度（融点）」は、示差走査熱量測定（ＤＳＣ）法で測定した融解ピークの最大値に対応する温度である。
　「Ｄ５０」は、パウダーまたは無機フィラー等の測定対象物を構成する粒子の平均粒子径であり、レーザー回折・散乱法によって求められる測定対象物を構成する粒子の体積基準累積５０％径である。すなわち、レーザー回折・散乱法によって測定対象物を構成する粒子の粒度分布を測定し、測定対象物の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が５０％となる点の粒子径である。
　「Ｄ９０」は、測定対象物を構成する粒子の累積体積粒径であり、「Ｄ５０」と同様にして求められる粒子の体積基準累積９０％径である。
　「キャピログラフ測定による粘度」はキャピラリー長が１０ｍｍ、キャピラリー半径が１ｍｍのキャピラリーを用いて、炉体径が９．５５ｍｍ、ロードセル容量を２ｔとして測定された粘度である。
　「Ｂ型粘度計で測定される粘度」は、Ｂ型粘度計を用いて、室温下（２５℃）で回転数が３０ｒｐｍの条件下で測定される値である。測定を３回繰り返し、３回分の測定値の平均値とする。
　「チキソ比」とは、Ｂ型粘度計を用いて、室温下（２５℃）で回転数が３０ｒｐｍの条件で測定して求められる粘度η１を回転数が６０ｒｐｍの条件で測定して求められる粘度η２で除して算出される値（η１／η２）である。
　ポリマーにおける「モノマーに基づく単位」とは、重合によりモノマー１分子から直接形成された原子団、および、前記ポリマーを処理することによって前記原子団の一部が別の構造に変換されてなる原子団を意味する。以下、モノマーａに基づく単位を、単に「モノマーａ単位」とも記す。 The following terms have the following meanings.
The "tetrafluoroethylene-based polymer" is a polymer containing a unit (hereinafter, also referred to as TFE unit) based on tetrafluoroethylene (hereinafter, also referred to as TFE).
The "glass transition point (Tg) of the polymer" is a value measured by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method.
The “polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
“D50” is the average particle size of the particles constituting the measurement object such as powder or an inorganic filler, and is the volume-based cumulative 50% diameter of the particles constituting the measurement object obtained by the laser diffraction / scattering method. That is, the particle size distribution of the particles constituting the object to be measured is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the object to be measured as 100%, and the cumulative volume is 50% on the cumulative curve. Particle size.
“D90” is the cumulative volume particle diameter of the particles constituting the measurement object, and is the volume-based cumulative 90% diameter of the particles obtained in the same manner as in “D50”.
"Viscosity measured by capillary graph" is a viscosity measured by using a capillary having a capillary length of 10 mm and a capillary radius of 1 mm, a furnace body diameter of 9.55 mm, and a load cell capacity of 2 tons.
The "viscosity measured by the B-type viscometer" is a value measured by using a B-type viscometer under the condition of a room temperature (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 "tixo ratio" is obtained by measuring the viscosity η 1 obtained by measuring the viscosity η 1 at room temperature (25 ° C.) at a rotation speed of 30 rpm using a B-type viscometer under the condition of a rotation speed of 60 rpm. It is a value (η 1 / η 2 ) calculated by dividing by the viscosity η 2 .
A "monomer-based unit" in a polymer is an atomic group formed directly from one molecule of a monomer by polymerization, and an atomic group obtained by processing a part of the atomic group into another structure. Means. Hereinafter, the unit based on the monomer a is also simply referred to as “monomer a unit”.
　以下、本発明におけるテトラフルオロエチレン系ポリマーを「Ｆポリマー」とも記す。また、比表面積が２５ｍ２／ｇ以下であるＦポリマーのパウダーを「本パウダー」とも記す。
　また、以下、液状媒体のうち、極性を有する液状媒体を「液状極性媒体」とも記す。 Hereinafter, the tetrafluoroethylene polymer in the present invention is also referred to as “F polymer”. Further, the powder of F polymer having a specific surface area of 25 m 2 / g or less is also referred to as "this powder".
Further, hereinafter, among the liquid media, the liquid medium having polarity is also referred to as “liquid polar medium”.
　本発明の組成物の１つは、本パウダーに由来する粒子と液状媒体を含有し、固形分濃度が４０質量％以上であり、温度を２５℃、回転数を３０ｒｐｍとしてＢ型粘度計で測定される粘度（以下、単に「Ｂ型粘度計で測定される粘度」という。）が８０００～１０００００ｍＰａ・ｓである、組成物である。以下、この発明の組成物を「本組成物（１）」という。
　本発明の組成物の他の１つは、本パウダーに由来する粒子、極性ポリマーまたはその前駆体、および液状極性媒体を含み、剪断速度を１ｓ－１とするキャピログラフ測定による粘度（以下、単に「キャピログラフ測定による粘度」という。）が１００００～１０００００Ｐａ・ｓである、組成物である。以下、この発明の組成物を「本組成物（２）」という。
　また、上記本組成物（１）および本組成物（２）を総称して「本組成物」ともいう。
　本組成物は、本パウダーに由来する粒子が液状媒体に分散した分散液を得るための中間体として適している。本組成物を液状媒体で希釈することによりかかる分散液を得ることができる。
　なお、本組成物の希釈に使用される第２の液状媒体と区別するために、必要により、本組成物中の液状媒体を「第１の液状媒体」ともいう。
　以下、まず、本組成物にかかわるＦポリマー、本パウダー、液状媒体および極性ポリマーとその前駆体について説明する。 One of the compositions of the present invention contains particles derived from the present powder and a liquid medium, has a solid content concentration of 40% by mass or more, is measured with a B-type viscometer at a temperature of 25 ° C. and a rotation speed of 30 rpm. It is a composition having a viscosity (hereinafter, simply referred to as "viscosity measured by a B-type viscometer") of 8000 to 100,000 mPa · s. Hereinafter, the composition of the present invention is referred to as "the present composition (1)".
The other one of the compositions of the present invention comprises particles derived from the powder, a polar polymer or precursor thereof, and a liquid polar medium and has a viscosity as measured by a capillograph with a shear rate of 1s -1 (hereinafter, simply "". It is a composition having a viscosity (referred to as viscosity measured by capillograph measurement) of 10,000 to 100,000 Pa · s. Hereinafter, the composition of the present invention is referred to as "the present composition (2)".
Further, the present composition (1) and the present composition (2) are collectively referred to as "the present composition".
The present composition is suitable as an intermediate for obtaining a dispersion liquid in which particles derived from the present powder are dispersed in a liquid medium. Such a dispersion can be obtained by diluting the composition with a liquid medium.
The liquid medium in the composition is also referred to as a "first liquid medium", if necessary, in order to distinguish it from the second liquid medium used for diluting the composition.
Hereinafter, first, the F polymer, the present powder, the liquid medium, the polar polymer and the precursor thereof related to the present composition will be described.
　本組成物におけるＦポリマーは、テトラフルオロエチレン（以下、「ＴＦＥ」とも記す）に基づく単位（以下、「ＴＦＥ単位」とも記す）を含むポリマーである。
　Ｆポリマーのフッ素含有量は、７０質量％以上が好ましい。かかるフッ素含有量が高いＦポリマーは、Ｆポリマーの電気物性等の物性に優れる反面、液状媒体との親和性が著しく低い。そのため、かかるＦポリマーの粒子の分散性がさらに低下する。本組成物によれば、それを使用して得られるかかるＦポリマーの粒子の分散液においても、全体のＦポリマーの物性が損なわれず、分散性に優れた分散液が得られる。
　Ｆポリマーのフッ素含有量は、７６質量％以下が好ましい。 The F polymer in the present composition is a polymer containing a unit (hereinafter, also referred to as “TFE unit”) based on tetrafluoroethylene (hereinafter, also referred to as “TFE”).
The fluorine content of the F polymer is preferably 70% by mass or more. The F polymer having a high fluorine content is excellent in physical properties such as electrical properties of the F polymer, but has a remarkably low affinity with a liquid medium. Therefore, the dispersibility of the particles of the F polymer is further lowered. According to the present composition, even in the dispersion liquid of the particles of the F polymer obtained by using the same composition, the physical characteristics of the entire F polymer are not impaired, and a dispersion liquid having excellent dispersibility can be obtained.
The fluorine content of the F polymer is preferably 76% by mass or less.
　Ｆポリマーは熱溶融性であってもよく、非熱溶融性であってもよい。
　熱溶融性のポリマーとは、荷重４９Ｎの条件下、溶融流れ速度が１～１０００ｇ／１０分となる温度が存在するポリマーを意味する。
　非熱溶融性のポリマーとは、荷重４９Ｎの条件下、溶融流れ速度が１～１０００ｇ／１０分となる温度が存在しないポリマーを意味する。
　熱溶融性であるＦポリマーの溶融温度は、１８０℃以上が好ましく、２００℃以上がより好ましく、２６０℃以上がさらに好ましい。Ｆポリマーの溶融温度は、３２５℃以下が好ましく、３２０℃以下がより好ましい。Ｆポリマーの溶融温度は、１８０～３２５℃が特に好ましい。
　Ｆポリマーのガラス転移点は、５０℃以上が好ましく、７５℃以上がより好ましい。Ｆポリマーのガラス転移点は、１５０℃以下が好ましく、１２５℃以下がより好ましい。 The F polymer may be heat-meltable or non-heat-meltable.
The heat-meltable polymer means a polymer having a temperature at which the melting flow rate is 1 to 1000 g / 10 minutes under the condition of a load of 49 N.
The non-thermally meltable polymer means a polymer in which there is no temperature at which the melt flow rate is 1 to 1000 g / 10 minutes under the condition of a load of 49 N.
The melting temperature of the heat-meltable F polymer is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and even more preferably 260 ° C. or higher. The melting temperature of the F polymer is preferably 325 ° C or lower, more preferably 320 ° C or lower. The melting temperature of the F polymer is particularly preferably 180 to 325 ° C.
The glass transition point of the F polymer is preferably 50 ° C. or higher, more preferably 75 ° C. or higher. The glass transition point of the F polymer is preferably 150 ° C. or lower, more preferably 125 ° C. or lower.
　Ｆポリマーとしては、ポリテトラフルオロエチレン（以下、「ＰＴＦＥ」とも記す）、ＴＦＥ単位とペルフルオロ（アルキルビニルエーテル）（以下、「ＰＡＶＥ」とも記す）に基づく単位（以下、「ＰＡＶＥ単位」とも記す）を含むポリマー（以下、「ＰＦＡ」とも記す）またはＴＦＥとヘキサフルオロプロピレンに基づく単位を含むコポリマー（以下、「ＦＥＰ」とも記す）が好ましく、ＰＦＡまたはＦＥＰがより好ましく、ＰＦＡがさらに好ましい。これらのポリマーには、さらに他のコモノマーに基づく単位が含まれていてもよい。
　ＰＡＶＥとしては、ＣＦ２＝ＣＦＯＣＦ３、ＣＦ２＝ＣＦＯＣＦ２ＣＦ３またはＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ３（以下、ＰＰＶＥとも記す）が好ましく、ＰＰＶＥがより好ましい。 As the F polymer, polytetrafluoroethylene (hereinafter, also referred to as “PTFE”), a unit based on TFE unit and perfluoro (alkyl vinyl ether) (hereinafter, also referred to as “PAVE”) (hereinafter, also referred to as “PAVE unit”) is used. Polymers containing (hereinafter, also referred to as “PFA”) or copolymers containing units based on TFE and hexafluoropropylene (hereinafter, also referred to as “FEP”) are preferable, PFA or FEP is more preferable, and PFA is further preferable. These polymers may further contain units based on other comonomeres.
As the PAVE, CF 2 = CFOCF 3 , CF 2 = CFOCF 2 CF 3 or CF 2 = CFOCF 2 CF 2 CF 3 (hereinafter, also referred to as PPVE) is preferable, and PPVE is more preferable.
　Ｆポリマーは、極性官能基を有するのが好ましい。この場合、本パウダーと液状媒体の親和性が向上しやすい。Ｆポリマーは、２種以上の極性官能基を有していてもよい。
　極性官能基としては、カルボニル基含有基、水酸基含有基およびホスホノ基含有基が好ましく、本パウダーの分散性等の物性が高まりやすい観点から、Ｆポリマーはカルボニル基含有基または水酸基含有基を有するＦポリマーがより好ましい。
　極性官能基は、Ｆポリマー中のモノマー単位に含まれていてもよく、ポリマーの主鎖の末端基に含まれていてもよい。後者の態様としては、重合開始剤、連鎖移動剤等に由来する末端基として極性官能基を有するＦポリマーが挙げられる。 The F polymer preferably has a polar functional group. In this case, the affinity between the powder and the liquid medium tends to improve. The F polymer may have two or more polar functional groups.
As the polar functional group, a carbonyl group-containing group, a hydroxyl group-containing group and a phosphono group-containing group are preferable, and the F polymer has a carbonyl group-containing group or a hydroxyl group-containing group from the viewpoint of easily enhancing physical properties such as dispersibility of the powder. Polymers are more preferred.
The polar functional group may be contained in the monomer unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter aspect include an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like.
　Ｆポリマーがカルボニル基含有基を有する場合、Ｆポリマー中のカルボニル基含有基の数は、主鎖炭素数１×１０６個あたり、１０個以上５０００個以下が好ましく、５０個以上２０００個以下がさらに好ましい。この場合、Ｆポリマーの粒子と液状媒体の親和性が向上しやすい。なお、Ｆポリマーにおけるカルボニル基含有基の数は、ポリマーの組成または国際公開２０２０／１４５１３３号に記載の方法によって定量できる。 When the F polymer has a carbonyl group-containing group, the number of carbonyl group-containing groups in the F polymer is preferably 10 or more and 5000 or less, and 50 or more and 2000 or less per 1 × 10 6 main chain carbon atoms. More preferred. In this case, the affinity between the F polymer particles and the liquid medium tends to be improved. 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.
　カルボニル基含有基としては、カルボキシル基、アルコキシカルボニル基、アミド基、イソシアネート基、カルバメート基（－ＯＣ（Ｏ）ＮＨ２）、酸無水物残基（－Ｃ（Ｏ）ＯＣ（Ｏ）－）、イミド残基（－Ｃ（Ｏ）ＮＨＣ（Ｏ）－等）およびカーボネート基（－ＯＣ（Ｏ）Ｏ－）が好ましく、酸無水物残基がより好ましい。水酸基含有基としては、アルコール性水酸基含有基が好ましく、－ＣＦ２ＣＨ２ＯＨ、－Ｃ（ＣＦ３）２ＯＨおよび１，２－グリコール基（－ＣＨ（ＯＨ）ＣＨ２ＯＨ）がより好ましい。 Examples of the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH 2 ), an acid anhydride residue (-C (O) OC (O)-), and the like. 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. As the hydroxyl group-containing group, an alcoholic hydroxyl group-containing group is preferable, and —CF 2 CH 2 OH, —C (CF 3 ) 2 OH and 1,2-glycol group (—CH (OH) CH 2 OH) are more preferable.
　Ｆポリマーの好適な態様としては、ＴＦＥ単位およびＰＡＶＥ単位を含み、カルボニル基含有基または水酸基を有するポリマー（１）、または、ＴＦＥ単位およびＰＡＶＥ単位を含み、全モノマー単位に対してＰＡＶＥ単位を２～５モル％含み、カルボニル基含有基および水酸基含有基のいずれをも有さないポリマー（２）が挙げられる。これらのポリマーは、塗膜や成形物において微小球晶を形成するため、得られる塗膜や成形物の特性が向上しやすい。 Suitable embodiments of the F polymer include a polymer (1) containing TFE and PAVE units and having a carbonyl group-containing group or hydroxyl group, or TFE and PAVE units, with 2 PAVE units for all monomer units. Examples thereof include the polymer (2) containing up to 5 mol% and having neither a carbonyl group-containing group nor a hydroxyl group-containing group. Since these polymers form microspherulites in the coating film or molded product, the characteristics of the obtained coating film or molded product can be easily improved.
　ポリマー（１）としては、ＴＦＥ単位と、ＰＡＶＥ単位と、水酸基含有基またはカルボニル基含有基を有するモノマーに基づく単位とを含むポリマーが好ましい。ポリマー（１）としては、全単位に対して、ＴＦＥ単位を９０～９９モル％、ＰＡＶＥ単位を０．５～９．９７モル％、および前記モノマーに基づく単位を０．０１～３モル％、それぞれ含むポリマーがより好ましい。
　また、前記水酸基含有基またはカルボニル基含有基を有するモノマーとしては、無水イタコン酸、無水シトラコン酸および５－ノルボルネン－２，３－ジカルボン酸無水物（別称：無水ハイミック酸；以下、「ＮＡＨ」とも記す。）が好ましい。
　ポリマー（１）の具体例としては、国際公開第２０１８／１６６４４号に記載されるポリマーが挙げられる。 As the polymer (1), a polymer containing a TFE unit, a PAVE unit, and a unit based on a monomer having a hydroxyl group-containing group or a carbonyl group-containing group is preferable. As the polymer (1), the TFE unit is 90 to 99 mol%, the PAVE unit is 0.5 to 9.97 mol%, and the unit based on the monomer is 0.01 to 3 mol%, based on all the units. Polymers containing each are more preferable.
Further, examples of the monomer having a hydroxyl group-containing group or a carbonyl group-containing group include itaconic anhydride, citraconic anhydride and 5-norbornen-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter, "NAH"). Note)) is preferable.
Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
　ポリマー（２）としては、ＴＦＥ単位およびＰＡＶＥ単位のみからなり、全モノマー単位に対して、ＴＦＥ単位を９５から９８モル％、ＰＡＶＥ単位を２～５モル％含有するポリマーが好ましい。
　上記好ましいポリマー（２）におけるＰＡＶＥ単位の含有量は、全モノマー単位に対して、２．１モル％以上が好ましく、２．２モル％以上がより好ましい。
　なお、ポリマー（２）がカルボニル基含有基および水酸基含有基のいずれをも有さないとは、ポリマー主鎖を構成する炭素原子数の１×１０６個あたりに対して、ポリマーが有するカルボニル基含有基または水酸基含有基の数が、５００個未満であることを意味する。カルボニル基含有基または水酸基含有基の数は、１００個以下が好ましく、５０個未満がより好ましい。カルボニル基含有基または水酸基含有基の数の下限は、通常、０個である。 The polymer (2) is preferably composed of only TFE units and PAVE units, and preferably contains 95 to 98 mol% of TFE units and 2 to 5 mol% of PAVE units with respect to all the monomer units.
The content of PAVE units in the preferred polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the monomer units.
It should be noted that the fact that the polymer (2) has neither a carbonyl group-containing group nor a hydroxyl group-containing group means that the carbonyl group possessed by the polymer per 1 × 10 6 carbon atoms constituting the polymer main chain. It means that the number of containing groups or hydroxyl group-containing groups is less than 500. The number of carbonyl group-containing groups or hydroxyl group-containing groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of carbonyl group-containing groups or hydroxyl group-containing groups is usually 0.
　ポリマー（２）は、ポリマー鎖の末端基として極性官能基を生じない、重合開始剤や連鎖移動剤等を使用して製造してもよく、重合開始剤に由来する極性官能基をポリマー鎖の末端基に有するポリマー等の極性官能基を有するポリマーをフッ素化処理して製造してもよい。
　フッ素化処理の方法としては、フッ素ガスを使用する方法（特開２０１９－１９４３１４号公報等を参照）が挙げられる。 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 the polar functional group derived from the polymerization initiator may be used in the polymer chain. A polymer having a polar functional group such as a polymer having a terminal group may be fluorinated to produce the polymer.
Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314).
　本パウダーはＦポリマーの粒子からなる。
　本パウダーの比表面積は、８ｍ２／ｇ以下が好ましく、５ｍ２／ｇ以下がより好ましく、３ｍ２／ｇ以下が特に好ましい。本パウダーの比表面積は１ｍ２／ｇ以上が好ましい。
　本パウダーのＤ５０は、２０μｍ以下が好ましく、８μｍ以下がさらに好ましい。本パウダーのＤ５０は、０．１μｍ以上が好ましく、０．３μｍ以上がより好ましく、１μｍ以上がさらに好ましい。また、本パウダーのＤ９０は、１００μｍ未満が好ましく、９０μｍ以下がより好ましい。本パウダーのＤ５０およびＤ９０が、かかる範囲にあれば、その表面積が大きくなり、本パウダーの分散性が一層改良されやすい。 This powder consists of F polymer particles.
The specific surface area of the powder is preferably 8 m 2 / g or less, more preferably 5 m 2 / g or less, and particularly preferably 3 m 2 / g or less. The specific surface area of this powder is preferably 1 m 2 / g or more.
The D50 of this powder is preferably 20 μm or less, more preferably 8 μm or less. The D50 of this powder is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 1 μm or more. The D90 of this powder is preferably less than 100 μm, more preferably 90 μm or less. If D50 and D90 of the present powder are in such a range, the surface area thereof becomes large, and the dispersibility of the present powder is likely to be further improved.
　本パウダーは、２種以上のＦポリマーの混合物からなる粒子から構成されるパウダーであってもよく、Ｆポリマーからなる粒子の２種以上から構成されるパウダーであってもよい。後者はあるＦポリマーからなる粒子とそれとは異なるＦポリマーからなる粒子とから構成されるパウダーであり、通常あるＦポリマーのパウダーとそれとは異なるＦポリマーのパウダーとの混合物（すなわち、パウダー混合物）である。
　パウダー混合物としては、熱溶融性Ｆポリマーのパウダー（ＴＦＥ単位およびＰＡＶＥ単位を含む、カルボニル基含有基を有する熱溶融性Ｆポリマーのパウダー等。）と非熱溶融性Ｆポリマーのパウダー（非熱溶融性ＰＴＦＥのパウダー等。）の混合物が好ましい。
　本パウダーが上記２種のパウダーの混合物である場合、本パウダーの総量に占める前者の粒子（熱溶融性Ｆポリマーの粒子）の割合は、５０質量％以下が好ましく、２５質量％以下がより好ましい。また、前記割合は、０．１質量％以上が好ましく、１質量％以上がより好ましい。また、前者の粒子のＤ５０は１～４μｍであり、かつ、後者の粒子（非熱溶融性Ｆポリマーの粒子）のＤ５０は０．１～１μｍであるのが好ましい。 The present powder may be a powder composed of particles composed of a mixture of two or more kinds of F polymers, or may be a powder composed of two or more kinds of particles composed of F polymers. The latter is a powder composed of particles made of one F polymer and particles made of a different F polymer, and is usually a mixture of a certain F polymer powder and a different F polymer powder (that is, a powder mixture). be.
The powder mixture includes a heat-meltable F-polymer powder (such as a heat-meltable F-polymer powder having a carbonyl group-containing group including TFE units and PAVE units) and a non-heat-meltable F-polymer powder (non-heat-melting). A mixture of sex PTFE powder and the like) is preferred.
When the present powder is a mixture of the above two kinds of powder, the ratio of the former particles (particles of the heat-meltable F polymer) to the total amount of the present powder is preferably 50% by mass or less, more preferably 25% by mass or less. .. The ratio is preferably 0.1% by mass or more, more preferably 1% by mass or more. The D50 of the former particles is preferably 1 to 4 μm, and the D50 of the latter particles (particles of the non-heat-meltable F polymer) is preferably 0.1 to 1 μm.
　本パウダーを構成する粒子は、Ｆポリマーと異なるポリマーもしくは樹脂または無機物を含有してもよい。ただし、この場合のＦポリマーと異なるポリマーもしくは樹脂または無機物は本組成物中の液状媒体に溶解しないものである。
　Ｆポリマーと異なるポリマーまたは樹脂の具体例としては、芳香族ポリイミド、芳香族マレイミド、スチレンエラストマーのような芳香族エラストマー、芳香族ポリアミック酸等のポリマーや硬化性樹脂の硬化物が挙げられる。ただし、これらのうちには後述の本組成物（２）の場合のように、本組成物中の液状媒体によっては液状媒体に溶解性を有し、本パウダーを構成する粒子の成分とはならないものがある。
　無機物の具体例としては、酸化ケイ素（シリカ）、金属酸化物（酸化ベリリウム、酸化セリウム、アルミナ、ソーダアルミナ、酸化マグネシウム、酸化亜鉛、酸化チタン等）、窒化ホウ素、メタ珪酸マグネシウム（ステアタイト）が挙げられる。 The particles constituting the powder may contain a polymer, resin or inorganic substance different from the F polymer. However, a polymer, resin or inorganic substance different from the F polymer in this case is insoluble in the liquid medium in the present composition.
Specific examples of the polymer or resin different from the F polymer include aromatic elastomers such as aromatic polyimides, aromatic maleimides and styrene elastomers, polymers such as aromatic polyamic acids, and cured products of curable resins. However, among these, as in the case of the present composition (2) described later, some of the liquid media in the present composition have solubility in the liquid medium and do not become a component of the particles constituting the present powder. There is something.
Specific examples of inorganic substances include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). Can be mentioned.
　Ｆポリマーと、Ｆポリマーと異なるポリマーもしくは樹脂または無機物とを含む粒子を含む本パウダーとしては、例えば、Ｆポリマーと、Ｆポリマーと異なるポリマーもしくは樹脂または無機物の微粒子との混合物からなる粒子から構成されたパウダー、Ｆポリマーをコアとし、Ｆポリマーと異なるポリマーもしくは樹脂または無機物微粒子をシェルとするか、または、ＦポリマーをシェルとしＦポリマーと異なるポリマーもしくは樹脂または無機物微粒子をコアとする、コアシェル構造を有する粒子から構成された本パウダー、が挙げられる。後者の本パウダーとしては、例えば、ＦポリマーのパウダーとＦポリマーと異なるポリマーもしくは樹脂のパウダーまたは無機物微粒子からなるパウダーとを衝突、凝集等して、合着させて得られるパウダーが挙げられる。 The powder containing the F polymer and particles containing a polymer or resin or inorganic substance different from the F polymer is composed of, for example, particles composed of a mixture of the F polymer and fine particles of the polymer or resin or inorganic substance different from the F polymer. A core-shell structure in which the powder or F polymer is used as the core and the polymer or resin or inorganic fine particles different from the F polymer is used as the shell, or the F polymer is used as the shell and the polymer or resin or inorganic fine particles different from the F polymer is used as the core. Examples thereof include the present powder composed of the particles having. Examples of the latter powder include a powder obtained by colliding and aggregating an F polymer powder with a polymer or resin powder different from the F polymer or a powder made of inorganic fine particles and coalescing them.
　液状媒体は本パウダーを構成するＦポリマーの粒子（以下、「本パウダー粒子」ともいう。）を溶解しない、２５℃で液状の不活性な液体である。液状媒体は、Ｆポリマー粒子と親和性を有するのが好ましく、例えば液状極性媒体は通常カルボニル基含有基または水酸基含有基を有するＦポリマーの粒子と親和性を有する。本組成物における液状媒体としては、低粘度のものでも高粘度のものでもよい。本組成物における液状媒体としては、低粘度の液状媒体が好ましい。
　以下、低粘度の液状媒体とは、２５℃におけるＢ型粘度計で測定される粘度が１０ｍＰａ・ｓ以下の液状媒体をいい、高粘度の液状媒体とは、２５℃におけるＢ型粘度計で測定される粘度が１０ｍＰａ・ｓ超である液状媒体をいう。 The liquid medium is an inert liquid liquid at 25 ° C. that does not dissolve the F polymer particles (hereinafter, also referred to as “powder particles”) constituting the powder. The liquid medium preferably has an affinity with F polymer particles, for example, a liquid polar medium usually has an affinity with F polymer particles having a carbonyl group-containing group or a hydroxyl group-containing group. The liquid medium in the present composition may be a low-viscosity one or a high-viscosity one. As the liquid medium in this composition, a low-viscosity liquid medium is preferable.
Hereinafter, the low-viscosity liquid medium means a liquid medium having a viscosity of 10 mPa · s or less measured by a B-type viscosity meter at 25 ° C., and the high-viscosity liquid medium means a liquid medium having a viscosity measured by a B-type viscosity meter at 25 ° C. A liquid medium having a viscosity of more than 10 mPa · s.
　低粘度の液状媒体の沸点は、７５℃以上が好ましく、１００℃以上がより好ましい。低粘度の液状媒体の沸点は、３００℃以下が好ましく、２５０℃以下がより好ましい。
　低粘度の液状媒体は、液状極性媒体であってもよく、炭化水素系液状媒体などの非極性の液状媒体であってもよい。液状極性媒体は極性基を有する液状媒体であり、アミド基、カルボニル基、カルボニルオキシ基等の極性基を有する有機化合物からなる液状媒体、および水等の極性を有する無機化合物からなる液状媒体をいう。上記極性基を有する有機化合物としては、アミド、ケトンおよびエステルが好ましく、上記極性を有する無機化合物としては、水が好ましい。
　本組成物（２）における液状極性媒体としては、低粘度の液状媒体である、水、アミド、ケトンおよびエステルから選ばれる液状極性媒体が好ましい。 The boiling point of the low-viscosity liquid medium is preferably 75 ° C. or higher, more preferably 100 ° C. or higher. The boiling point of the low-viscosity liquid medium is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
The low-viscosity liquid medium may be a liquid polar medium or a non-polar liquid medium such as a hydrocarbon-based liquid medium. The liquid polar medium is a liquid medium having a polar group, and refers to a liquid medium made of an organic compound having a polar group such as an amide group, a carbonyl group or a carbonyloxy group, and a liquid medium made of an inorganic compound having a polarity such as water. .. The organic compound having the polar group is preferably an amide, a ketone and an ester, and the inorganic compound having the polarity is preferably water.
As the liquid polar medium in the composition (2), a liquid polar medium selected from water, amides, ketones and esters, which are low-viscosity liquid media, is preferable.
　低粘度の液状媒体であるアミドの具体例としては、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルプロパンアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、Ｎ，Ｎ－ジエチルホルムアミド、ヘキサメチルホスホリックトリアミド、１，３－ジメチル－２－イミダゾリジノンが挙げられる。 Specific examples of amides, which are low-viscosity liquid media, include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropanamide, 3-methoxy-N, Examples thereof include N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N, N-diethylformamide, hexamethylphosphoric triamide and 1,3-dimethyl-2-imidazolidinone.
　低粘度の液状媒体であるケトンの具体例としては、アセトン、メチルエチルケトン、メチルイソプロピルケトン、メチルイソブチルケトン、メチルｎ－ペンチルケトン、メチルイソペンチルケトン、２－へプタノン、シクロペンタノン、シクロヘキサノン、シクロヘプタノンが挙げられる。
　低粘度の液状媒体であるエステルの具体例としては、酢酸メチル、酢酸エチル、酢酸ブチル、乳酸メチル、乳酸エチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、γ－ブチロラクトン、γ－バレロラクトンが挙げられる。
　低粘度の液状媒体としては、水、Ｎ－メチル－２－ピロリドン、γ－ブチロラクトン、シクロヘキサノン、シクロペンタノンが好ましい。 Specific examples of ketones that are low-viscosity liquid media include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone. Non is mentioned.
Specific examples of esters that are low-viscosity liquid media include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and 3-ethoxy. Examples thereof include ethyl propionate, γ-butyrolactone and γ-valerolactone.
As the low-viscosity liquid medium, water, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, and cyclopentanone are preferable.
　高粘度の液状媒体の沸点は、１００℃以上が好ましい。高粘度の液状媒体の沸点は、３５０℃以下が好ましく、３００℃以下がより好ましい。
　高粘度の液状媒体としては、エチレングリコール、ジチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール等のグリコール、かかるグリコールのエーテルやエステル等の誘導体が好ましい。かかるグリコールのエーテルの誘導体としては、グリコールモノアルキルエーテル、グリコールモノアリールエーテル、グリコールモノアルキルエーテルアルキルエステル、グリコールモノアリールエーテルアルキルエステル、グリコールジアルキルエーテルがより好ましく、グリコールモノアルキルエーテルがさらに好ましい。
　高粘度の液状媒体の具体例としては、エチレングリコールモノ－２－エチルヘキシルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、プロピレングリコールモノフェニルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテートが挙げられる。 The boiling point of the high-viscosity liquid medium is preferably 100 ° C. or higher. The boiling point of the high-viscosity liquid medium is preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
As the high-viscosity liquid medium, glycols such as ethylene glycol, ditylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, and derivatives such as ethers and esters of such glycols are preferable. As the derivative of such glycol ether, glycol monoalkyl ether, glycol monoaryl ether, glycol monoalkyl ether alkyl ester, glycol monoaryl ether alkyl ester, and glycol dialkyl ether are more preferable, and glycol monoalkyl ether is further preferable.
Specific examples of the high-viscosity liquid medium include ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, and tripropylene glycol monobutyl ether. , Propylene Glycol Monophenyl Ether, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate.
　本組成物（１）はＦポリマー以外のポリマーや樹脂を含んでいてもよい。ただし、この本組成物（１）が含んでいてもよいとは、前記した本パウダーを構成する粒子以外の部分に含んでいてもよいことを意味する。本組成物（１）におけるＦポリマー以外のポリマーや樹脂は、液状媒体に溶解していてもよく、溶解せずに無機フィラーと同様の粒子として含まれていてもよく、液状媒体を含んで膨潤した粒子として含まれていてもよい。
　一方、本組成物（２）は、Ｆポリマー以外のポリマーや樹脂である極性ポリマーまたはその前駆体を含む。
　以下、まず本組成物（１）に含まれていてもよいＦポリマー以外のポリマーや樹脂を説明し、次いで、そのうちの本組成物（２）に含まれる極性ポリマーおよびその前駆体について説明する。 The present composition (1) may contain a polymer or resin other than the F polymer. However, the fact that the present composition (1) may be contained means that the present powder may be contained in a portion other than the particles constituting the present powder. The polymer or resin other than the F polymer in the present composition (1) may be dissolved in a liquid medium, may be contained as particles similar to the inorganic filler without being dissolved, and may swell including the liquid medium. It may be contained as particles.
On the other hand, the present composition (2) contains a polar polymer which is a polymer other than the F polymer or a resin, or a precursor thereof.
Hereinafter, polymers and resins other than the F polymer that may be contained in the present composition (1) will be described, and then the polar polymer and its precursor contained in the present composition (2) will be described.
　前記Ｆポリマー以外のポリマーや樹脂とは、Ｆポリマーとは異なるものであって、ポリマーやその前駆体（重合や架橋等によりそのポリマーとなりうる低分子化合物やオリゴマーを意味する）、縮合等の反応によりポリマーとなりうる２種以上の化合物の組み合わせ、等を意味する。例えば、熱可塑性樹脂と呼ばれている樹脂は通常ポリマーであり、硬化性樹脂と呼ばれている樹脂は通常反応硬化してポリマーとなる低分子化合物、オリゴマー、低分子化合物の組み合わせ、である。また、ポリマーの物性に応じて、エラストマーやゴムと呼ばれるものであってもよい。以下、Ｆポリマー以外のポリマーや樹脂を総称して、「他の樹脂」ともいう。
　他の樹脂としては芳香族ポリエステル、芳香族ポリイミド、芳香族ポリアミック酸、芳香族ポリアミドイミド、芳香族ポリアミドイミドの前駆体、エポキシ樹脂、マレイミド樹脂、ウレタン樹脂、熱可塑性エラストマー、ポリアミドイミド、ポリフェニレンエーテル、ポリフェニレンオキシド、液晶ポリエステル、多糖類、ナイロン、アクリル樹脂、メタクリル樹脂、ブチラール、シアン酸エステル樹脂、ＡＢＲゴム、セルロース、ＰＶＡアクリル メタクリル、ポリアルキレンエーテル、ポリオキシエチレンアルキルエーテル、Ｆポリマー以外のフルオロポリマーが挙げられる。 Polymers and resins other than the F polymer are different from the F polymer, and are reactions such as polymers, precursors thereof (meaning low molecular weight compounds and oligomers that can become the polymers by polymerization, cross-linking, etc.), condensation, and the like. It means a combination of two or more kinds of compounds that can be polymerized by the above, and the like. For example, a resin called a thermoplastic resin is usually a polymer, and a resin called a curable resin is a combination of a low molecular weight compound, an oligomer, and a low molecular weight compound which are usually reaction-cured to become a polymer. Further, depending on the physical characteristics of the polymer, it may be called an elastomer or rubber. Hereinafter, polymers and resins other than F polymer are collectively referred to as "other resins".
Other resins include aromatic polyesters, aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, precursors of aromatic polyamideimides, epoxy resins, maleimide resins, urethane resins, thermoplastic elastomers, polyamideimides, polyphenylene ethers, etc. Fluoropolymers other than polyphenylene oxide, liquid crystal polyester, polysaccharides, nylon, acrylic resin, methacrylic resin, butyral, cyanate resin, ABR rubber, cellulose, PVA acrylic methacryl, polyalkylene ether, polyoxyethylene alkyl ether, and F polymer Can be mentioned.
　他の樹脂としては、芳香族ポリエステル、芳香族ポリイミド、芳香族ポリアミック酸、芳香族ポリアミドイミド、芳香族ポリアミドイミドの前駆体、ポリフェニレンエーテル、エポキシ樹脂、マレイミド樹脂および熱可塑性エラストマーが好ましい。芳香族ポリイミドは、熱可塑性であってもよく、熱硬化性であってもよい。
　芳香族ポリイミドの具体例としては、「ネオプリム（登録商標）」シリーズ（三菱ガス化学社製）、「スピクセリア（登録商標）」シリーズ（ソマール社製）、「Ｑ－ＰＩＬＯＮ（登録商標）」シリーズ（ピーアイ技術研究所製）、「ＷＩＮＧＯ」シリーズ（ウィンゴーテクノロジー社製）、「トーマイド（登録商標）」シリーズ（Ｔ＆Ｋ　ＴＯＫＡ社製）、「ＫＰＩ－ＭＸ」シリーズ（河村産業社製）、「ユピア（登録商標）－ＡＴ」シリーズ（宇部興産社製）が挙げられる。
　芳香族ポリアミドイミドおよび芳香族ポリアミドイミドの前駆体の具体例としては、「ＨＰＣ－１０００」、「ＨＰＣ－２１００Ｄ」（いずれも昭和電工マテリアルズ社製）が挙げられる。 As other resins, aromatic polyester, aromatic polyimide, aromatic polyamic acid, aromatic polyamideimide, precursor of aromatic polyamideimide, polyphenylene ether, epoxy resin, maleimide resin and thermoplastic elastomer are preferable. The aromatic polyimide may be thermoplastic or thermosetting.
Specific examples of aromatic polyimides include "Neoprim (registered trademark)" series (manufactured by Mitsubishi Gas Chemical Company), "Spixeria (registered trademark)" series (manufactured by Somar), and "Q-PILON (registered trademark)" series ( PI Technology Research Institute), "WINGO" series (Wingo Technology), "Toamide (registered trademark)" series (T & K TOKA), "KPI-MX" series (Kawamura Sangyo), "Yupia (" Registered trademark) -AT "series (manufactured by Ube Kosan Co., Ltd.) can be mentioned.
Specific examples of the aromatic polyamide-imide and the precursor of the aromatic polyamide-imide include "HPC-1000" and "HPC-2100D" (both manufactured by Showa Denko Materials Co., Ltd.).
　スチレンエラストマーとしては、スチレン－ブタジエン共重合体、水添－スチレン－ブタジエン共重合体、水添－スチレン－イソプレン共重合体、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物、およびスチレン－イソプレン－スチレンブロック共重合体の水素添加物が挙げられる。 Examples of the styrene elastomer include styrene-butadiene copolymer, hydrogenated-styrene-butadiene copolymer, hydrogenated-styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene block copolymer. Examples thereof include hydrogenated products of styrene-butadiene-styrene block copolymers, and hydrogenated products of styrene-isoprene-styrene block copolymers.
　ウレタン樹脂としては、例えば、アクリル成分が含まれるウレタン微粒子、また、ホモポリマーであっても、コポリマーであってもよい。具体的には、市販のダイミックビーズＣ Ｍ （大日精化工業株式会社製）、アートパール（根上工業株式会社製）、グランパール（アイカ工業株式会社製）が挙げられる。 The urethane resin may be, for example, urethane fine particles containing an acrylic component, or a homopolymer or a copolymer. Specific examples thereof include commercially available dimic beads CM (manufactured by Dainichiseika Kogyo Co., Ltd.), Art Pearl (manufactured by Negami Kogyo Co., Ltd.), and Grand Pearl (manufactured by Aica Kogyo Co., Ltd.).
　多糖類としては、グリコーゲン、アミロース、アガロース、アミロペクチン、セルロース、デキストリン、グルカン、フルクタン、キサンタンガム、グアーガム、カゼイン、アラビアガム、ゼラチン、アガロペクチン、アラビナン、カードラン、カロース、カルボキシメチルデンプン、キチン、キトサン、クインスシード、グルコマンナン、ジェランガム、タマリンシードガム、デキストラン、ニゲラン、ヒアルロン酸、プスツラン、フノラン、ペクチン、ポルフィラン、ラミナラン、リケナン、カラギーナン、アルギン酸、トラガカントガム、アルカシーガム、ローカストビーンガムが挙げられる。 Polysaccharides include glycogen, amylose, agarose, amyropectin, cellulose, dextrin, glucan, fructan, xanthan gum, guar gum, casein, arabic gum, gelatin, agaropectin, arabinan, curdlan, carose, carboxymethyl starch, chitin, chitosan, quince. Seeds, glucomannan, gellan gum, tamarin seed gum, dextrin, nigeran, hyaluronic acid, pustulose, funoran, pectin, porphyran, laminaran, likenan, curdlanan, alginic acid, tragacanth gum, alkathy gum, locust bean gum.
　アクリル樹脂、メタクリル樹脂としては、ポリアクリレート、ポリメタクリレート、エチレン－メチルメタクリレート共重合体、エチレン－メチルアクリレート共重合体、エチレン－エチルアクリレート共重合体、エチレン－ブチルアクリレート共重合体、エチレン－酢酸ビニル共重合体が挙げられる。
　アクリル樹脂、メタクリル樹脂としては、例えば、市販品では、楠本化成社製Ｎｅｏｃｒｙｌシリーズが挙げられる。 Acrylic resins and methacrylic resins include polyacrylates, polymethacrylates, ethylene-methylmethacrylate copolymers, ethylene-methylacrylate copolymers, ethylene-ethylacrylate copolymers, ethylene-butylacrylate copolymers, and ethylene-vinyl acetates. Examples include copolymers.
Examples of the acrylic resin and the methacrylic resin include the Neocryl series manufactured by Kusumoto Kasei Co., Ltd. as a commercially available product.
　ナイロンとしては、ナイロン６、ナイロン１１、およびナイロン１２が挙げられる。
　ブチラール樹脂の市販品としては、積水化学工業社製エスレック（登録商標）Ｂシリーズ、Ｋ（ＫＳ）シリーズ、ＳＶシリーズ、クラレ社製モビタール（登録商標）シリーズが挙げられる。
　シアン酸エステル樹脂としては、ビスフェノールＡ型シアン酸、ビスフェノールＦ型シアン酸エステル樹脂、６ＦビスフェノールＡジシアン酸エステル樹脂、ビスフェノールＥ型ジシアン酸エステル樹脂、テトラメチルビスフェノールＦジシアン酸エステル樹脂、ビスフェノールＭジシアン酸エステル樹脂、ジシクロペンタジエンビスフェノールジシアン酸エステル樹脂、およびシアン酸ノボラック樹脂が挙げられる。 Examples of nylon include nylon 6, nylon 11, and nylon 12.
Examples of commercially available butyral resins include Sekisui Chemical's Eslek (registered trademark) B series, K (KS) series, SV series, and Kuraray's Mobital (registered trademark) series.
Examples of the bisphenol ester resin include bisphenol A type cyanic acid, bisphenol F type cyanate ester resin, 6F bisphenol A dicyan acid ester resin, bisphenol E type dicyan acid ester resin, tetramethyl bisphenol F dicyan acid ester resin, and bisphenol M dicyan acid. Examples thereof include ester resins, dicyclopentadienbisphenol disyanic acid ester resins, and novolak cyanate resins.
　エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ｔｅｒｔ－ブチル－カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、トリメチロール型エポキシ樹脂、ハロゲン化エポキシ樹脂が挙げられる。 Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, and glycidylamine type epoxy resin. Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogen Epoxy resin can be mentioned.
　熱可塑性エラストマーの市販品としては、ＴＲシリーズ（スチレン・ブタジエン熱可塑性エラストマー、ＪＳＲ株式会社製）、ＲＢシリーズ（ポリブタジエン系熱可塑性エラストマー、ＪＳＲ株式会社製）、ＪＳＲ　ＥＸＥＬＩＮＫ（オレフィン系熱可塑性エラストマー、ＪＳＲ株式会社製）、ＤＹＮＡＲＯＮ（登録商標）シリーズ（水添熱可塑性エラストマー、ＪＳＲ株式会社製）、サーモラン（登録商標）（オレフィン系熱可塑性エラストマー、三菱化学株式会社製）、エポックスＴＰＥシリーズ（オレフィン系熱可塑性エラストマー、住友化学株式会社製）、セプトン（登録商標）シリーズ（水添スチレン系熱可塑性エラストマー、株式会社クラレ製）、タフテック（登録商標）（水添スチレン系熱可塑性エラストマー、旭化成株式会社製）が挙げられる。
　Ｆポリマーの以外のフルオロポリマーとしては、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリクロロトリフロオロエチレン等が挙げられる。 Commercially available thermoplastic elastomers include TR series (styrene / butadiene thermoplastic elastomer, manufactured by JSR Co., Ltd.), RB series (polybutadiene-based thermoplastic elastomer, manufactured by JSR Co., Ltd.), and JSR EXELINK (olefin-based thermoplastic elastomer, JSR). DYNARON (registered trademark) series (hydrogenated thermoplastic elastomer, manufactured by JSR Co., Ltd.), Thermolan (registered trademark) (olefin-based thermoplastic elastomer, manufactured by Mitsubishi Chemical Corporation), Epox TPE series (olefin-based heat) Plastic Elastomer, Sumitomo Chemical Co., Ltd.), Septon (Registered Trademark) Series (Hydrogenized styrene Thermoplastic Elastomer, Claret Co., Ltd.), Tough Tech (Registered Trademark) (Hydrogenized Styrene Thermoplastic Elastomer, Asahi Kasei Co., Ltd.) Can be mentioned.
Examples of the fluoropolymer other than the F polymer include polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene and the like.
　前記のように、本組成物（２）は、前記他の樹脂として極性ポリマーまたはその前駆体を含む。
　本組成物（２）における極性ポリマーは、ポリマーの主鎖または側鎖に極性官能基を有するポリマーであり、かかる極性ポリマーの前駆体は、加熱等により重合が進行して極性ポリマーになり得る前駆体である。極性官能基は通常、ヘテロ原子またはヘテロ原子を含む原子団である。ヘテロ原子は例えば酸素、硫黄、窒素、フッ素以外のハロゲン原子が挙げられる。極性ポリマーの前駆体は、このような極性官能基または重合によりこのような極性官能基となりうる基を有する前駆体である。
　ポリマーの主鎖に極性官能基を有するポリマーとしては、主鎖にエーテル結合、エステル結合、アミド結合、イミド結合、チオエーテル結合、スルフィド結合またはジスルフィド結合を有するポリマーが挙げられる。 As described above, the composition (2) contains a polar polymer or a precursor thereof as the other resin.
The polar polymer in the present composition (2) is a polymer having a polar functional group in the main chain or side chain of the polymer, and the precursor of the polar polymer is a precursor that can be polymerized by heating or the like to become a polar polymer. The body. Polar functional groups are usually heteroatoms or atomic groups containing heteroatoms. Heteroatoms include, for example, halogen atoms other than oxygen, sulfur, nitrogen and fluorine. A precursor of a polar polymer is such a polar functional group or a precursor having a group that can become such a polar functional group by polymerization.
Examples of the polymer having a polar functional group in the main chain of the polymer include a polymer having an ether bond, an ester bond, an amide bond, an imide bond, a thioether bond, a sulfide bond or a disulfide bond in the main chain.
　ポリマーの側鎖に極性官能基を有するポリマーにおける極性官能基としては、前記カルボニル基含有基、前記水酸基含有基、チオール基、スルフィド基、スルホニル基、スルホキシル基、アミノ基、アミド基等が挙げられ、カルボニル基含有基および水酸基含有基が好ましい。この場合、Ｆポリマーと極性ポリマー（またはその前期体）および液状媒体との相互作用が向上しやすく、上述した作用機構が顕著に発現しやすくなる。 Examples of the polar functional group in the polymer having a polar functional group on the side chain of the polymer include the carbonyl group-containing group, the hydroxyl group-containing group, the thiol group, the sulfide group, the sulfonyl group, the sulfoxyl group, the amino group and the amide group. , A carbonyl group-containing group and a hydroxyl group-containing group are preferable. In this case, the interaction between the F polymer and the polar polymer (or its predecessor) and the liquid medium is likely to be improved, and the above-mentioned mechanism of action is likely to be remarkably developed.
　極性ポリマーおよびその前駆体の分子量は３０００以上が好ましく、５０００以上がより好ましく、１００００以上がより好ましい。極性ポリマーおよびその前駆体の分子量は５００００以下が好ましく、３００００以下がより好ましい。この場合、極性ポリマーおよびその前駆体がＦポリマーおよび液状極性媒体と相互作用しやすく、本組成物（２）が分散安定性等の物性に優れやすい。
　極性ポリマーおよびその前駆体は、液状極性媒体に溶解するものであるのが好ましい。 The molecular weight of the polar polymer and its precursor is preferably 3000 or more, more preferably 5000 or more, and even more preferably 10,000 or more. The molecular weight of the polar polymer and its precursor is preferably 50,000 or less, more preferably 30,000 or less. In this case, the polar polymer and its precursor easily interact with the F polymer and the liquid polar medium, and the present composition (2) tends to have excellent physical properties such as dispersion stability.
The polar polymer and its precursor are preferably those that are soluble in a liquid polar medium.
　極性ポリマーとしては、ポリアセタール、ポリアルキレングリコール、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエーテルスルホン等のエーテル系ポリマー、ポリアルキレンテレフタレート、ポリアルキレンナフタレート等のエステル系ポリマー、ナイロン、アラミド等のアミド系ポリマー、ポリイミド、ポリアミドイミド等のイミド系ポリマー、ポリチオール、ポリスルフィド、ポリジスルフィド等のスルフィド系ポリマー、ポリエーテルスルホン、ポリフェニルスルホン等のスルホン系ポリマー、ポリビニルアルコール、ポリアクリレート、ポリメタクリレート、ポリビニルピロリドン、ポリ酢酸ビニル、カルボキシビニルポリマー、Ｆポリマー以外のポリハロゲン化ビニル、ポリハロゲン化ビニリデン等のビニル系ポリマー、多糖類およびこれらの前駆体が挙げられる。また極性ポリマーとしてポリオレフィンに前記極性官能基が導入されたポリマーも挙げられる。なお、多糖類としては、前記他の樹脂として挙げた多糖類が挙げられる。
　これら極性ポリマーは複数種の単量体からなる共重合体であってもよい。 Examples of the polar polymer include ether polymers such as polyacetal, polyalkylene glycol, polyether ketone, polyether ether ketone, and polyether sulfone, ester polymers such as polyalkylene terephthalate and polyalkylene naphthalate, and amide polymers such as nylon and aramid. Polymers, imide-based polymers such as polyimide and polyamideimide, sulfide-based polymers such as polythiol, polysulfide, and polydisulfide, sulfonate-based polymers such as polyether sulfone and polyphenyl sulfone, polyvinyl alcohol, polyacrylate, polymethacrylate, polyvinylpyrrolidone, and poly. Examples thereof include vinyl acetate, carboxyvinyl polymers, polyhalogenated vinyls other than F polymers, vinyl-based polymers such as polyhalogenated vinylidene, polysaccharides and precursors thereof. Further, as a polar polymer, a polymer in which the polar functional group is introduced into polyolefin can also be mentioned. Examples of the polysaccharide include the polysaccharides mentioned as the other resins.
These polar polymers may be copolymers composed of a plurality of types of monomers.
　前記極性ポリマーおよびその前駆体としては、イミド系ポリマー、イミド系ポリマーの前駆体、ビニル系ポリマーおよび多糖類が好ましい。
　好ましいイミド系ポリマーおよびその前駆体としては、ポリイミド、ポリアミドイミド、ポリアミック酸、ポリアミドイミド前駆体が挙げられ、芳香族ポリイミド、芳香族ポリアミドイミド、芳香族ポリアミック酸、芳香族ポリアミドイミド前駆体がより好ましい。
　イミド系ポリマーの具体例としては、「ネオプリム（登録商標）」シリーズ（三菱ガス化学社製）、「スピクセリア（登録商標）」シリーズ（ソマール社製）、「Ｑ－ＰＩＬＯＮ（登録商標）」シリーズ（ピーアイ技術研究所製）、「ＷＩＮＧＯ」シリーズ（ウィンゴーテクノロジー社製）、「トーマイド（登録商標）」シリーズ（Ｔ＆Ｋ　ＴＯＫＡ社製）、「ＫＰＩ－ＭＸ」シリーズ（河村産業社製）、「ユピア（登録商標）－ＡＴ」シリーズ（宇部興産社製）、「ＨＰＣ－１０００」、「ＨＰＣ－２１００Ｄ」（以上、昭和電工マテリアルズ社製）が挙げられる。 As the polar polymer and its precursor, an imide-based polymer, a precursor of the imide-based polymer, a vinyl-based polymer and a polysaccharide are preferable.
Preferred imide-based polymers and precursors thereof include polyimide, polyamide-imide, polyamic acid, and polyamide-imide precursors, with aromatic polyimides, aromatic polyamideimides, aromatic polyamic acids, and aromatic polyamide-imide precursors being more preferred. ..
Specific examples of imide-based polymers include "Neoprim (registered trademark)" series (manufactured by Mitsubishi Gas Chemical Company), "Spixeria (registered trademark)" series (manufactured by Somar), and "Q-PILON (registered trademark)" series ( PI Technology Research Institute), "WINGO" series (Wingo Technology), "Tombide (registered trademark)" series (T & K TOKA), "KPI-MX" series (Kawamura Sangyo), "Yupia (" Examples include the "AT" series (manufactured by Ube Kosan Co., Ltd.), "HPC-1000", and "HPC-2100D" (manufactured by Showa Denko Materials Co., Ltd.).
　好ましいビニル系ポリマーとしては、ポリビニルアルコール等のビニルアルコール系ポリマー、ポリビニルピロリドン等のビニルピロリドン系ポリマー、ポリアクリル酸等のアクリル酸系ポリマー、カルボキシビニルポリマー等のカルボキシビニル系ポリマーが挙げられ、ビニルアルコール系ポリマーがより好ましい。
　ビニルアルコール系ポリマーとしては、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルアルコールの部分アセチル化物、ポリビニルアルコールの部分アセタール化物、ビニルアルコールとビニルブチラールと酢酸ビニルの共重合体が好ましい。
　ビニルアルコール系ポリマーの具体例としては、「エスレック（登録商標）Ｂ」シリーズ、「エスレック（登録商標）Ｋ（ＫＳ）」シリーズ、「エスレック（登録商標）ＳＶ」シリーズ（以上、積水化学工業社製」、「モビタール（登録商標）」シリーズ（クラレ社製）が挙げられる。
　アクリル酸系ポリマーとしては、ポリアクリル酸、ポリアクリル酸メチル、ポリアクリル酸エチル等のポリアクリレート、ポリ－α－ハロアクリレート、ポリ－α－シアノアクリレート、ポリアクリルアミド、ポリアクリル酸ナトリウムが挙げられる。 Preferred vinyl-based polymers include vinyl alcohol-based polymers such as polyvinyl alcohol, vinylpyrrolidone-based polymers such as polyvinylpyrrolidone, acrylic acid-based polymers such as polyacrylic acid, and carboxyvinyl-based polymers such as carboxyvinyl polymer. The based polymer is more preferable.
As the vinyl alcohol-based polymer, polyvinyl alcohol, polyvinyl acetate, a partially acetylated product of polyvinyl alcohol, a partially acetal product of polyvinyl alcohol, and a copolymer of vinyl alcohol, vinyl butyral, and vinyl acetate are preferable.
Specific examples of vinyl alcohol polymers include "Eslek (registered trademark) B" series, "Eslek (registered trademark) K (KS)" series, and "Eslek (registered trademark) SV" series (all manufactured by Sekisui Chemical Co., Ltd.). , "Mobital (registered trademark)" series (manufactured by Kuraray).
Examples of the acrylic acid-based polymer include polyacrylates such as polyacrylic acid, methyl polyacrylate and ethyl polyacrylate, poly-α-haloacrylate, poly-α-cyanoacrylate, polyacrylamide, and sodium polyacrylate.
　好ましい多糖類としては、前記多糖類のうち、グリコーゲン、アミロース、アガロース、アミロペクチン、セルロース、デキストリン、グルカン、フルクタン、キチンが挙げられる。セルロースとしてはカルボキシメチルセルロースが好ましい。カルボキシメチルセルロースは、カルボキシメチルセルロースナトリウム、カルボキシメチルセルロースアンモニウム等のカルボキシメチルセルロース塩であってもよい。 Preferred polysaccharides include glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, and chitin among the polysaccharides. Carboxymethyl cellulose is preferable as the cellulose. The carboxymethyl cellulose may be a carboxymethyl cellulose salt such as sodium carboxymethyl cellulose or ammonium carboxymethyl cellulose.
　本組成物がＦポリマー以外のポリマー等の他の樹脂を含む場合、本組成物中の他の樹脂は液状媒体に溶解しているまたは液状媒体により膨潤していることが好ましく、特に極性ポリマーやその前駆体は液状媒体に溶解していることが好ましい。
　液状媒体に溶解しない他の樹脂は、下記無機フィラーの粒子と同様の粒子として本組成物に含まれていることが好ましい。無機フィラーの粒子と同様の粒子としては硬化性樹脂の硬化物からなる粒子が好ましい。 When the present composition contains other resins such as polymers other than the F polymer, the other resins in the present composition are preferably dissolved in a liquid medium or swollen by a liquid medium, particularly polar polymers and The precursor is preferably dissolved in a liquid medium.
It is preferable that the other resin that does not dissolve in the liquid medium is contained in the present composition as particles similar to the particles of the following inorganic filler. As the particles similar to the particles of the inorganic filler, particles made of a cured product of a curable resin are preferable.
　本組成物は、無機フィラーの粒子を含んでいてもよい。
　無機フィラーは、本組成物や本組成物を希釈して得られる分散液を種々の塗膜や成形物の形成に使用した時、得られる塗膜や成形物の物性を向上させるために使用され、その種類は、塗膜や成形物の目的に応じて適宜選択される。
　例えば、塗膜や成形物の誘電率を向上させる目的の場合には、無機フィラーとしては、ペロブスカイト型強誘電体フィラーおよびビスマス層状ペロブスカイト型強誘電体フィラーが好ましい。
　ペロブスカイト型強誘電体としては、チタン酸バリウム、ジルコン酸チタン酸鉛、チタン酸鉛、酸化ジルコニウム、酸化チタンが挙げられる。一方、ビスマス層状ペロブスカイト型強誘電体としては、タンタル酸ビスマスストロンチウム、ニオブ酸ビスマスストロンチウム、チタン酸ビスマスが挙げられる。 The composition may contain particles of the inorganic filler.
The inorganic filler is used to improve the physical properties of the coating film or the molded product obtained when the composition or the dispersion obtained by diluting the composition is used for forming various coating films or molded products. , The type is appropriately selected according to the purpose of the coating film or the molded product.
For example, for the purpose of improving the dielectric constant of a coating film or a molded product, the perovskite-type ferroelectric filler and the bismuth layered perovskite-type ferroelectric filler are preferable as the inorganic filler.
Examples of the perovskite-type ferroelectric substance include barium titanate, lead zirconate titanate, lead titanate, zirconium oxide, and titanium oxide. On the other hand, examples of the bismuth layered perovskite type ferroelectric substance include bismuth strontium tantalate, bismuth strontium niobate, and bismuth titanate.
　例えば、塗膜や成形物の誘電率および誘電正接、若しくは線膨張率を低下させる目的の場合には、無機フィラーとしては、低誘電率、低誘電正接または低線膨張率の無機フィラーが用いられる。
　かかる無機フィラーとしては、窒化ホウ素フィラー、酸化ベリリウムフィラー（べリリアフィラー）、酸化ケイ素フィラー（シリカフィラー）、ウォラストナイトフィラー、およびメタ珪酸マグネシウムフィラー（ステアタイトフィラー）が好ましい。 For example, for the purpose of reducing the dielectric constant and dielectric loss tangent or linear expansion rate of a coating film or a molded product, a low dielectric constant, low dielectric loss tangent or low linear expansion rate inorganic filler is used as the inorganic filler. ..
As such an inorganic filler, a boron nitride filler, a beryllium oxide filler (berilia filler), a silicon oxide filler (silica filler), a wollastonite filler, and a magnesium metasilicate filler (steatite filler) are preferable.
　例えば、塗膜や成形物の熱伝導性または耐擦傷性を向上させる目的の場合には、無機フィラーとしては、金属酸化物のフィラーが用いられる。
　金属酸化物としては、酸化アルミニウム、酸化鉛、酸化鉄、酸化錫、酸化マグネシウム、酸化チタン、酸化亜鉛、五酸化アンチモン、酸化ジルコニウム、酸化ランタン、酸化ネオジウム、酸化セリウムおよび酸化ニオブが好ましく、酸化アルミニウムがより好ましい。 For example, for the purpose of improving the thermal conductivity or scratch resistance of a coating film or a molded product, a metal oxide filler is used as the inorganic filler.
As the metal oxide, aluminum oxide, lead oxide, iron oxide, tin oxide, magnesium oxide, titanium oxide, zinc oxide, antimony pentoxide, zirconium oxide, lanthanum oxide, neodium oxide, cerium oxide and niobium oxide are preferable, and aluminum oxide is preferable. Is more preferable.
　また、これら以外の無機フィラーとして、ガラス繊維フィラーやカーボンフィラーを用いてもよい。
　カーボンフィラーとしては、炭素繊維（カーボンファイバー）、カーボンブラック、グラフェン、グラフェンオキシド、フラーレン、グラファイトおよびグラファイトオキシドが挙げられる。炭素繊維としては、ポリアクリロニトリル系炭素繊維、ピッチ系炭素繊維、気相成長炭素繊維、カーボンナノチューブ（シングルウォール、ダブルウォール、マルチウォール、カップ積層型等）が挙げられる。 Further, as the inorganic filler other than these, a glass fiber filler or a carbon filler may be used.
Examples of the carbon filler include carbon fiber (carbon fiber), carbon black, graphene, graphene oxide, fullerene, graphite and graphite oxide. Examples of carbon fibers include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, vapor-phase-grown carbon fibers, and carbon nanotubes (single-wall, double-wall, multi-wall, cup-laminated type, etc.).
　分散性の観点から、無機フィラーとしては、窒化ホウ素フィラー、シリカフィラーおよびメタ珪酸マグネシウムフィラーが好ましく、シリカフィラーがより好ましい。これらのフィラーは、焼成されたセラミックスフィラーであってもよい。 From the viewpoint of dispersibility, as the inorganic filler, a boron nitride filler, a silica filler and a magnesium metasilicate filler are preferable, and a silica filler is more preferable. These fillers may be fired ceramic fillers.
　無機フィラー粒子（すなわち、無機フィラーを構成する粒子）の形状は、目的に応じて適宜選定され、塊状粒子でも繊維状粒子でもよい。塊状粒子からなるフィラーを使用すれば、塗膜や成形物の表面平坦性が向上し、その表面の摺動性が良好となり、耐擦傷性が向上しやすい。一方、繊維状粒子からなる無機フィラーを使用すれば、塗膜や成形物の表面にフィラー粒子の一部が露出し、例えば製品表面の耐摩耗性と耐擦傷性とを改良しやすい。
　塊状粒子からなる無機フィラーの場合、その平均粒子径（Ｄ５０）は、０．０２～２００μｍが好ましい。また、繊維状粒子からなる無機フィラーの場合、その平均繊維長は、０．０５～３００μｍが好ましい。繊維状の無機フィラーの平均繊維径は、０．０１～１５μｍが好ましい。また上記形状に加えて前記無機フィラーを構成する粒子は板状、中空状、ハニカム状等の種々の形状を有してもよい。 The shape of the inorganic filler particles (that is, the particles constituting the inorganic filler) is appropriately selected depending on the intended purpose, and may be agglomerate particles or fibrous particles. If a filler composed of agglomerated particles is used, the surface flatness of the coating film or the molded product is improved, the slidability of the surface is improved, and the scratch resistance is likely to be improved. On the other hand, if an inorganic filler composed of fibrous particles is used, a part of the filler particles is exposed on the surface of the coating film or the molded product, and it is easy to improve the wear resistance and scratch resistance of the product surface, for example.
In the case of an inorganic filler composed of agglomerated particles, the average particle size (D50) is preferably 0.02 to 200 μm. Further, in the case of an inorganic filler composed of fibrous particles, the average fiber length thereof is preferably 0.05 to 300 μm. The average fiber diameter of the fibrous inorganic filler is preferably 0.01 to 15 μm. In addition to the above shapes, the particles constituting the inorganic filler may have various shapes such as a plate shape, a hollow shape, and a honeycomb shape.
　前記無機フィラー粒子は、その表面の少なくとも一部が、表面処理されているのが好ましい。
　前記無機フィラーは、シランカップリング剤で表面処理されている無機フィラー粒子からなるのが好ましい。かかる無機フィラーは、本パウダーとの親和性に優れ、本分散液の分散性を向上させやすい。
　シランカップリング剤としては、３－アミノプロピルトリエトキシシラン、ビニルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシランおよび３－イソシアネートプロピルトリエトキシシランが好ましい。 It is preferable that at least a part of the surface of the inorganic filler particles is surface-treated.
The inorganic filler is preferably composed of inorganic filler particles surface-treated with a silane coupling agent. Such an inorganic filler has an excellent affinity with the present powder and tends to improve the dispersibility of the present dispersion.
Silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-. Ixylpropyltriethoxysilane is preferred.
　無機フィラーの好適な具体例としては、シリカフィラー（アドマテックス社製の「アドマファイン（登録商標）」シリーズ等）、ジカプリン酸プロピレングリコール等のエステルで表面処理された酸化亜鉛フィラー（堺化学工業株式会社製の「ＦＩＮＥＸ（登録商標）」シリーズ等）、球状溶融シリカフィラー（デンカ社製の「ＳＦＰ（登録商標）」シリーズ等）、多価アルコールおよび無機物で被覆処理された酸化チタンフィラー（石原産業社製の「タイペーク（登録商標）」シリーズ等）、アルキルシランで表面処理されたルチル型酸化チタンフィラー（テイカ社製の「ＪＭＴ（登録商標）」シリーズ等）、中空状シリカフィラー（太平洋セメント社製の「Ｅ-ＳＰＨＥＲＥＳ」シリーズ、日鉄鉱業社製の「シリナックス」シリーズ、エマーソン・アンド・カミング社製「エココスフイヤー」シリーズ等）、タルクフィラー（日本タルク社製の「ＳＧ」シリーズ等）、ステアタイトフィラー（日本タルク社製の「ＢＳＴ」シリーズ等、窒化ホウ素フィラー（昭和電工社製の「ＵＨＰ」シリーズ、デンカ製の「ＨＧＰ」シリーズ、「ＧＰ」シリーズ等））が挙げられる。 Suitable specific examples of the inorganic filler are zinc oxide fillers surface-treated with esters such as silica fillers (“Admafine (registered trademark)” series manufactured by Admatex) and propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.). Company's "FINEX (registered trademark)" series, etc.), spherical molten silica filler (Denka's "SFP (registered trademark)" series, etc.), titanium oxide filler coated with polyhydric alcohol and inorganic substances (Ishihara Sangyo) "Typake (registered trademark)" series manufactured by Teika Co., Ltd.), rutile-type titanium oxide filler surface-treated with alkylsilane ("JMT (registered trademark)" series manufactured by Teika Co., Ltd.), hollow silica filler (Pacific Cement Co., Ltd.) "E-SPHERES" series, "Sirinax" series manufactured by Nittetsu Mining Co., Ltd., "Ecocos Fire" series manufactured by Emerson & Cumming, etc.), Tarkufiller ("SG" series manufactured by Nippon Taruku Co., Ltd., etc.), Examples thereof include steatite fillers (“BST” series manufactured by Nippon Tarku Co., Ltd., boron nitride fillers (“UHP” series manufactured by Showa Denko Co., Ltd., “HGP” series, “GP” series manufactured by Denka Co., Ltd., etc.)).
　さらに本組成物においては、前記本パウダー粒子、液状媒体、他の樹脂および無機フィラー以外の成分を含んでいてもよい。他の成分の例としては、分散安定性とハンドリング性とを向上させる観点から界面活性剤が挙げられる。
　界面活性剤は、ノニオン性界面活性剤が好ましい。
　界面活性剤の親水部位は、オキシアルキレン基またはアルコール性水酸基を有するのが好ましい。
　オキシアルキレン基は、１種から構成されていてもよく、２種以上から構成されていてもよい。後者の場合、種類の違うオキシアルキレン基は、ランダム状に配置されていてもよく、ブロック状に配置されていてもよい。
　オキシアルキレン基としては、オキシエチレン基が好ましい。 Further, the composition may contain components other than the powder particles, the liquid medium, other resins and the inorganic filler. Examples of other components include surfactants from the viewpoint of improving dispersion stability and handleability.
The surfactant is preferably a nonionic surfactant.
The hydrophilic moiety of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
The oxyalkylene group may be composed of one kind or two or more kinds. In the latter case, the different types of oxyalkylene groups may be randomly arranged or may be arranged in a block shape.
As the oxyalkylene group, an oxyethylene group is preferable.
　界面活性剤の疎水部位は、アセチレン基、ポリシロキサン基、ペルフルオロアルキル基またはペルフルオロアルケニル基を有するのが好ましい。換言すれば、界面活性剤は、アセチレン系界面活性剤、シリコーン系界面活性剤またはフッ素系界面活性剤が好ましく、シリコーン系界面活性剤がより好ましい。
　フッ素系界面活性剤としては、水酸基、特に、アルコール性水酸基、またはオキシアルキレン基と、ペルフルオロアルキル基またはペルフルオロアルケニル基とを有するフッ素系界面活性剤が好ましい。
　界面活性剤の具体例としては、「フタージェント」シリーズ（ネオス社製）、「サーフロン」シリーズ（ＡＧＣセイミケミカル社製）、「メガファック」シリーズ（ＤＩＣ社製）、「ユニダイン」シリーズ（ダイキン工業社製）、「ＢＹＫ－３４７」、「ＢＹＫ－３４９」、「ＢＹＫ－３７８」、「ＢＹＫ－３４５０」、「ＢＹＫ－３４５１」、「ＢＹＫ－３４５５」、「ＢＹＫ－３４５６」（ビックケミー・ジャパン社製）、「ＫＦ－６０１１」、「ＫＦ－６０４３」（信越化学工業社製）、「Ｔｅｒｇｉｔｏｌ」シリーズ（ダウケミカル社製、「Ｔｅｒｇｉｔｏｌ　ＴＭＮ－１００Ｘ」等。）が挙げられる。
　本組成物が界面活性剤を含む場合（ただし、無機フィラーがあらかじめ界面活性剤で処理された無機フィラーである場合、その無機フィラーに付着した界面活性剤を除く）、その量は本組成物が第２の液状媒体で希釈して得られる後述の本分散液において、本分散液中の含有量は、１から１５質量％が好ましい。この場合、成分間の親和性が増し、本分散液の分散安定性がより向上しやすい。 The hydrophobic moiety of the surfactant preferably has an acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group. In other words, the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
As the fluorine-based surfactant, a fluorine-based surfactant having a hydroxyl group, particularly an alcoholic hydroxyl group or an oxyalkylene group, and a perfluoroalkyl group or a perfluoroalkenyl group is preferable.
Specific examples of surfactants include "Futergent" series (manufactured by Neos), "Surflon" series (manufactured by AGC Seimi Chemical), "Megafuck" series (manufactured by DIC), and "Unidyne" series (Daikin Industries). (Made by), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (Big Chemie Japan) , "KF-6011", "KF-6043" (manufactured by Shin-Etsu Chemical Co., Ltd.), "Tergitol" series (manufactured by Dow Chemical Corporation, "Tergitol TMN-100X", etc.).
When the present composition contains a surfactant (however, when the inorganic filler is an inorganic filler previously treated with a surfactant, the surfactant attached to the inorganic filler is excluded), the amount thereof is determined by the present composition. In the present dispersion obtained by diluting with a second liquid medium, the content in the present dispersion is preferably 1 to 15% by mass. In this case, the affinity between the components is increased, and the dispersion stability of the present dispersion is more likely to be improved.
　本組成物は、上記成分以外にも、チキソ性付与剤、粘度調節剤、消泡剤、シランカップリング剤、脱水剤、可塑剤、耐候剤、酸化防止剤、熱安定剤、滑剤、帯電防止剤、増白剤、着色剤、導電剤、離型剤、表面処理剤、難燃剤、各種フィラー等の添加剤をさらに含んでいてもよい。 In addition to the above components, the present composition also contains a tyxicity-imparting 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. It may further contain additives such as agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, and various fillers.
　本組成物（１）は、Ｆポリマーのパウダーに由来する粒子と液状媒体を含有し、固形分濃度が４０質量％以上であり、Ｂ型粘度計で測定される粘度が８０００～１０００００ｍＰａ・ｓである、組成物である。本組成物（１）はスラリー状、ペースト状またはゲル状の組成物であり、ペーストと呼ばれる高粘度の組成物であることが好ましい。
　本組成物（１）の固形分濃度は、５０質量％以上であることが好ましい。本組成物（１）の固形分濃度は、９０質量％以下であることが好ましく、８０質量％以下であることがより好ましい。
　本組成物（１）のＢ型粘度計で測定される粘度は、１００００ｍＰａ・ｓ以上が好ましい。上記粘度は、８００００ｍＰａ・ｓ以下が好ましく、４００００ｍＰａ・ｓ以下がより好ましく、２００００ｍＰａ・ｓ以下がさらに好ましい。
　本組成物（１）における液状媒体は低粘度の液状媒体であることが好ましく、また、本組成物（１）は２種以上の液状媒体を含んでいてもよい。
　本組成物（１）は、前記他の樹脂や無機フィラー等の他の成分を含んでいてもよい。他の樹脂が極性ポリマーやその前駆体以外の他の樹脂である場合、他の樹脂は液状媒体に溶解していることが好ましく、その場合他の樹脂を溶解した液状媒体としては液状極性媒体以外の液状媒体であってもよい。 The composition (1) contains particles derived from F polymer powder and a liquid medium, has a solid content concentration of 40% by mass or more, and has a viscosity measured by a B-type viscometer of 8000 to 100,000 mPa · s. There is a composition. The present composition (1) is a slurry-like, paste-like or gel-like composition, and is preferably a high-viscosity composition called a paste.
The solid content concentration of the composition (1) is preferably 50% by mass or more. The solid content concentration of the composition (1) is preferably 90% by mass or less, more preferably 80% by mass or less.
The viscosity measured by the B-type viscometer of the present composition (1) is preferably 10,000 mPa · s or more. The viscosity is preferably 80,000 mPa · s or less, more preferably 40,000 mPa · s or less, and even more preferably 20,000 mPa · s or less.
The liquid medium in the present composition (1) is preferably a low-viscosity liquid medium, and the present composition (1) may contain two or more kinds of liquid media.
The present composition (1) may contain other components such as the other resin and the inorganic filler. When the other resin is a resin other than the polar polymer or its precursor, the other resin is preferably dissolved in a liquid medium, and in that case, the liquid medium in which the other resin is dissolved is other than the liquid polar medium. It may be a liquid medium of.
　本組成物（１）としては、その泡沫体積比率が１０％以下であるものが好ましい。
　泡沫体積比率は、標準大気圧かつ２０℃における本組成物（１）の体積（ＶＮ）と、それを０．００３ＭＰａまで減圧した際の泡を合わせた体積（ＶＶ）とを測定し、以下の算出式で求められる値である。
　泡沫体積比率［％］＝１００×（ＶＶ－ＶＮ）／ＶＮ The composition (1) preferably has a foam volume ratio of 10% or less.
The foam volume ratio was measured by measuring the volume ( VN ) of the present composition (1) at standard atmospheric pressure and 20 ° C. and the combined volume ( VV ) of the foam when the pressure was reduced to 0.003 MPa. It is a value obtained by the following formula.
Foam volume ratio [%] = 100 x ( VV - VN) / VN
　本組成物（１）は、例えば、Ｆポリマーのパウダーと液状媒体とを含む混合物を混練するとともに、かかる混練中もしくは混練後の脱気または混練後の静置の少なくともいずれかを行うことで得ることができる。
　かかる方法で本組成物（１）を作成すれば泡沫体積比率を前記範囲とすることができる。 The present composition (1) is obtained, for example, by kneading a mixture containing an F polymer powder and a liquid medium, and at least either degassing during or after the kneading or allowing the mixture to stand after the kneading. be able to.
If the present composition (1) is prepared by such a method, the foam volume ratio can be within the above range.
　本組成物（１）中の液状媒体の含有量は、１０質量％以上が好ましい。液状媒体の含有量は、６０質量％以下が好ましく、２５質量％以下がより好ましい。これにより、本パウダーを構成する個々の粒子が常に液状媒体に接した状態で液状媒体との混練が進行し、本パウダー粒子および液状媒体が均一に混合する。
　本組成物（１）の固形分濃度はＦポリマーおよび液状媒体の量を適宜設定することで前記範囲とすることができる。他の樹脂や無機フィラーを含む場合も、同様に適宜設定することで本組成物（１）中の固形分濃度を前記範囲とすることができる。
　また液状媒体の粘度を選定することで本組成物（１）の粘度を前記範囲とすることができる。 The content of the liquid medium in the composition (1) is preferably 10% by mass or more. The content of the liquid medium is preferably 60% by mass or less, more preferably 25% by mass or less. As a result, kneading with the liquid medium proceeds in a state where the individual particles constituting the powder are always in contact with the liquid medium, and the powder particles and the liquid medium are uniformly mixed.
The solid content concentration of the present composition (1) can be set within the above range by appropriately setting the amounts of the F polymer and the liquid medium. Even when other resins or inorganic fillers are contained, the solid content concentration in the composition (1) can be set within the above range by appropriately setting the same.
Further, by selecting the viscosity of the liquid medium, the viscosity of the present composition (1) can be within the above range.
　本組成物（１）が他の樹脂を含む場合、本パウダー粒子と他の樹脂との質量比は、本パウダー粒子の質量を１として、他の樹脂の質量が０．０１～０．５の割合が好ましく、０．１～０．３の割合がより好ましい。 When the composition (1) contains another resin, the mass ratio of the powder particles to the other resin is such that the mass of the powder particles is 1 and the mass of the other resin is 0.01 to 0.5. The ratio is preferable, and the ratio of 0.1 to 0.3 is more preferable.
　本組成物（１）が無機フィラーを含む場合、固形分中の無機フィラーの含有量は２５質量％以上が好ましく、５０質量％以上がより好ましい。また、無機フィラーは、７５質量％以下が好ましく、６０質量％以下がより好ましい。 When the composition (1) contains an inorganic filler, the content of the inorganic filler in the solid content is preferably 25% by mass or more, more preferably 50% by mass or more. The inorganic filler is preferably 75% by mass or less, more preferably 60% by mass or less.
　本組成物（１）を第２の液状媒体で希釈して得られる分散液の泡沫体積比率は、本組成物（１）の泡沫体積比率と同様の範囲とすることが容易である。したがってかかる分散液から得られる塗膜や成形物の成分分布の均一性の低下や空隙の抑制が可能となる。 The foam volume ratio of the dispersion obtained by diluting the present composition (1) with a second liquid medium can be easily set to the same range as the foam volume ratio of the present composition (1). Therefore, it is possible to reduce the uniformity of the component distribution of the coating film or the molded product obtained from the dispersion liquid and suppress the voids.
　本組成物（２）は、Ｆポリマーのパウダーに由来する粒子、極性ポリマーまたはその前駆体および液状極性媒体を含み、キャピログラフ測定による粘度が１００００～１０００００Ｐａ・ｓである、組成物である。本組成物（２）としては、ウェットパウダーとも呼ばれる、高粘度の組成物であることが好ましい。
　本組成物（２）は、さらに、無機フィラー、界面活性剤等の他の成分を含んでいてもよい。 The present composition (2) is a composition containing particles derived from F polymer powder, a polar polymer or a precursor thereof, and a liquid polar medium, and having a viscosity as measured by capillograph of 10,000 to 100,000 Pa · s. The composition (2) is preferably a highly viscous composition, also called a wet powder.
The composition (2) may further contain other components such as an inorganic filler and a surfactant.
　本組成物（２）における、本パウダー粒子と極性ポリマーの合計質量の割合は、本組成物（２）の全質量を１００質量％として、５０質量％超が好ましく、６０質量％以上がより好ましく、８０質量％以上がさらに好ましい。かかる合計質量の割合は、９９質量％以下が好ましく、９０質量％以下がより好ましい。
　本組成物（２）における、液状極性媒体の質量割合は、本組成物（２）の全質量を１００質量％として、４０質量％以下が好ましく、２０質量％以下がより好ましい。かかる質量割合は、１質量％以上が好ましく、５質量％以上がより好ましい。 The ratio of the total mass of the powder particles to the polar polymer in the composition (2) is preferably more than 50% by mass, more preferably 60% by mass or more, with the total mass of the composition (2) being 100% by mass. , 80% by mass or more is more preferable. The ratio of the total mass is preferably 99% by mass or less, more preferably 90% by mass or less.
The mass ratio of the liquid polar medium in the composition (2) is preferably 40% by mass or less, more preferably 20% by mass or less, with the total mass of the composition (2) being 100% by mass. The mass ratio is preferably 1% by mass or more, more preferably 5% by mass or more.
　本組成物（２）における、本パウダー粒子の含有量に対する極性ポリマーの含有量の比は、本パウダー粒子の含有量を１として、０．００１以上、０．５未満が好ましい。かかる比は、０．００５以上がより好ましく、０．０１以上がさらに好ましい。またかかる比は、０．２５以下がより好ましく、０．１未満がさらに好ましい。 The ratio of the content of the polar polymer to the content of the powder particles in the composition (2) is preferably 0.001 or more and less than 0.5, where the content of the powder particles is 1. The ratio is more preferably 0.005 or more, still more preferably 0.01 or more. The ratio is more preferably 0.25 or less, still more preferably less than 0.1.
　本組成物（２）のキャピログラフ測定による粘度は１５０００Ｐａ・ｓ以上がより好ましい。また本組成物（２）の粘度は５００００Ｐａ・ｓ以下がより好ましく、３００００Ｐａ・ｓ以下がさらに好ましい。 The viscosity of the composition (2) measured by capillograph is more preferably 15,000 Pa · s or more. The viscosity of the composition (2) is more preferably 50,000 Pa · s or less, and even more preferably 30,000 Pa · s or less.
　かかる範囲のキャピログラフ測定による粘度を有する本組成物（２）の状態は、充分に極性ポリマー（またはその前駆体）を溶解した液状極性媒体に濡れた本パウダー粒子を含む組成物であり、そのうち塊状または粘土状のものはウェットパウダーとも呼ばれる組成物である。本組成物（２）において、本組成物（２）中の本パウダー粒子は、少量の、極性ポリマー（またはその前駆体）を溶解した液状極性媒体中に分散している状態にあるか、または、本組成物（２）中の本パウダー粒子が互いに接し、その粒子間隙に極性ポリマー（またはその前駆体）を溶解した液状極性媒体が存在している状態にあると考えられる。
　また、本組成物（２）は界面活性剤を含むことが好ましい。 The state of the present composition (2) having a viscosity as measured by capillograph in such a range is a composition containing the present powder particles wet with a liquid polar medium in which a polar polymer (or a precursor thereof) is sufficiently dissolved, and is in the form of a lump. Alternatively, the clay-like composition is also called a wet powder. In the present composition (2), the present powder particles in the present composition (2) are in a state of being dispersed in a small amount of a liquid polar medium in which a polar polymer (or a precursor thereof) is dissolved, or are in a state of being dispersed. It is considered that the powder particles in the composition (2) are in contact with each other and a liquid polar medium in which the polar polymer (or its precursor) is dissolved is present in the particle gaps thereof.
Further, the composition (2) preferably contains a surfactant.
　つまり、本組成物（２）の具体例としては、比表面積が２５ｍ２／ｇ以下である、前記カルボニル基含有基または水酸基含有基を有するＦポリマーのパウダーに由来する粒子と、カルボニル基含有基または水酸基含有基を有する極性ポリマーまたはその前駆体と、アミド、ケトンおよびエステルからなる群から選ばれる少なくとも１種の液状極性媒体とを含むウェットパウダーが挙げられる。 That is, as a specific example of the present composition (2), particles derived from the powder of the F polymer having a carbonyl group-containing group or a hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, and a carbonyl group-containing group. Alternatively, a wet powder containing a polar polymer having a hydroxyl group or a precursor thereof and at least one liquid polar medium selected from the group consisting of amides, ketones and esters can be mentioned.
　本組成物（２）の固形分濃度は、５０質量％超が好ましく、６０質量％以上がより好ましい。固形分濃度は、９９質量％以下が好ましく、９５質量％以下がより好ましい。この場合、本組成物（２）が第２の液状媒体に対して分散性に優れ、得られる分散液が分散安定性に優れる。
　なお、本組成物（２）における固形分とは、本組成物（２）または得られる分散液から形成される塗膜や成形物において固形分を形成する物質の総量を意味する。例えば、本組成物（２）が、Ｆポリマーと極性ポリマーと、無機フィラーとを含む場合には、これらの成分の総含有量が本組成物（２）における固形分量となる。
　本組成物（２）が無機フィラーを含む場合、本パウダー粒子に対する無機フィラーの質量比は、０．５～２が好ましく、０．６～１．５がより好ましく、０．７～１がさらに好ましい。 The solid content concentration of the composition (2) is preferably more than 50% by mass, more preferably 60% by mass or more. The solid content concentration is preferably 99% by mass or less, more preferably 95% by mass or less. In this case, the composition (2) is excellent in dispersibility with respect to the second liquid medium, and the obtained dispersion is excellent in dispersion stability.
The solid content in the present composition (2) means the total amount of substances forming the solid content in the coating film or the molded product formed from the present composition (2) or the obtained dispersion liquid. For example, when the composition (2) contains an F polymer, a polar polymer, and an inorganic filler, the total content of these components is the solid content in the composition (2).
When the composition (2) contains an inorganic filler, the mass ratio of the inorganic filler to the powder particles is preferably 0.5 to 2, more preferably 0.6 to 1.5, and further preferably 0.7 to 1. preferable.
　本組成物（２）において、固形分に占める本パウダー粒子の含有量は、２５質量％以上が好ましく、３０質量％以上がより好ましい。また、本パウダー粒子の含有量は、６０質量％以下が好ましく、５０質量％以下がより好ましい。
　本組成物（２）が無機フィラーを含む場合、固形分に占める無機フィラーの含有量は、１０質量％以上が好ましく、２５質量％以上がより好ましい。無機フィラーの含有量は、７５質量％以下が好ましく、６０質量％以下がより好ましい。 In the composition (2), the content of the powder particles in the solid content is preferably 25% by mass or more, more preferably 30% by mass or more. The content of the powder particles is preferably 60% by mass or less, more preferably 50% by mass or less.
When the present composition (2) contains an inorganic filler, the content of the inorganic filler in the solid content is preferably 10% by mass or more, more preferably 25% by mass or more. The content of the inorganic filler is preferably 75% by mass or less, more preferably 60% by mass or less.
　Ｆポリマーは、低表面張力かつ剛直性なポリマーであるため、そのパウダーを液状分散媒に分散させた分散液においてはＦポリマー粒子同士は凝集しやすい。したがって加工性と分散安定性に優れた分散液を得ることは困難であった。分散性を改良するために一般に行われるような剪断をかけてＦポリマーのパウダーと分散媒とを混合する方法では、分散液の調製の際に、泡立ちが激しくなり、凝集により分散安定性が低下する場合があった。
　また、このＦポリマーの特性ゆえに、そのパウダー粒子と他の成分とを含む分散液において、本パウダーと他の成分とが相互作用し難い。そのため、剪断をかけて両者を分散媒中で混合する方法では、必ずしも成分間の相互作用が高まらず、Ｆポリマー粒子の凝集が生じて緻密で均一な分散液を形成し難い。特にＦポリマーを極性ポリマーと混合して均一な分散液を得ようとする場合、この傾向は顕著であった。
　本発明においては、本組成物を用いることで、本パウダーの濡れおよび成分間の相互作用を促進でき、上記のような問題のない分散液を得ることができる。 Since the F polymer is a polymer having low surface tension and rigidity, the F polymer particles tend to aggregate with each other in a dispersion liquid in which the powder is dispersed in a liquid dispersion medium. Therefore, it has been difficult to obtain a dispersion liquid having excellent processability and dispersion stability. In the method of mixing the F polymer powder and the dispersion medium by shearing, which is generally performed to improve the dispersibility, foaming becomes intense during the preparation of the dispersion liquid, and the dispersion stability decreases due to aggregation. There was a case.
Further, due to the characteristics of this F polymer, it is difficult for this powder to interact with other components in a dispersion liquid containing the powder particles and other components. Therefore, in the method of shearing and mixing the two in a dispersion medium, the interaction between the components does not necessarily increase, and agglomeration of F polymer particles occurs, making it difficult to form a dense and uniform dispersion. This tendency was particularly remarkable when the F polymer was mixed with the polar polymer to obtain a uniform dispersion liquid.
In the present invention, by using the present composition, wetting of the present powder and interaction between the components can be promoted, and a dispersion liquid without the above-mentioned problems can be obtained.
　また、本組成物（２）においては、極性ポリマーは、同じく極性を有する液状極性媒体と相互作用して、その少なくとも一部が溶解される。その結果、極性ポリマーの分子運動の自由度が上がり、極性ポリマーと本パウダー粒子との相互作用が促進されると考えられる。そして、これにより、極性ポリマーを溶解している液状極性媒体と本パウダー粒子との相互作用も促進され、本パウダー粒子が濡れ易くなると考えられる。その結果、３成分が緻密かつ均一に混合された所定の粘度範囲にある組成物である本組成物（２）が形成されると考えられる。
　本組成物（２）は本パウダー粒子と極性ポリマーと液状極性媒体とが高度に相互作用しているため、本組成物（２）を第２の極性溶媒で希釈して得られる分散液においても分散安定性が向上したと考えられる。 Further, in the present composition (2), the polar polymer interacts with a liquid polar medium having the same polarity, and at least a part thereof is dissolved. As a result, it is considered that the degree of freedom of the molecular motion of the polar polymer is increased and the interaction between the polar polymer and the powder particles is promoted. It is considered that this also promotes the interaction between the liquid polar medium in which the polar polymer is dissolved and the powder particles, and makes the powder particles easy to get wet. As a result, it is considered that the present composition (2), which is a composition in which the three components are densely and uniformly mixed in a predetermined viscosity range, is formed.
Since the composition (2) has a high degree of interaction between the powder particles, the polar polymer, and the liquid polar medium, the dispersion obtained by diluting the composition (2) with a second polar solvent can also be used. It is considered that the dispersion stability has improved.
　本組成物（２）は、本組成物（１）と同様に、好適には、Ｆポリマーのパウダーと前記液状極性媒体とを含む混合物を混練するとともに、かかる混練中もしくは混練後の脱気または混練後の静置の少なくともいずれかを行うことで得るのが好ましい。 The present composition (2) is preferably kneaded with a mixture containing the powder of the F polymer and the liquid polar medium, and is degassed during or after such kneading, as in the present composition (1). It is preferably obtained by performing at least one of standing after kneading.
　本発明はまた前記本組成物の製造方法であり、本パウダーと液状媒体とを含む混合物（以下、「本混合物」ともいう。）を混練するとともに、かかる混練中もしくは混練後の脱気および混練後の静置の少なくともいずれかを行うことにより本組成物を製造する方法である。本パウダーとともに極性ポリマーを使用し、液状媒体として液状極性媒体を使用することにより、この方法で本組成物（２）を製造することができる。
　混練中もしくは混練後の混練物の脱気は、本パウダーの粒子間隙に存在する空気等のガスや本組成物の調製に際して持ち込まれた雰囲気ガスの効率的な除去を促し、本パウダー粒子の濡れ性を向上させる。また、混練後の混練物の静置は、液状媒体の本パウダー粒子間への浸透を促し、本パウダー粒子の濡れを促す。
　上記脱気と静置は両方行うことが好ましい。 The present invention is also a method for producing the present composition, in which a mixture containing the present powder and a liquid medium (hereinafter, also referred to as “the present mixture”) is kneaded, and deaeration and kneading during or after such kneading are performed. It is a method of producing the present composition by performing at least one of the subsequent standing. The composition (2) can be produced by this method by using a polar polymer together with the powder and using a liquid polar medium as the liquid medium.
Deaeration of the kneaded product during or after kneading promotes efficient removal of gas such as air existing in the particle gaps of the powder and atmospheric gas brought in during the preparation of the composition, and wets the powder particles. Improve sex. Further, the standing of the kneaded product after kneading promotes the penetration of the liquid medium between the powder particles and promotes the wetting of the powder particles.
It is preferable to perform both degassing and standing.
　混練機中の本混合物は、混練機外で各成分を混合して得られた本混合物を混練機に導入したものであっても、混練機中に各成分やその一部の混合物を混練機に導入して混練機中で本混合物としたものであってもよい。また、各成分の一部は各成分の混練中に混練機に導入してもよい。例えば、混練中の混練物（液状媒体を含む）にさらに液状媒体を追加してもよい。
　また、極性ポリマーは液状極性媒体に溶解させた溶液を本混合物形成に使用することが好ましい。さらに、液状媒体等の液状成分は、本混合物形成前に脱気して使用することも好ましい。 Even if the main mixture in the kneader is the one in which the main mixture obtained by mixing each component outside the kneader is introduced into the kneader, each component or a part of the mixture is mixed in the kneader. It may be introduced into the kneader to make the present mixture in a kneader. Further, a part of each component may be introduced into the kneader during the kneading of each component. For example, a liquid medium may be further added to the kneaded product (including the liquid medium) being kneaded.
Further, as the polar polymer, it is preferable to use a solution dissolved in a liquid polar medium for forming the present mixture. Further, it is also preferable that the liquid component such as a liquid medium is degassed and used before the formation of the present mixture.
　本混合物の混練に際しては、本混合物の質量が実質的に変化しないように混練するのが好ましく、閉鎖系で混練するのが好ましい。言い換えれば、混練中に本混合物の液状成分が蒸発しないように混練するのが好ましい。
　混練に際しては、撹拌槽と、一軸あるいは多軸の撹拌羽根を備えた混練機を使用するのが好ましい。撹拌羽根の数は、高い混練作用を得るためには二つ以上の撹拌羽根のものが好ましい。混練の方法はバッチ式、連続式いずれでもよい。 When kneading the present mixture, it is preferable to knead the mixture so that the mass of the present mixture does not substantially change, and it is preferable to knead the mixture in a closed system. In other words, it is preferable to knead the mixture so that the liquid components of the present mixture do not evaporate during kneading.
For kneading, it is preferable to use a kneader equipped with a stirring tank and uniaxial or multiaxial stirring blades. The number of stirring blades is preferably two or more in order to obtain a high kneading action. The kneading method may be either a batch method or a continuous method.
　バッチ式混練に用いられる混練機としてはヘンシェルミキサー、加圧ニーダー、バンバリーミキサー、自転公転撹拌機またはプラネタリーミキサーが好ましく、プラネタリーミキサーがより好ましい。プラネタリーミキサーは、互いに自転と公転を行う２軸の攪拌羽根を有し、攪拌槽中の混練物を攪拌、混練する構造を有している。そのため、攪拌槽中に攪拌羽根の到達しないデッドスペースが少ない。羽根の形状が肉厚で高負荷をかけることができるが、攪拌羽根を攪拌槽中で回す通常の攪拌機の様に使用することもできる。そのため、撹拌槽中に撹拌羽根の到達しないデッドスペースが少なく、羽根の負荷を軽減して、高度に本混合物を混練できる。 As the kneader used for the batch type kneading, a Henschel mixer, a pressurized kneader, a Banbury mixer, a rotation / revolution stirrer or a planetary mixer is preferable, and a planetary mixer is more preferable. The planetary mixer has a biaxial stirring blade that rotates and revolves with each other, and has a structure in which the kneaded material in the stirring tank is stirred and kneaded. Therefore, there is little dead space in the stirring tank where the stirring blades do not reach. The shape of the blade is thick and a high load can be applied, but it can also be used like a normal stirrer in which the stirring blade is rotated in a stirring tank. Therefore, there is little dead space in the stirring tank where the stirring blades do not reach, the load on the blades can be reduced, and the present mixture can be highly kneaded.
　本混合物の混練は、冷却しながら行うのが好ましい。この場合、液状媒体の気化が抑制されるとともに、本混合物が粘ちょうとなり、混練機の撹拌羽根に負荷がかかり、その結果本混合物への剪断力が大きくなる。特に、複数の撹拌羽根を用いた場合、撹拌羽根同士、または撹拌羽根と撹拌槽との間で、材料に剪断力が印加されやすくなる。その結果、本パウダーがＦポリマー粒子の凝集塊を含んでいた場合にはその凝集塊の解凝集が効率的に行われるとともに、本パウダーと液状媒体は充分に混合される。
　混練における温度は、液状媒体の沸点以下が好ましく、３０℃以下が好ましい。混練における温度は、０℃以上が好ましく、１０℃以上がより好ましい。 The kneading of the present mixture is preferably carried out while cooling. In this case, the vaporization of the liquid medium is suppressed, the mixture becomes sticky, and a load is applied to the stirring blades of the kneader, and as a result, the shearing force on the mixture increases. In particular, when a plurality of stirring blades are used, a shearing force is likely to be applied to the material between the stirring blades or between the stirring blades and the stirring tank. As a result, when the present powder contains agglomerates of F polymer particles, the agglomerates are efficiently deaggregated, and the present powder and the liquid medium are sufficiently mixed.
The temperature in the kneading is preferably not less than the boiling point of the liquid medium, and more preferably 30 ° C. or less. The temperature in kneading is preferably 0 ° C. or higher, more preferably 10 ° C. or higher.
　本組成物（２）を得るための混練は、温度を２５℃、剪断速度を１ｓ－１としてキャピログラフを測定した時、混練物の粘度の変動幅が±５％以下となるまで行うのが好ましい。変動幅は±３％以下がより好ましい。
　粘度の変動幅は、混練しながら１０分毎に、混練物を混練機からサンプリングし、前記上限でキャピログラフ測定による粘度を測定することで確認することができる。ｎ回目の測定の粘度をηｎ、（ｎ＋１）回目の測定の粘度をηｎ＋１とした時、下記式（１）により得られるｎ回目の変動幅ｒｎが連続３回、前記範囲内となればよい。
　（ηｎ＋１／ηｎ）×１００＝ｒｎ　　　　　　　　　　（１） The kneading for obtaining the present composition (2) is preferably carried out until the fluctuation range of the viscosity of the kneaded product becomes ± 5% or less when the capillograph is measured at a temperature of 25 ° C. and a shear rate of 1s -1 . .. The fluctuation range is more preferably ± 3% or less.
The fluctuation range of the viscosity can be confirmed by sampling the kneaded product from the kneader every 10 minutes while kneading and measuring the viscosity by capillograph measurement at the upper limit. When the viscosity of the nth measurement is η n and the viscosity of the (n + 1) th measurement is η n + 1 , the nth fluctuation range rn obtained by the following formula (1) should be within the above range three times in a row. Just do it.
(Η n + 1 / η n ) × 100 = r n (1)
　混練の終点は、混練の進行にともない、撹拌羽根にかかる負荷が小さくなり、混練機の消費電流が減少するため、消費電流のモニターにより判断できる。
　また、混練機の負荷電流を混練機の剪断速度で除した値を混練物に与える力およびエネルギーとして、混練を制御してもよい。具体的には、混練開始から負荷電流を増大させて、徐々に減少させるのが好ましい。 The end point of kneading can be determined by monitoring the current consumption because the load applied to the stirring blade becomes smaller and the current consumption of the kneader decreases as the kneading progresses.
Further, the kneading may be controlled by using the value obtained by dividing the load current of the kneader by the shear rate of the kneader as the force and energy given to the kneaded product. Specifically, it is preferable to increase the load current from the start of kneading and gradually decrease it.
　連続式混練機としては二軸型押出混練機や石臼型混練機が挙げられる。
二軸型押出混練機とは、例えば被混練物を平行に近接配置された二本のスクリュ間のせん断力によって混練する二軸スクリュ式の連続混練装置である。
　石臼型混練機とは、例えば被混練物が通過可能な内部空間を備える筒状の固定部と、固定部の内部空間に配置され、回転することで内部空間を通過する被混練物を連続的に混練しながら回転軸方向に搬送する回転部とを有する混練機である。 Examples of the continuous kneader include a twin-screw extrusion kneader and a stone mill type kneader.
The twin-screw extrusion kneader is, for example, a twin-screw-type continuous kneading device that kneads an object to be kneaded by a shear force between two screws arranged in parallel in close proximity to each other.
The stone mill type kneader is, for example, a tubular fixed portion having an internal space through which the kneaded material can pass, and a kneaded material which is arranged in the internal space of the fixed portion and passes through the internal space by rotating. It is a kneading machine having a rotating portion that conveys in the direction of the rotation axis while kneading.
　脱気は前記混練中に行なってもよいし、前記混練後に行なってもよいし、前記混練と交互に複数回行ってもよい。脱気は連続的に行ってもよいし、間欠的に行ってもよい。
　脱気は本混合物の質量が実質的に変化しないように行うのが好ましい。脱気の方法は例えば、液状組成物を減圧状態にする方法、液状組成物を加温状態にする方法、液状組成物を凍結する方法、本混合物に超音波を照射する方法、およびこれら方法を組合わせた方法が挙げられる。これらの方法の内、本混合物を減圧状態にする方法または本混合物を加温状態にする方法が操作の簡便性から好ましく、両者を組み合わせた方法が脱気の効率の観点からより好ましい。さらに、前記のように、冷却しながら行うのが特に好ましい。 Degassing may be performed during the kneading, after the kneading, or alternately with the kneading a plurality of times. Degassing may be performed continuously or intermittently.
Degassing is preferably performed so that the mass of the present mixture does not change substantially. The degassing method includes, for example, a method of depressurizing the liquid composition, a method of heating the liquid composition, a method of freezing the liquid composition, a method of irradiating the mixture with ultrasonic waves, and these methods. The combined method can be mentioned. Of these methods, a method of putting the present mixture in a depressurized state or a method of putting the present mixture in a heated state is preferable from the viewpoint of simplicity of operation, and a method in which both are combined is more preferable from the viewpoint of degassing efficiency. Further, as described above, it is particularly preferable to carry out the process while cooling.
　本混合物を減圧または加温状態にする場合、脱気の際の温度および圧力は液状組成物中の本混合物に応じて適宜設定され、本混合物が沸騰しない圧力および温度が選定される。例えば圧力は０Ｐａから０．０１ＭＰａ程度、温度は本混合物中の液状媒体の沸点より１００℃から２５０℃低い温度が好ましい。
　脱気の時間は特に制限はないが、脱気の時間が長すぎても脱気の効果は大きく変わらないことから、通常、１０分間から６時間である。
　脱気に際して、突沸を防ぐために撹拌等の操作を行ってもよい。 When the present mixture is depressurized or heated, the temperature and pressure at the time of degassing are appropriately set according to the present mixture in the liquid composition, and the pressure and temperature at which the present mixture does not boil are selected. For example, the pressure is preferably about 0 Pa to 0.01 MPa, and the temperature is preferably 100 ° C. to 250 ° C. lower than the boiling point of the liquid medium in the present mixture.
The degassing time is not particularly limited, but it is usually 10 minutes to 6 hours because the degassing effect does not change significantly even if the degassing time is too long.
At the time of degassing, an operation such as stirring may be performed to prevent bumping.
　混練物の静置は通常、前記混練後に行なわれる。混練後の混練物を容器内にて一定時間静置する。静置は前記混練物の質量が実質的に変化しないように行うことが好ましく、密閉された容器内のような密閉系で静置するのが好ましい。
　混練物を静置する雰囲気の温度および圧力は通常、１０から３０℃、１気圧程度であり、恒温恒湿下が好ましい。場合によっては、静置のあいだ、混練物中の本パウダー粒子が凝集沈降しない程度に撹拌してもよい。
　静置の時間は２４時間以上が好ましく、４８時間以上がより好ましい。静置の時間は、静置の時間が長すぎても得られる効果は大きく変わらないことから、１６８時間以下が好ましい。 The kneaded product is usually allowed to stand after the kneading. The kneaded product after kneading is allowed to stand in a container for a certain period of time. It is preferable to allow the kneaded product to stand so that the mass of the kneaded product does not substantially change, and it is preferable to allow the kneaded product to stand in a closed system such as in a closed container.
The temperature and pressure of the atmosphere in which the kneaded material is allowed to stand are usually about 10 to 30 ° C. and 1 atm, preferably under constant temperature and humidity. In some cases, the powder particles in the kneaded product may be agitated to the extent that they do not coagulate and settle during standing.
The standing time is preferably 24 hours or more, more preferably 48 hours or more. The standing time is preferably 168 hours or less because the effect obtained does not change significantly even if the standing time is too long.
　本組成物（１）を得るための静置に際する混練物の粘度は、４００００ｍＰａ・ｓ以下が好ましく、２００００ｍＰａ・ｓ以下がより好ましい。前記粘度は、８０００ｍＰａ・ｓ以上が好ましい。この場合、液状媒体の本パウダー粒子間への浸透が一層促され、上述した作用機構が亢進しやすい。静置に際する混練物の粘度は、その温度、または、混練物への液状極性媒体等の液状媒体の添加により、調整してもよい。 The viscosity of the kneaded product at the time of standing to obtain the present composition (1) is preferably 40,000 mPa · s or less, and more preferably 20,000 mPa · s or less. The viscosity is preferably 8000 mPa · s or more. In this case, the permeation of the liquid medium between the powder particles is further promoted, and the above-mentioned mechanism of action is likely to be enhanced. The viscosity of the kneaded product at the time of standing may be adjusted by the temperature thereof or by adding a liquid medium such as a liquid polar medium to the kneaded product.
　本法において、前記脱気および静置はいずれか一方を行えばよいが、本組成物を希釈して得られる分散液の分散安定性の観点から、両者を行うのが好ましい。
　両者を行う態様としては、例えば、本混合物を混練し、その後脱気を連続的または断続的に行い、引続き脱気をせずに静置する態様、本混合物を連続的または断続的に脱気しながら混練し、得られた混練物の静置を行う態様、本混合物を連続的または断続的に脱気しながら混練し、得られた混練物の静置を行い、静置後さらに脱気する態様、本混合物を混練し、混練後に脱気しながら静置を行い、さらに脱気をせずに静置する態様、前記液状組成物を混練し、混練後に静置を行い、さらに静置後連続的または断続的に脱気する態様、とが挙げられる。これら複数の態様を組合わせてもよく、一つの態様を繰り返してもよい。 In this method, either degassing or standing may be performed, but it is preferable to perform both from the viewpoint of the dispersion stability of the dispersion obtained by diluting the composition.
Examples of performing both are a mode in which the mixture is kneaded, then degassing is continuously or intermittently performed, and then the mixture is allowed to stand without degassing, and the mixture is continuously or intermittently degassed. Kneading while kneading and allowing the obtained kneaded product to stand still, kneading the mixture while continuously or intermittently degassing, and then allowing the obtained kneaded product to stand still, and then further degassing. In the embodiment, the present mixture is kneaded, and after kneading, the mixture is allowed to stand while being degassed, and then the mixture is allowed to stand without being degassed. A mode of degassing continuously or intermittently is mentioned. These plurality of embodiments may be combined, or one embodiment may be repeated.
　前記脱気または静置の少なくともいずれかを前記混練および前記混合の間のいずれかの段階で行うことで、本パウダー粒子の凝集が抑えられ、本組成物と第２の液状媒体を混合する際の泡立ちが抑制される。その結果、得られる塗膜や成形物の表面平滑性が優れる。 By performing at least one of the degassing and standing at any stage between the kneading and the mixing, the agglomeration of the powder particles is suppressed, and when the composition and the second liquid medium are mixed. Foaming is suppressed. As a result, the surface smoothness of the obtained coating film or molded product is excellent.
　本組成物は第２の液状媒体で希釈して本組成物よりも低粘度の分散液として利用されることが好ましい。本組成物は、また、他の用途に使用することもできる。
　本組成物を第２の液状媒体で希釈して得られる分散液（以下、「本分散液」ともいう。）は、コーティング剤や塗料等の用途に適している。
　第２の液状媒体は前記第１の液状媒体と相溶性の液状媒体であり、前記第１の液状媒体と同じ液状媒体であってもよい。また、第２の液状媒体は、本組成物の希釈によって本組成物中の本パウダー粒子や無機フィラー等の非溶解成分を溶解させない液状媒体であり、第１の液状媒体中に溶解している成分を析出させない液状媒体であることが好ましい。ただし、本組成物において第１の液状媒体の量が少ないことより第１の液状媒体にその全量が十分溶解していない成分がある場合、例えば、本組成物（２）において極性ポリマーが膨潤していても溶解した状態にない場合、第２の液状媒体による希釈によってその成分の全量が溶解した状態になることがあってもよい。第２の液状媒体としては、希釈される本組成物中の第１の液状媒体と同じ液状媒体であることが特に好ましい。
　第２の液状媒体としては、第１の液状媒体として用いてもよい液状媒体が挙げられ、中でも、低粘度の液状媒体が好ましい。 It is preferable that the present composition is diluted with a second liquid medium and used as a dispersion having a lower viscosity than the present composition. The composition can also be used for other purposes.
The dispersion obtained by diluting the composition with a second liquid medium (hereinafter, also referred to as “the dispersion”) is suitable for applications such as coating agents and paints.
The second liquid medium is a liquid medium compatible with the first liquid medium, and may be the same liquid medium as the first liquid medium. The second liquid medium is a liquid medium that does not dissolve insoluble components such as powder particles and inorganic fillers in the composition by diluting the composition, and is dissolved in the first liquid medium. It is preferably a liquid medium that does not precipitate components. However, if there is a component in the first liquid medium in which the entire amount is not sufficiently dissolved due to the small amount of the first liquid medium in the present composition, for example, the polar polymer swells in the present composition (2). However, if it is not in a dissolved state, dilution with a second liquid medium may result in a dissolved state in the entire amount of the component. The second liquid medium is particularly preferably the same liquid medium as the first liquid medium in the diluted composition.
Examples of the second liquid medium include liquid media that may be used as the first liquid medium, and among them, a liquid medium having a low viscosity is preferable.
　第２の液状媒体で希釈するための本組成物と第２の液状媒体との混合は、得られる分散液の分散性と分散安定性の観点から、例えば分散機を用いた混合が好ましい。分散機としては、メディアを用いたものでは、超音波ホモジナイザードベイントシェーカー、ボールミル、アトライター、バスケットミル、サンドミル、サンドグラインダー、ダイノーミル、ディスパーマット、ＳＣミル、スパイク ミル、アジテーターミルなどが挙げられる。またメディアを用いないものとしては、超音波ホモジナイザー、ナノマイザー、デゾルバー、ディスパー、高速インペラー分散機、自転公転撹拌機、薄膜旋回型高速ミキサーなどがあげられる。これらの中でもメディアを用いた分散機は分散能力が高いため好ましい。 The mixing of the present composition for diluting with the second liquid medium and the second liquid medium is preferably mixed using, for example, a disperser from the viewpoint of the dispersibility and dispersion stability of the obtained dispersion liquid. Examples of the disperser using media include an ultrasonic homogenized baint shaker, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, and an agitator mill. Examples of those that do not use media include an ultrasonic homogenizer, a nanomizer, a resolver, a disper, a high-speed impeller disperser, a rotation / revolution agitator, and a thin-film swirling high-speed mixer. Among these, a disperser using media is preferable because it has a high dispersive capacity.
　また衝突式分散機を用いて混合を行うと分散安定性が向上するので、第２の液状媒体との混合は衝突式分散機を用いた混合が好ましい。
　衝突式分散機とは、高圧ポンプにて一度加圧した液媒体を衝突させこの時の衝撃力等によって分散を行う分散機である。衝突型分散機は衝突させる対象によって大きく２種類に分けることができる。液媒体同士を衝突させる方式と、衝突対象物に液媒体を衝突させる方式である。液媒体同士を衝突させる方式の例として、ナノマイザー、ジーナスＰＹ、アルティマイザー、Ａｑｕａ、マイクロフルイダイザー等が挙げられる。衝突対象物に液媒体を衝突させる方式の例として、ホモゲナイザー等が挙げられる。 Further, since the dispersion stability is improved by mixing using the collision type disperser, it is preferable to mix with the second liquid medium by using the collision type disperser.
The collision type disperser is a disperser that collides with a liquid medium once pressurized by a high-pressure pump and disperses by the impact force or the like at this time. The collision type disperser can be roughly divided into two types depending on the object to be collided. There are a method in which liquid media collide with each other and a method in which the liquid medium collides with an object to collide. Examples of the method of colliding liquid media with each other include nanomizer, Genus PY, ultimateizer, Aqua, microfluidizer and the like. An example of a method of colliding a liquid medium with a collision object is a homogenizer or the like.
　また上記分散機を用いた混合以外に、本組成物と第２の液状媒体とを混合する方法として、前記混練に用いた撹拌槽と撹拌羽根を有する混練機の中で本組成物と第２の液状媒体とを混合する方法、異なる混練機によって本組成物と第２の液状媒体と混合する方法等が挙げられる。混練機は上記バッチ式および連続式の混練機と同じものが挙げられる。 Further, as a method of mixing the present composition and the second liquid medium in addition to the mixing using the above-mentioned disperser, the present composition and the second liquid medium are mixed in the kneader having the stirring tank and the stirring blade used for the kneading. Examples thereof include a method of mixing the liquid medium of the above, a method of mixing the present composition with the second liquid medium by a different kneading machine, and the like. Examples of the kneader are the same as those of the batch type and continuous type kneaders.
　本分散液の製造において、必要に応じてさらに他の樹脂、無機フィラー、界面活性剤等を添加してもよい。他の樹脂と無機フィラーの両方を添加する場合、他の樹脂と無機フィラーは別々に添加してもよいし、一緒に添加してよいし、予め他の樹脂と無機フィラーとを混合したマスターバッチを作成し、このマスターバッチを添加してもよい。 In the production of this dispersion, other resins, inorganic fillers, surfactants and the like may be added as needed. When both the other resin and the inorganic filler are added, the other resin and the inorganic filler may be added separately or together, or a masterbatch in which the other resin and the inorganic filler are mixed in advance. May be prepared and this masterbatch may be added.
　本分散液中の固形分濃度は４０質量％以上が好ましく、５０質量％以上がより好ましい。また本分散液の分散性の観点から、固形分濃度は９０質量％以下が好ましく、７５質量％以下がより好ましい。なお、本分散液の固形分とは本分散液からすべての液状媒体を除いた成分を意味し、通常本分散液から形成される塗膜や成形物において固形成分を形成する物質の総量を意味する。 The solid content concentration in the dispersion is preferably 40% by mass or more, more preferably 50% by mass or more. Further, from the viewpoint of dispersibility of the present dispersion, the solid content concentration is preferably 90% by mass or less, more preferably 75% by mass or less. The solid content of the present dispersion means the components obtained by removing all the liquid media from the present dispersion, and means the total amount of substances forming the solid components in the coating film or the molded product normally formed from the present dispersion. do.
　本分散液の分散安定性の観点から、本分散液中の固形分量に対する本パウダー粒子の含有量は、２０質量％以上が好ましく、３０質量％以上がより好ましい。本パウダー粒子の含有量は、７０質量％以下が好ましく、５０質量％以下がより好ましい。 From the viewpoint of the dispersion stability of the dispersion, the content of the powder particles with respect to the solid content in the dispersion is preferably 20% by mass or more, more preferably 30% by mass or more. The content of the powder particles is preferably 70% by mass or less, more preferably 50% by mass or less.
　本分散液のＢ型粘度計で測定される粘度は、５０ｍＰａ・ｓ以上が好ましく、７５ｍＰａ・ｓ以上がより好ましく、１００ｍＰａ・ｓ以上がさらに好ましい。上記粘度は、８０００ｍＰａ・ｓ未満が好ましく、５０００ｍＰａ・ｓ以下がより好ましく、１０００ｍＰａ・ｓ以下がさらに好ましい。かかる粘度を有する分散液は塗工性に優れる。
　また本分散液のチキソ比は、１から１０が好ましい。
　本分散液から得られる塗膜や成形物の成分分布の均一性の低下や空隙の抑制の観点から、分散液中の泡沫体積比率は、１０％未満が好ましく、５％未満がより好ましい。泡沫体積比率は、０％以上が好ましい。
　上述した作用機構により、本法によれば、かかる液物性に優れた分散液が容易に得られる。 The viscosity of this dispersion measured by a B-type viscometer is preferably 50 mPa · s or more, more preferably 75 mPa · s or more, and even more preferably 100 mPa · s or more. The viscosity is preferably less than 8000 mPa · s, more preferably 5000 mPa · s or less, and even more preferably 1000 mPa · s or less. The dispersion having such a viscosity is excellent in coatability.
The thixotropic ratio of this dispersion is preferably 1 to 10.
From the viewpoint of reducing the uniformity of the component distribution of the coating film and the molded product obtained from the present dispersion and suppressing the voids, the foam volume ratio in the dispersion is preferably less than 10%, more preferably less than 5%. The foam volume ratio is preferably 0% or more.
According to this method, a dispersion having excellent physical characteristics can be easily obtained by the above-mentioned mechanism of action.
　本分散液を、基材の表面に塗布し、加熱して、Ｆポリマーからなる層（以下、「Ｆ層」とも記す）を形成すれば、基材とＦ層とを有する積層体が製造できる。分散液は、その使用に際して、さらに静置してもよい。
　積層体の好適な態様としては、金属箔とその少なくとも一方の表面に形成されたＦ層とを有する金属張積層体、樹脂フィルムとその少なくとも一方の表面に形成されたＦ層とを有する多層フィルムが挙げられる。
　金属張積層体における金属箔は、銅箔であるのが好ましい。かかる金属張積層体は、プリント基板材料として特に有用である。
　多層フィルムにおける樹脂フィルムは、ポリイミドフィルムであるのが好ましい。かかる多層フィルムは、電線被覆材料、プリント基板材料として有用である。 If this dispersion is applied to the surface of a base material and heated to form a layer made of an F polymer (hereinafter, also referred to as “F layer”), a laminate having the base material and the F layer can be produced. .. The dispersion may be further allowed to stand before its use.
Preferable embodiments of the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof. Can be mentioned.
The metal foil in the metal-clad laminate is preferably a copper foil. Such a metal-clad laminate is particularly useful as a printed circuit board material.
The resin film in the multilayer film is preferably a polyimide film. Such a multilayer film is useful as an electric wire coating material and a printed circuit board material.
　上記積層体の製造においては、基材の表面の少なくとも片面にＦ層が形成されればよく、基材の片面のみにＦ層が形成されてもよく、基材の両面にＦ層が形成されてもよい。基材の表面は、シランカップリング剤等により表面処理されていてもよい。本分散液の塗布に際しては、スプレー法、ロールコート法、スピンコート法、グラビアコート法、マイクログラビアコート法、グラビアオフセット法、ナイフコート法、キスコート法、バーコート法、ダイコート法、ファウンテンメイヤーバー法、スロットダイコート法、ディップコート法の塗布方法を使用できる。 In the production of the above-mentioned laminate, the F layer may be formed on at least one side of the surface of the base material, the F layer may be formed on only one side of the base material, and the F layer is formed on both sides of the base material. You may. The surface of the base material may be surface-treated with a silane coupling agent or the like. When applying this dispersion, the 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. , Slot die coat method, dip coat method can be used.
　Ｆ層は、本分散液から加熱により液状媒体を除去した後に、さらに加熱によりポリマーを焼成して形成するのが好ましい。液状媒体の除去の温度は、できるだけ低温が好ましく、液状媒体の沸点より５０から１５０℃低い温度が好ましい。例えば沸点が約２００℃のＮ－メチル－２－ピロリドンを用いた場合、１８０℃以下、好ましくは１００から１５０℃で加熱することが好ましい。液状媒体を除去する工程で空気を吹き付けるのが好ましい。 The F layer is preferably formed by removing the liquid medium from the dispersion by heating and then firing the polymer by further heating. The temperature for removing the liquid medium is preferably as low as possible, preferably 50 to 150 ° C. lower than the boiling point of the liquid medium. For example, when N-methyl-2-pyrrolidone having a boiling point of about 200 ° C. is used, it is preferable to heat it at 180 ° C. or lower, preferably 100 to 150 ° C. It is preferable to blow air in the step of removing the liquid medium.
　液状媒体を除去後、基材をポリマーが焼成する温度領域に加熱して形成するのが好ましく、例えば３００から４００℃の範囲でポリマーを焼成するのが好ましい。Ｆ層は、Ｆポリマーの焼成物を含むのが好ましい。
　Ｆ層は、上述のとおり本分散液の塗布、乾燥、焼成の工程を経て形成される。これら工程は１回でも２回以上でもよい。例えば、Ｆ層は、基材の表面に本分散液を塗布し、加熱により液状媒体を除去して膜を形成する工程を２回繰り返し、厚さを大きくした膜を加熱して、Ｆポリマーを焼成して形成してもよい。平滑性に優れた厚いＦ層を得やすい観点から、本分散液の塗布、乾燥の工程を２回以上行ってもよい。 After removing the liquid medium, it is preferable to heat the substrate to a temperature range in which the polymer is fired, and it is preferable to fire the polymer in the range of, for example, 300 to 400 ° C. The F layer preferably contains a fired product of the F polymer.
The F layer is formed through the steps of applying, drying, and firing the present dispersion as described above. These steps may be performed once or twice or more. For example, in the F layer, the step of applying the present dispersion liquid to the surface of the base material, removing the liquid medium by heating to form a film is repeated twice, and the film having an increased thickness is heated to form an F polymer. It may be formed by firing. From the viewpoint of easily obtaining a thick F layer having excellent smoothness, the steps of applying and drying the dispersion may be performed twice or more.
　Ｆ層の厚さは、０．１μｍ以上が好ましく、１μｍ以上がより好ましい。厚さの上限は、１００μｍである。この範囲において、耐クラック性に優れたＦ層を容易に形成できる。Ｆ層と基材層との剥離強度は、１０Ｎ／ｃｍ以上が好ましく、１５Ｎ／ｃｍ以上がより好ましい。上記剥離強度は、１００Ｎ／ｃｍ以下が好ましい。本分散液を用いれば、Ｆ層におけるＦポリマーの物性を損なわずに、かかる積層体を容易に形成できる。
　Ｆ層の空隙率は、５％以下が好ましく、４％以下がより好ましい。空隙率は、０．０１％以上が好ましく、０．１％以上がより好ましい。なお、空隙率は、走査型電子顕微鏡（ＳＥＭ）を用いて観察される塗膜や成形物の断面における、空隙部分の面積の割合（％）である。 The thickness of the F layer is preferably 0.1 μm or more, and more preferably 1 μm or more. The upper limit of the thickness is 100 μm. In this range, the F layer having excellent crack resistance can be easily formed. 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. By using this dispersion, such a laminate can be easily formed without impairing the physical properties of the F polymer in the F layer.
The porosity of the F layer is preferably 5% or less, more preferably 4% or less. The porosity is preferably 0.01% or more, more preferably 0.1% or more. The porosity is the ratio (%) of the area of the void portion in the cross section of the coating film or the molded product observed using a scanning electron microscope (SEM).
　基材の材質としては、金属基板（銅、ニッケル、アルミニウム、チタン、それらの合金等の金属箔等）、樹脂フィルム（ポリイミド、ポリアリレート、ポリスルホン、ポリアリルスルホン、ポリアミド、ポリエーテルアミド、ポリフェニレンスルフィド、ポリアリルエーテルケトン、ポリアミドイミド、液晶性ポリエステル、液晶性ポリエステルアミド等のフィルム）、プリプレグ（繊維強化樹脂基板の前駆体）、セラミックス基板、ガラス基板が挙げられる。基材の形状としては、平面状、曲面状、凹凸状が挙げられ、さらに、箔状、板状、膜状、繊維状のいずれであってもよい。　
　基材の表面の十点平均粗さは、０．０１～０．０５μｍが好ましい。 Materials for the base material include metal substrates (copper, nickel, aluminum, titanium, metal foils such as alloys thereof, etc.), resin films (polyimide, polyarylate, polysulfone, polyallyl sulfone, polyamide, polyetheramide, polyphenylene sulfide, etc.). , Polyallyl ether ketone, polyamideimide, liquid crystal polyester, liquid crystal polyester amide and other films), prepreg (precursor of fiber reinforced resin substrate), ceramics substrate, glass substrate and the like. Examples of the shape of the base material include a planar shape, a curved surface shape, and an uneven shape, and may be any of a foil shape, a plate shape, a film shape, and a fibrous shape.
The ten-point average roughness of the surface of the base material is preferably 0.01 to 0.05 μm.
　積層体の好適な態様としては、金属箔とその少なくとも一方の表面に形成されたＦ層とを有する金属張積層体、樹脂フィルムとその少なくとも一方の表面に形成されたＦ層とを有する多層フィルムが挙げられる。
　金属張積層体における金属箔は、銅箔であるのが好ましい。かかる金属張積層体は、プリント基板材料として特に有用である。
　多層フィルムにおける樹脂フィルムは、ポリイミドフィルムであるのが好ましい。かかる多層フィルムは、電線被覆材料、プリント基板材料として有用である。
　ポリイミドフィルムの具体例としては、「カプトン５０ＥＮ－Ｓ」（東レ・デュポン株式会社製）、「カプトン１００ＥＮ」（東レ・デュポン株式会社製）、「カプトン１００Ｈ」（東レ・デュポン株式会社製）、「カプトン１００ＫＪ」（デュポン社製）、「カプトン１００ＪＰ」（米国デュポン社製）、「カプトン１００ＬＫ」（東レ・デュポン株式会社製）が挙げられる。
　なお、プリント基板には、フレキシブルプリント基板、リジッドプリント基板が含まれる。 Preferable embodiments of the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof. Can be mentioned.
The metal foil in the metal-clad laminate is preferably a copper foil. Such a metal-clad laminate is particularly useful as a printed circuit board material.
The resin film in the multilayer film is preferably a polyimide film. Such a multilayer film is useful as an electric wire coating material and a printed circuit board material.
Specific examples of the polyimide film include "Kapton 50EN-S" (manufactured by Toray DuPont Co., Ltd.), "Kapton 100EN" (manufactured by Toray DuPont Co., Ltd.), "Kapton 100H" (manufactured by Toray DuPont Co., Ltd.), and " Examples include "Kapton 100KJ" (manufactured by DuPont), "Kapton 100JP" (manufactured by DuPont in the United States), and "Kapton 100LK" (manufactured by Toray DuPont Co., Ltd.).
The printed circuit board includes a flexible printed circuit board and a rigid printed circuit board.
　Ｆ層の基材と反対側には、さらに他の基材を積層して、多層積層体としてもよい。積層は、例えば、熱圧着により行うことができる。
　かかる多層積層体の構成としては、基材／Ｆ層／他の基材／Ｆ層／基材、金属基板層／他の基材層／Ｆ層／他の基材層／金属基板層等が挙げられる。それぞれの層には、さらに、ガラスクロスやフィラーが含まれていてもよい。
　かかる積層体は、アンテナ部品、プリント基板、航空機用部品、自動車用部品、スポーツ用具、食品工業用品、塗料、化粧品等として有用であり、具体的には、航空機用電線等の電線被覆材、電気絶縁性テープ、石油掘削用絶縁テープ、プリント基板用材料、精密濾過膜、限外濾過膜、逆浸透膜、イオン交換膜、透析膜、気体分離膜等の分離膜、リチウム二次電池用、燃料電池用等の電極バインダー、コピーロール、家具、自動車ダッシュボート、家電製品等のカバー、荷重軸受、すべり軸、バルブ、ベアリング、歯車、カム、ベルトコンベア、食品搬送用ベルト等の摺動部材、シャベル、やすり、きり、のこぎり等の工具、ボイラー、ホッパー、パイプ、オーブン、焼き型、シュート、ダイス、便器、コンテナ被覆材、離型フィルムとして有用である。 Another substrate may be laminated on the opposite side of the F layer to the substrate to form a multilayer laminate. Lamination can be performed, for example, by thermocompression bonding.
The structure of the multilayer laminate includes a base material / F layer / another base material / F layer / base material, a metal substrate layer / another base material layer / F layer / another base material layer / metal substrate layer, and the like. Can be mentioned. Each layer may further contain a glass cloth or filler.
Such a laminate 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. Insulating tape, insulating tape for oil drilling, material for printed substrate, precision filtration membrane, ultrafiltration membrane, reverse osmosis membrane, ion exchange membrane, dialysis membrane, separation membrane such as gas separation membrane, lithium secondary battery, fuel Electrode binders for batteries, copy rolls, furniture, automobile dash boats, covers for home appliances, load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, sliding members such as food transport belts, shovels. It is useful as tools for shavings, cuttings, saws, boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container covering materials, and mold release films.
　本分散液を、織布に含浸させ、加熱により乾燥させれば、Ｆポリマーが織布に含浸された含浸織布が得られる。含浸織布は、織布がＦ層で被覆された被覆織布とも言える。織布は、ガラス繊維織布、カーボン繊維織布、アラミド繊維織布または金属繊維織布が好ましく、ガラス繊維織布またはカーボン繊維織布がより好ましい。織布は、Ｆ層との密着接着性を高める観点から、シランカップリング剤で処理されていてもよい。
　含浸織布における、Ｆポリマーの含有量は、３０から８０質量％が好ましい。分散液を織布に含浸させる方法は、分散液に織布を浸漬する方法、分散液を織布に塗布する方法が挙げられる。 When the woven fabric is impregnated with the present dispersion and dried by heating, an impregnated woven fabric in which the F polymer is impregnated in the woven fabric can be obtained. The impregnated woven fabric can also be said to be a coated woven fabric in which the woven fabric is covered with an F layer. The woven fabric is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric, and more preferably a glass fiber woven fabric or a carbon fiber woven fabric. The woven fabric may be treated with a silane coupling agent from the viewpoint of enhancing the adhesiveness with the F layer.
The content of the F polymer in the impregnated woven fabric is preferably 30 to 80% by mass. Examples of the method of impregnating the woven fabric with the dispersion liquid include a method of immersing the woven fabric in the dispersion liquid and a method of applying the dispersion liquid to the woven fabric.
　織布を乾燥させた後に、Ｆポリマーを焼成させてもよい。Ｆポリマーを焼成させる方法は、織布を３００から４００℃の雰囲気にある通風乾燥炉に通す方法が挙げられる。なお、織布の乾燥とポリマーの焼成とは、一段階で実施してもよい。このようにして得られた織布は、Ｆ層と織布との密着性または接着性が高い、表面の平滑性が高い、歪が少ない等の特性に優れている。かかる織布と金属箔とを熱圧着させれば、剥離強度が高く、反りにくい金属張積層体が得られ、プリント基板材料として好適に使用できる。 After the woven fabric is dried, the F polymer may be fired. Examples of the method of firing the F polymer include a method of passing the woven fabric through a ventilation drying oven in an atmosphere of 300 to 400 ° C. The drying of the woven fabric and the firing of the polymer may be carried out in one step. The woven fabric thus obtained is excellent in characteristics such as high adhesion or adhesiveness between the F layer and the woven fabric, high surface smoothness, and little distortion. By thermocompression bonding the woven fabric and the metal foil, a metal-clad laminate having high peel strength and resistance to warping can be obtained, which can be suitably used as a printed circuit board material.
　また、含浸織布の製造において、分散液を含浸させた織布を、基材の表面に貼着等により配置し、加熱させ乾燥させることにより、Ｆポリマーと織布とを含む含浸織布層を形成して、基材と含浸織布層とが、この順に積層された積層体を製造してもよい。その態様も、特に限定されず、例えば槽、配管、容器等の部材の内壁面の一部または全部に本分散液を含浸させた織布を配置し、上記部材を回転させながら加熱すれば、部材の内壁面の一部または全部に含浸織布層を形成できる。この製造方法は、槽、配管、容器等の部材の内壁面のライニング方法としても有用である。 Further, in the production of the impregnated woven fabric, the woven fabric impregnated with the dispersion liquid is placed on the surface of the base material by sticking or the like, heated and dried to form an impregnated woven fabric layer containing the F polymer and the woven fabric. May be formed to produce a laminated body in which the base material and the impregnated woven fabric layer are laminated in this order. The embodiment is also not particularly limited, and for example, if a woven fabric impregnated with the present dispersion is placed on a part or all of the inner wall surface of a member such as a tank, a pipe, or a container, and the member is heated while rotating. An impregnated woven fabric layer can be formed on a part or all of the inner wall surface of the member. This manufacturing method is also useful as a method for lining the inner wall surface of members such as tanks, pipes, and containers.
　本分散液は、上述のとおり、分散安定性に優れており、多孔質または繊維状の材料中に、効率的に含浸できる。かかる多孔質または繊維状の材料としては、上述した織布以外の材料、具体的には、板状、柱状または繊維状の材料も挙げられる。これらの材料は、硬化性樹脂、シランカップリング剤等で予め前処理されていてもよく、無機フィラーや他の樹脂等がさらに充填されていてもよい。また、これらの材料は、撚り合わせて、糸、ケーブル、ワイヤーを形成していてもよい。撚り合わせに際しては、ポリエチレン等の他のポリマーからなる介在層を配置してもよい。かかる材料に分散液を含浸させて成形物を製造する態様としては、硬化性樹脂またはその硬化物が担持された繊維状の材料に分散液を含浸させる態様が挙げられる。 As described above, this dispersion has excellent dispersion stability and can be efficiently impregnated into a porous or fibrous material. Examples of such porous or fibrous materials include materials other than the above-mentioned woven fabrics, specifically, plate-shaped, columnar or fibrous materials. These materials may be pretreated with a curable resin, a silane coupling agent, or the like, or may be further filled with an inorganic filler, another resin, or the like. In addition, these materials may be twisted together to form a thread, a cable, or a wire. At the time of twisting, an intervening layer made of another polymer such as polyethylene may be arranged. As an embodiment in which such a material is impregnated with a dispersion liquid to produce a molded product, there is an embodiment in which a curable resin or a fibrous material on which the cured product thereof is supported is impregnated with the dispersion liquid.
　繊維状の材料としては、炭素繊維、アラミド繊維、炭化珪素繊維等の高強度かつ低伸度の繊維が挙げられる。硬化性樹脂としては、エポキシ樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂等の熱硬化性樹脂が好ましい。かかる態様の具体例としては、熱硬化性樹脂が担持された炭素繊維を撚り合わせたケーブルに分散液を含浸させ、さらに加熱してＦポリマーを焼成させて形成される複合ケーブルが挙げられる。かかる複合ケーブルは、大型構造物用、グラウンドアンカー用、石油掘削用、クレーン用、索道用、エレベーター用、農林水産用、玉掛索用のケーブルとして有用である。 Examples of the fibrous material include high-strength and low-elongation fibers such as carbon fiber, aramid fiber, and silicon carbide fiber. As the curable resin, a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, or a polyurethane resin is preferable. Specific examples of such an embodiment include a composite cable formed by impregnating a cable made by twisting carbon fibers carrying a thermosetting resin with a dispersion liquid and further heating the cable to bake an F polymer. Such a composite cable is useful as a cable for large structures, ground anchors, oil excavation, cranes, cableways, elevators, agriculture, forestry and fisheries, and slinging cables.
　上述のとおり本組成物の希釈よって分散性と分散安定性に優れた本分散液が得られる。かかる本分散液はＦポリマー粒子の凝集が抑えられ、本分散液の製造や使用の際の泡立ちが抑制される。その結果、得られる塗膜や成形物の表面平滑性が優れる。 As described above, by diluting the present composition, the present dispersion having excellent dispersibility and dispersion stability can be obtained. In this dispersion, aggregation of F polymer particles is suppressed, and foaming during production and use of this dispersion is suppressed. As a result, the surface smoothness of the obtained coating film or molded product is excellent.
　以上、本組成物、本組成物の製法、本組成物からの本分散液の製法について説明したが、本発明は、上述した実施形態の構成に限定されない。
　例えば、本組成物や本分散液の製法は、上記実施形態の構成において、他の任意の工程を追加で有してもよいし、同様の作用を生じる任意の工程と置換されていてよい。また、本組成物およびや本分散液は上記実施形態の構成において、他の任意の構成を追加してもよいし、同様の機能を発揮する任意の構成と置換されていてよい。 Although the present composition, the method for producing the present composition, and the method for producing the present dispersion liquid from the present composition have been described above, the present invention is not limited to the configuration of the above-described embodiment.
For example, the method for producing the present composition and the present dispersion 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. Further, the present composition and the present dispersion may be added to any other composition in the configuration of the above embodiment, or may be replaced with an arbitrary composition exhibiting the same function.
　以下、実施例によって本発明を詳細に説明するが、本発明はこれらに限定されない。
［例１］
１－１．各成分の準備
　［パウダー］
　パウダー１１：ＴＦＥ単位、ＮＡＨ単位およびＰＰＶＥ単位を、この順に９７．９モル％、０．１モル％、２．０モル％含み、カルボニル基含有基を主鎖炭素数１×１０６個あたり１０００個有するポリマー（フッ素含有量：７６質量％）からなるパウダー（Ｄ５０：２．０μｍ、比表面積：３ｍ２／ｇ）
　パウダー１２：：ＴＦＥ単位およびＰＰＶＥ単位からなる、カルボニル基含有基を主鎖炭素数１×１０６個あたり４０個有するポリマー（フッ素含有量：７６質量％）からなるパウダー（Ｄ５０：２．４μｍ、比表面積：４ｍ２／ｇ）
　［芳香族ポリマー］
　ワニス１：熱可塑性の芳香族ポリイミド（ＰＩ１）がＮＭＰに溶解したワニス
　［界面活性剤］
　界面活性剤１：ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）ＯＣＨ２ＣＨ２（ＣＦ２）６ＦとＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）（ＯＣＨ２ＣＨ２）２３ＯＨとのコポリマーであり、フッ素含有量が、３５質量％であるノニオン性ポリマー
　［液状媒体］
　ＮＭＰ：Ｎ－メチル－２－ピロリドン
　［粘度］
　以下の例１における粘度は、温度を２５℃、回転数を３０ｒｐｍとしてＢ型粘度計で測定される粘度をいう。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
[Example 1]
1-1. Preparation of each ingredient [Powder]
Powder 11: Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order, and contains carbonyl group-containing groups 1000 per 1 × 10 6 main chain carbon atoms. Powder (D50: 2.0 μm, specific surface area: 3 m 2 / g) composed of individual polymers (fluorine content: 76% by mass)
Powder 12 :: A powder consisting of a polymer (fluorine content: 76% by mass) having 40 carbonyl group-containing groups per 1 × 10 6 main chain carbon atoms (D50: 2.4 μm, consisting of TFE units and PPVE units). Specific surface area: 4m 2 / g)
[Aromatic polymer]
Varnish 1: Varnish in which thermoplastic aromatic polyimide (PI1) is dissolved in NMP [surfactant]
Surfactant 1: CH 2 = C (CH 3 ) C (O) OCH 2 CH 2 (CF 2 ) 6 F and CH 2 = C (CH 3 ) C (O) (OCH 2 CH 2 ) 23 OH Nonionic polymer that is a copolymer and has a fluorine content of 35% by mass [Liquid medium]
NMP: N-methyl-2-pyrrolidone [viscosity]
The viscosity in Example 1 below refers to the viscosity measured by a B-type viscometer at a temperature of 25 ° C. and a rotation speed of 30 rpm.
１－２．分散液の製造例
　［例１－１]
　プラネタリーミキサーに、パウダー１１、ワニス１、界面活性剤１、ＮＭＰを混合して得られた、パウダー１１（７０質量部）、ＰＩ１（１．８質量部）、界面活性剤１（３．５質量部）およびＮＭＰ（３０質量部）を含む液状組成物を投入し、プラネタリーミキサー内を減圧保持して脱気しながら液状組成物を混練し、ＮＭＰを添加して粘度が１００００ｍＰａ・ｓに粘度調整されたペースト状の組成物１を得た。組成物１を、大気圧下、２５℃にて４８時間静置した後、全体としてＮＭＰが７０質量部となるように、組成物１にＮＭＰを複数回に分けて投入し、撹拌して混合し、粘度が１０００ｍＰａ・ｓの分散液１１を得た。 1-2. Production Example of Dispersion Liquid [Example 1-1]
Powder 11 (70 parts by mass), PI1 (1.8 parts by mass), and surfactant 1 (3.5 by mass) obtained by mixing powder 11, varnish 1, surfactant 1, and NMP in a planetary mixer. A liquid composition containing (parts by mass) and NMP (30 parts by mass) was added, the liquid composition was kneaded while holding the inside of the planetary mixer under reduced pressure and degassed, and NMP was added to bring the viscosity to 10,000 mPa · s. A viscosity-adjusted paste-like composition 1 was obtained. After allowing the composition 1 to stand at 25 ° C. for 48 hours under atmospheric pressure, the NMP is added to the composition 1 in a plurality of times so that the NMP becomes 70 parts by mass as a whole, and the mixture is stirred and mixed. Then, a dispersion liquid 11 having a viscosity of 1000 mPa · s was obtained.
　［例１－２から例１－６]
　パウダーの種類と、脱気または静置の有無と、静置に際しての粘度調整、すなわちペースト状組成物を製造する際のＮＭＰの追加添加の有無とを、表１に記載のとおり変更した以外は例１－１と同様に行いペースト状の組成物２から６を得た。得られたペースト２から６を用い、例１－１と同様にして分散液１２～１６を得た。なお、表１中の「静置」欄における括弧内の数値は、静置時間（単位：ｈｒ）を示す。 [Examples 1-2 to 1-6]
Except for changing the type of powder, the presence or absence of degassing or standing, and the viscosity adjustment during standing, that is, the presence or absence of additional addition of NMP when producing a paste-like composition, as shown in Table 1. The same procedure as in Example 1-1 was carried out to obtain paste-like compositions 2 to 6. Using the obtained pastes 2 to 6, dispersion liquids 12 to 16 were obtained in the same manner as in Example 1-1. The numerical value in parentheses in the "static" column in Table 1 indicates the static time (unit: hr).
　なお、組成物１、組成物３、分散液１１、分散液１３の泡沫体積比率は０％以上５％未満であり、組成物２、組成物４、組成物６、分散液１２、分散液１４、分散液１６の泡沫体積比率は５％超１０％未満であった。組成物５、分散液１５の泡沫体積比率は１０％以上であった The foam volume ratio of the composition 1, the composition 3, the dispersion liquid 11, and the dispersion liquid 13 is 0% or more and less than 5%, and the composition 2, the composition 4, the composition 6, the dispersion liquid 12, and the dispersion liquid 14 The foam volume ratio of the dispersion liquid 16 was more than 5% and less than 10%. The foam volume ratio of the composition 5 and the dispersion liquid 15 was 10% or more.
１－３．分散液の評価
　希釈した分散液を２枚の石英ガラス間に挟み込み、光学顕微鏡の透光モードを用いて透光像を観察し、分散液中のパウダーの分散状態を、以下の評価基準で評価した。なお、透光像は、コントラストまたは模様がない程、分散液の流動性と分散性が高いことを示す。
　＜評価基準＞
　〇：透光像にコントラストと網目状の模様がない。
　△：透光像にコントラストがあるが、網目状の模様がない。
　×：透光像にコントラストと網目状の模様がある。 1-3. Evaluation of dispersion liquid A diluted dispersion is sandwiched between two quartz glasses, a translucent image is observed using the translucency mode of an optical microscope, and the dispersion state of the powder in the dispersion is evaluated according to the following evaluation criteria. bottom. The translucent image shows that the fluidity and dispersibility of the dispersion are higher as there is no contrast or pattern.
<Evaluation criteria>
〇: There is no contrast and mesh pattern in the translucent image.
Δ: There is contrast in the translucent image, but there is no mesh pattern.
X: The translucent image has contrast and a mesh pattern.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
１－４．積層体の製造例
　［積層体１］
　厚さ１８μｍの長尺の銅箔の表面に、バーコーターを用いて分散液１１を塗布して、ウェット膜を形成した。次いで、このウェット膜が形成された金属箔を、１１０℃にて５分間、乾燥炉に通し、加熱により乾燥させて、ドライ膜を得た。その後、窒素オーブン中で、ドライ膜を３８０℃にて３分間、加熱した。これにより、金属箔と、その表面にパウダー１１の溶融焼成物およびＰＩ１を含む、成形物として厚さ２０μｍのポリマー層とを有する積層体１１を製造した。 1-4. Manufacturing example of laminated body [Laminated body 1]
The dispersion liquid 11 was applied to the surface of a long copper foil having a thickness of 18 μm 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 11 having a metal foil and a polymer layer having a thickness of 20 μm as a molded product containing a melt-fired product of powder 11 and PI1 on the surface thereof was produced.
　［積層体２～６］
　積層体１の製造において、分散液１１を分散液１２から１６に変更して、同様に積層体を製造し、それぞれ積層体２～６を得た。 [Laminates 2 to 6]
In the production of the laminate 1, the dispersion liquid 11 was changed from the dispersion liquid 12 to 16, and the laminates were similarly produced to obtain the laminates 2 to 6, respectively.
１－５．積層体の評価
　得られた積層体１～６の塗工むらと誘電正接を下記基準に従い評価した。
結果を表２に示した。 1-5. Evaluation of Laminates The coating unevenness and dielectric loss tangent of the obtained laminates 1 to 6 were evaluated according to the following criteria.
The results are shown in Table 2.
１－５－１.積層体の塗工むらの評価
　＜評価基準＞
　〇：ポリマー層の表面にブツが視認されず、面全体としても平滑である。
　△：ポリマー層の一部にブツが視認されるが、面全体としては平滑である。
　×：ポリマー層の全面にブツが視認され、面全体として凹凸がある。 1-5-1. Evaluation of coating unevenness of laminated body <Evaluation criteria>
〇: No lumps are visible on the surface of the polymer layer, and the entire surface is smooth.
Δ: Although lumps are visible on a part of the polymer layer, the entire surface is smooth.
X: The lumps are visually recognized on the entire surface of the polymer layer, and the entire surface is uneven.
１－５－２.積層体の誘電正接の評価
　それぞれの積層体について、積層体の銅箔を塩化第二鉄水溶液でエッチングにより除去して単独のポリマー層を作製し、ＳＰＤＲ（スプリットポスト誘電体共振）法にて、上記ポリマー層の誘電正接を測定周波数１０ＧＨｚで測定し、下記の基準に従って評価した。 1-5-2. Evaluation of Dielectric Dissipation Factor of Laminates For each laminate, the copper foil of the laminate is removed by etching with an aqueous ferric chloride solution to prepare a single polymer layer, and SPDR (split post dielectric) is prepared. By the resonance) method, the dielectric loss tangent of the polymer layer was measured at a measurement frequency of 10 GHz and evaluated according to the following criteria.
　＜評価基準＞
　〇：その誘電正接が０．００１０未満である。
　△：その誘電正接が０．００１０以上０．００２５以下である。
　×：その誘電正接が０．００２５超である。 <Evaluation criteria>
〇: The dielectric loss tangent is less than 0.0010.
Δ: The dielectric loss tangent is 0.0010 or more and 0.0025 or less.
X: The dielectric loss tangent is more than 0.0025.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［例２］
　２－１．各成分の準備
［パウダー］
　パウダー２１：ＴＦＥ単位、ＮＡＨ単位およびＰＰＶＥ単位を、この順に９７．９モル％、０．１モル％、２．０モル％含み、カルボニル基を主鎖炭素数１×１０６個あたり１０００個有し、溶融温度が３００℃であるポリマーからなるパウダー（Ｄ５０：２．１μｍ） [Example 2]
2-1. Preparation of each ingredient [powder]
Powder 21: Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order, and has 1000 carbonyl groups per 1 × 10 6 main chain carbon atoms. A powder (D50: 2.1 μm) made of a polymer having a melting temperature of 300 ° C.
［極性ポリマー］
　極性ポリマー１：芳香族ポリイミド（宇部興産社製、「Ｕ－ワニス」）
　極性ポリマー２：カルボキシメチルセルロース（日本製紙社製、「サンローズＭＡＣシリーズ２００ＨＣ」）
　極性ポリマー３：ポリビニルアルコール（積水化学工業社製、「エスレックＢＬ－１」） [Polar polymer]
Polar Polymer 1: Aromatic Polyimide (manufactured by Ube Kosan Co., Ltd., "U-Varnish")
Polar Polymer 2: Carboxymethyl Cellulose (Nippon Paper Industries, Ltd., "Sunrose MAC Series 200HC")
Polar polymer 3: Polyvinyl alcohol (manufactured by Sekisui Chemical Co., Ltd., "Eslek BL-1")
［無機フィラー］
　無機フィラー１：アミノシランカップリング剤で表面処理されているシリカフィラー（Ｄ５０：０．２μｍ） [Inorganic filler]
Inorganic filler 1: Silica filler surface-treated with an aminosilane coupling agent (D50: 0.2 μm)
［液状媒体］
　ＮＭＰ：Ｎ－メチル－２－ピロリドン
　［粘度］
　以下の例２における組成物の粘度は、温度を２５℃、剪断速度を１ｓ－１とするキャピログラフ測定による粘度をいい、分散液の粘度は、温度を２５℃、回転数を３０ｒｐｍとしてＢ型粘度計で測定される粘度をいう。 [Liquid medium]
NMP: N-methyl-2-pyrrolidone [viscosity]
The viscosity of the composition in Example 2 below refers to the viscosity measured by capillograph at a temperature of 25 ° C. and a shear rate of 1s -1 , and the viscosity of the dispersion liquid is a B-type viscosity at a temperature of 25 ° C. and a rotation speed of 30 rpm. Viscosity measured by a meter.
　２－２．組成物の製造例
［例２－１］
　ポットに、極性ポリマー１のワニス（溶媒：ＮＭＰ）とＮＭＰとを投入し混合した。さらに、ポットに、パウダー２１と無機フィラー１の粉体混合物を投入して混合し、混合物を調製した。この混合物をプラネタリーミキサー中にて混練してから取り出し、パウダー２１（５０質量部）、無機フィラー１（４０質量部）および極性ポリマー１（１０質量部）、ＮＭＰ（３０質量部）を含む組成物２１を得た。組成物２１は、塊状かつ粘土状であり、ウェットパウダーであった。
　温度を２５℃、剪断速度を１ｓ－１としてキャピログラフを測定した時の、組成物２１の粘度は１８０００Ｐａ・ｓであり、さらに組成物２１を混練しても、その粘度の変動幅は±３％以内であった。
　組成物２１に、ＮＭＰを複数回に分けて添加しつつ、自転公転撹拌機にて２０００ｒｐｍで脱気しながら撹拌した。さらに、ＮＭＰを、複数回に分けて添加しながら撹拌し、全体として８０質量部のＮＭＰを組成物２１に添加して分散液を調製し、分散液２１を得た。分散液２１の粘度は、３００ｍＰａ・ｓであった。 2-2. Production Example of Composition [Example 2-1]
The varnish (solvent: NMP) of polar polymer 1 and NMP were put into a pot and mixed. Further, a powder mixture of the powder 21 and the inorganic filler 1 was put into a pot and mixed to prepare a mixture. This mixture is kneaded in a planetary mixer and then taken out, and has a composition containing powder 21 (50 parts by mass), inorganic filler 1 (40 parts by mass) and polar polymer 1 (10 parts by mass), and NMP (30 parts by mass). I got the thing 21. The composition 21 was lumpy, clay-like, and wet powder.
When the capillograph was measured at a temperature of 25 ° C. and a shear rate of 1s -1 , the viscosity of the composition 21 was 18,000 Pa · s, and even if the composition 21 was further kneaded, the fluctuation range of the viscosity was ± 3%. It was within.
NMP was added to the composition 21 in a plurality of times, and the mixture was stirred while degassing at 2000 rpm with a rotating revolution stirrer. Further, NMP was added in a plurality of times and stirred, and 80 parts by mass of NMP as a whole was added to the composition 21 to prepare a dispersion liquid, and a dispersion liquid 21 was obtained. The viscosity of the dispersion 21 was 300 mPa · s.
［例２－２］
　極性ポリマー１を極性ポリマー２に変更した以外は例２－１と同様にして組成物２２と分散液２２を得た。組成物２２の粘度は、２００００Ｐａ・ｓであり、さらに組成物２２を混練しても、その粘度の変動幅は±３％以内であった。分散液２２の粘度は４００ｍＰａ・ｓであった。
［例２－３］
　極性ポリマー１を極性ポリマー３に変更した以外は例２－１と同様にして組成物２３と分散液２３を得た。組成物２３の粘度は、２１０００Ｐａ・ｓであり、さらに組成物２３を混練しても、その粘度の変動幅は±３％以内であった。分散液２３の粘度は４００ｍＰａ・ｓであった。
［例２－４］
　混練時間を半分にした以外は、例２－１と同様にして組成物２４と分散液２４を得た。組成物２４の粘度は６００００Ｐａ・ｓであり、さらに組成物２４を混練すると、その粘度は±５％を超えて変動した。分散液２４の粘度は８００ｍＰａ・ｓであった。 [Example 2-2]
The composition 22 and the dispersion liquid 22 were obtained in the same manner as in Example 2-1 except that the polar polymer 1 was changed to the polar polymer 2. The viscosity of the composition 22 was 20000 Pa · s, and even when the composition 22 was further kneaded, the fluctuation range of the viscosity was within ± 3%. The viscosity of the dispersion 22 was 400 mPa · s.
[Example 2-3]
The composition 23 and the dispersion liquid 23 were obtained in the same manner as in Example 2-1 except that the polar polymer 1 was changed to the polar polymer 3. The viscosity of the composition 23 was 21000 Pa · s, and even when the composition 23 was further kneaded, the fluctuation range of the viscosity was within ± 3%. The viscosity of the dispersion liquid 23 was 400 mPa · s.
[Example 2-4]
The composition 24 and the dispersion liquid 24 were obtained in the same manner as in Example 2-1 except that the kneading time was halved. The viscosity of the composition 24 was 60,000 Pa · s, and when the composition 24 was further kneaded, the viscosity fluctuated by more than ± 5%. The viscosity of the dispersion liquid 24 was 800 mPa · s.
［例２－５］
　パウダー２１の量を２５質量部に、極性ポリマー１の量を５質量部に変更した以外は、例２－１と同様にして組成物２５と分散液２５を得た。組成物２５の粘度は８０００Ｐａ・ｓであった。分散液２５の粘度は４００ｍＰａ・ｓであった。 [Example 2-5]
The composition 25 and the dispersion liquid 25 were obtained in the same manner as in Example 2-1 except that the amount of the powder 21 was changed to 25 parts by mass and the amount of the polar polymer 1 was changed to 5 parts by mass. The viscosity of the composition 25 was 8000 Pa · s. The viscosity of the dispersion liquid 25 was 400 mPa · s.
［例２－６］
　ＮＭＰをｎ－デカンに変更した以外は例２－１と同様にして組成物２６と分散液２６を得た。組成物２６の粘度は、８００００Ｐａ・ｓであり、さらに組成物２６を混練しても、その粘度の変動幅は±３％以内であった。分散液２６の粘度は３０００ｍＰａ・ｓであった。 [Example 2-6]
The composition 26 and the dispersion liquid 26 were obtained in the same manner as in Example 2-1 except that the NMP was changed to n-decane. The viscosity of the composition 26 was 80,000 Pa · s, and even when the composition 26 was further kneaded, the fluctuation range of the viscosity was within ± 3%. The viscosity of the dispersion liquid 26 was 3000 mPa · s.
　２－３．評価
　２－３－１．分散液の分散安定性の評価
　それぞれの分散液を容器中に２５℃にて長期保管保存後、その分散性を目視にて確認し、下記の基準に従って分散安定性を評価した。
　［評価基準］
　〇：凝集物が視認されない。
　△：容器側壁に細かな凝集物の付着が視認される。軽く撹拌すると均一に再分散した。
　×：容器底部にも凝集物が沈殿しているのが視認される。再分散には強いせん断撹拌を要した。 2-3. Evaluation 2-3-1. Evaluation of Dispersion Stability of Dispersions After storing each dispersion in a container at 25 ° C for a long period of time, the dispersibility was visually confirmed and the dispersion stability was evaluated according to the following criteria.
[Evaluation criteria]
〇: Aggregates are not visible.
Δ: Fine agglomerates are visually recognized on the side wall of the container. With light stirring, it was uniformly redispersed.
X: It can be visually confirmed that the agglomerates are also settled on the bottom of the container. Strong shear agitation was required for redispersion.
　２－３－２．分散液のチキソ安定性の評価
　それぞれの分散液を容器中に２５℃にて３０日保管し、保管前後におけるチキソ比の変動幅を測定し、下記の基準に従ってチキソ安定性を評価した。
　［評価基準］
　〇：チキソ比の変動幅が、絶対値で１未満である
　△：チキソ比の変動幅が、絶対値で１以上３以下である
　×：チキソ比の変動幅が、絶対値で３超である
　それぞれの評価結果を、まとめて下表３に示す。 2-3-2. Evaluation of thixotropy stability of dispersions Each dispersion was stored in a container at 25 ° C. for 30 days, the fluctuation range of thixotropy before and after storage was measured, and the thixotropy was evaluated according to the following criteria.
[Evaluation criteria]
〇: Thixotropy fluctuation range is less than 1 in absolute value Δ: Thixotropy fluctuation range is 1 or more and 3 or less in absolute value ×: Thixotropy fluctuation range is more than 3 in absolute value The results of each evaluation are summarized in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記結果から明らかなように、本法で作成した分散液は分散性、分散安定性、チキソ安定性に優れており、したがって本法により得られた分散液を用いた積層体は成分分布の均一性に優れ、諸物性に優れていた。
　なお、２０２０年１０月２９日に出願された日本特許出願２０２０－１８１７７１号および２０２１年０３月２５日に出願された日本特許出願２０２１－０５１４３７号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 As is clear from the above results, the dispersion prepared by this method is excellent in dispersibility, dispersion stability, and thixotropic stability, and therefore, the laminate using the dispersion obtained by this method has a uniform component distribution. It was excellent in properties and various physical properties.
The entire specification, claims and abstracts of Japanese Patent Application No. 2020-181771 filed on October 29, 2020 and Japanese Patent Application No. 2021-051437 filed on March 25, 2021. The contents are cited here and incorporated as disclosure of the specification of the present invention.

Claims (15)

  1. 　比表面積が２５ｍ２／ｇ以下であるテトラフルオロエチレン系ポリマーのパウダーに由来する粒子と液状媒体を含有し、固形分濃度が４０質量％以上であり、温度を２５℃、回転数を３０ｒｐｍとしてＢ型粘度計で測定される粘度が８０００～１０００００ｍＰａ・ｓである、組成物。 Contains particles and liquid medium derived from tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less, a solid content concentration of 40% by mass or more, a temperature of 25 ° C., and a rotation speed of 30 rpm. A composition having a viscosity measured by a type viscometer of 8000 to 100,000 mPa · s.
  2. 　さらに前記液状媒体に溶解性の、前記テトラフルオロエチレン系ポリマー以外のポリマーまたは樹脂を含む、請求項１に記載の組成物。 The composition according to claim 1, further comprising a polymer or resin other than the tetrafluoroethylene polymer, which is soluble in the liquid medium.
  3. 　比表面積が２５ｍ２／ｇ以下であるテトラフルオロエチレン系ポリマーのパウダーに由来する粒子、極性ポリマーまたはその前駆体、およびかかる極性ポリマーまたはその前駆体を溶解しうる極性を有する液状媒体を含み、温度を２５℃、剪断速度を１ｓ－１とするキャピログラフ測定による粘度が１００００～１０００００Ｐａ・ｓである、組成物。 Contains particles derived from a powder of a tetrafluoroethylene-based polymer having a specific surface area of 25 m 2 / g or less, a polar polymer or a precursor thereof, and a liquid medium having a polarity capable of dissolving the polar polymer or the precursor thereof, and the temperature. A composition having a viscosity of 10,000 to 100,000 Pa · s as measured by a capillograph at 25 ° C. and a shear rate of 1 s -1 .
  4. 　前記粒子の含有量と前記極性ポリマーまたはその前駆体の含有量の合計が５０質量％超であり、前記極性を有する液状媒体の含有量が４０質量％以下であり、前記粒子の含有量に対する前記極性ポリマーまたはその前駆体の含有量の比が０．００１以上０．５未満である、請求項３に記載の組成物。 The total content of the particles and the content of the polar polymer or its precursor is more than 50% by mass, the content of the liquid medium having the polarity is 40% by mass or less, and the content of the particles is relative to the content of the particles. The composition according to claim 3, wherein the ratio of the contents of the polar polymer or the precursor thereof is 0.001 or more and less than 0.5.
  5. 　前記極性ポリマーまたはその前駆体が、イミド系ポリマー、イミド系ポリマーの前駆体、ビニル系ポリマーまたは多糖類である、請求項３または４に記載の組成物。 The composition according to claim 3 or 4, wherein the polar polymer or its precursor is an imide-based polymer, a precursor of an imide-based polymer, a vinyl-based polymer, or a polysaccharide.
  6. 　前記極性を有する液状媒体が、水、アミド、ケトンおよびエステルからなる群から選ばれる液状媒体である、請求項３～５のいずれか１項に記載の組成物。 The composition according to any one of claims 3 to 5, wherein the liquid medium having the polarity is a liquid medium selected from the group consisting of water, amides, ketones and esters.
  7. 　前記テトラフルオロエチレン系ポリマーがカルボニル基含有基または水酸基含有基を有するポリマーである、請求項１～６のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 6, wherein the tetrafluoroethylene polymer is a polymer having a carbonyl group-containing group or a hydroxyl group-containing group.
  8. 　前記テトラフルオロエチレン系ポリマーのフッ素含有量が７０質量％以上である、請求項１～７のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the tetrafluoroethylene polymer has a fluorine content of 70% by mass or more.
  9. 　前記テトラフルオロエチレン系ポリマーの溶融温度が１８０～３２５℃である、請求項１～８のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 8, wherein the tetrafluoroethylene polymer has a melting temperature of 180 to 325 ° C.
  10. 　前記テトラフルオロエチレン系ポリマーのパウダーを構成する粒子の平均粒子径が０.１～２０μｍである、請求項１～９のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 9, wherein the average particle size of the particles constituting the tetrafluoroethylene polymer powder is 0.1 to 20 μm.
  11. 　さらに無機フィラーを含む、請求項１～１０のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 10, further comprising an inorganic filler.
  12. 　比表面積が２５ｍ２／ｇ以下であるテトラフルオロエチレン系ポリマーのパウダーに由来する粒子と液状媒体とを含む混合物を混練するとともに、かかる混練中もしくは混練後の脱気および混練後の静置の少なくともいずれかを行うことにより請求項１～１１のいずれか１項に記載の組成物を製造する、組成物の製造方法。 A mixture containing particles derived from a tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less and a liquid medium is kneaded, and at least the degassing during or after the kneading and the standing after the kneading are performed. A method for producing a composition, wherein the composition according to any one of claims 1 to 11 is produced by performing any of these.
  13. 　前記脱気および前記静置の両方を行う、請求項１２に記載の製造方法。 The manufacturing method according to claim 12, wherein both the degassing and the standing still are performed.
  14. 　請求項１～１１のいずれか１項に記載の組成物を第２の液状媒体で希釈して分散液を得る、分散液の製造方法。 A method for producing a dispersion liquid, wherein the composition according to any one of claims 1 to 11 is diluted with a second liquid medium to obtain a dispersion liquid.
  15. 　比表面積が２５ｍ２／ｇ以下であるカルボニル基含有基または水酸基含有基を有するテトラフルオロエチレン系ポリマーのパウダーに由来する粒子と、カルボニル基含有基または水酸基含有基を有する極性ポリマーまたはその前駆体と、アミド、ケトンおよびエステルからなる群から選ばれる少なくとも１種の極性を有する液状媒体とを含む、ウェットパウダー。 Particles derived from a powder of a tetrafluoroethylene-based polymer having a carbonyl group-containing group or a hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, and a polar polymer having a carbonyl group-containing group or a hydroxyl group-containing group or a precursor thereof. , A wet powder comprising at least one polar liquid medium selected from the group consisting of amides, ketones and esters.
PCT/JP2021/039342 2020-10-29 2021-10-25 Composition including powder particles of tetrafluoroethylene polymer, method for producing same, method for producing dispersion from said composition WO2022092036A1 (en)

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