Composition comprising powder particles of tetrafluoroethylene-based polymer, method for producing the same, method for producing a dispersion from the composition

Abstract

The present invention provides a high viscosity composition of a powder particle of a tetrafluoroethylene-based polymer and a liquid medium, a method for producing the composition, and a method for producing a dispersion liquid having excellent dispersion stability from the composition. A composition comprising: a particle derived from a tetrafluoroethylene-based polymer powder having a specific surface area of 25 m 2 / g or less, a liquid medium, and, optionally, another polymer dissolved in the liquid medium, wherein the viscosity determined with a B-type viscometer at a temperature of 25°C and a rotation speed of 30 rpm is 8000 to 100000 mPa·s, or the viscosity obtained from a capillary rheometer measurement at a temperature of 25°C and a shear rate of 1 s ‑1 -1 is 10000 to 100000 Pa·s. Also provided is a method for producing the composition by mixing the components of the composition and performing at least one of degassing during or after the mixing and standing after the mixing, and a method for producing a dispersion liquid having the particles derived from the powder dispersed in the liquid medium by diluting the composition with the liquid medium.

Description

TECHNICAL FIELD

[0001] The present application relates to a high-viscosity composition comprising powder particles of a tetrafluoroethylene-based polymer and a liquid medium, a method for producing the high-viscosity composition, and a method for producing a dispersion liquid in which tetrafluoroethylene-based polymer particles are dispersed from the high-viscosity composition. BACKGROUND

[0002] Tetrafluoroethylene-based polymers have excellent properties such as electrical insulation, water / oil repellency, chemical resistance, and heat resistance. Therefore, a dispersion liquid in which the powder of a tetrafluoroethylene-based polymer is dispersed in water or an oily solvent can be used as a material for forming a resist, an adhesive, an electrical insulation layer, a lubricant, an ink, a paint, or the like. However, the surface energy of a tetrafluoroethylene-based polymer is low, and the particles that constitute the powder thereof (hereinafter also referred to as "powder particles") easily agglomerate with each other. Therefore, it is difficult to obtain a low-viscosity dispersion liquid having excellent dispersion stability.

[0003] For example, Patent Literature 1 discloses a non-aqueous dispersion liquid in which an additive is used from the viewpoint of improving the dispersibility of the dispersion liquid and adjusting the liquid properties thereof.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: International Publication No. 2016 / 159102 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, the dispersion liquid described in Patent Literature 1 is still insufficient in terms of dispersion stability.

[0009] In particular, in the case of a tetrafluoroethylene-based polymer powder having a high fluorine content and a small specific surface area, the dispersion liquid thereof is prepared with intense foaming, and sometimes the dispersion stability decreases due to agglomeration. In addition, the surface smoothness of a coating film or a molded article obtained from such a dispersion liquid sometimes decreases.

[0010] The present inventors earnestly studied a method for producing a dispersion liquid in which powder particles of a tetrafluoroethylene-based polymer having a small specific surface area have excellent dispersion stability, and as a result, the present application was completed.

[0011] In addition, a dispersion liquid containing powder particles of a tetrafluoroethylene-based polymer and further containing other functional materials (inorganic fillers, polymers or resins different from the tetrafluoroethylene-based polymer, or the like) can also impart the properties of the other functional materials to a coating film or a molded article formed therefrom.

[0012] However, the affinity of tetrafluoroethylene-based polymers with other functional materials is generally low, and the dispersion stability of the dispersion liquid has a tendency to further decrease.

[0013] When other functional materials are added, if high shear is applied to disperse the tetrafluoroethylene-based polymer powder, foaming or coagulation tends to occur due to air entrainment, deterioration of the tetrafluoroethylene-based polymer, and the like.

[0014] As a result, the water resistance tends to decrease due to a decrease in the uniformity of the composition distribution or the occurrence of voids in a coating film or a molded article obtained from the dispersion liquid.

[0015] The present application has the following technical contents.

[0016] Further, the present application has the following technical contents.

[0017] Further, the present application has the following technical contents.

[0018] Technical solution adopted to solve the technical problem

[0019] The present application has the following technical contents.

[0020] [1] A composition comprising particles derived from a tetrafluoroethylene-based polymer powder having a specific surface area of 25 m 2 / g or less and a liquid medium, the solid content concentration being 40 mass% or more and the viscosity measured at a temperature of 25°C and a rotation speed of 30 rpm using a B-type viscometer being 8000 to 100000 mPa-s.

[0021] [2] The composition according to [1], further comprising a polymer or a resin other than the tetrafluoroethylene-based polymer, which is soluble in the liquid medium.

[0022] [3] A composition comprising particles derived from a tetrafluoroethylene-based polymer powder having a specific surface area of 25 m 2 / g or less, a polar polymer or a precursor thereof, and a liquid medium having polarity capable of dissolving the polar polymer or the precursor thereof, the viscosity being 10000 to 100000 Pa-s according to capillary rheometry at a temperature of 25°C and a shear rate of 1 s -1

[0023] ​[4] The composition according to [3], wherein the total content of the particles and the polar polymer or precursor thereof is more than 50 mass%, the content of the liquid medium having polarity is 40 mass% or less, and the ratio of the content of the polar polymer or precursor thereof to the content of the particles is 0.001 or more and less than 0.5.

[0024] [5] The composition according to [3] or [4], wherein the polar polymer or precursor thereof is an imide-based polymer, a precursor of an imide-based polymer, an ethylene-based polymer, or a polysaccharide.

[0025] [6] The composition according to any one of [3] to [5], wherein the liquid medium having polarity is a liquid medium selected from water, amide, ketone, and ester.

[0026] [7] The composition according to any one of [1] to [6], wherein the tetrafluoroethylene-based polymer is a polymer having a carbonyl group-containing group or a hydroxyl group-containing group.

[0027] [8] The composition according to any one of [1] to [7], wherein the fluorine content of the tetrafluoroethylene-based polymer is 70 mass% or more.

[0028] [9] The composition according to any one of [1] to [8], wherein the melting temperature of the tetrafluoroethylene-based polymer is 180 to 325°C.

[0029]

[10] The composition according to any one of [1] to [9], wherein the average particle diameter of the particles constituting the tetrafluoroethylene-based polymer powder is 0.1 to 20 μm.

[0030]

[11] The composition according to any one of [1] to

[10] , further comprising an inorganic filler.

[0031]

[12] A method for producing a composition according to any one of [1] to

[11] , which kneads a mixture containing particles derived from a tetrafluoroethylene-based polymer powder having a specific surface area of 25 m 2 / g or less and a liquid medium, and performs at least one of degassing during or after the kneading and standing after the kneading.

[0032]

[13] The production method according to

[12] , wherein both the degassing and the standing are performed.

[0033]

[14] A method for producing a dispersion liquid, which dilutes the composition according to any one of [1] to

[11] with a second liquid medium to obtain a dispersion liquid.

[0034]

[15] A wet powder, which comprises: particles derived from a tetrafluoroethylene-based polymer powder having a specific surface area of 25 m2 Particles of a tetrafluoroethylene-based polymer powder having a carbonyl group-containing or hydroxyl group-containing group, a polar polymer having a carbonyl group-containing or hydroxyl group-containing group or a precursor thereof, and a liquid medium having a polarity selected from at least one of an amide, a ketone and an ester, having a polarity of 0.1 or less.

[0035] Effects of the Invention

[0036] By using the high viscosity composition of the present application, a dispersion liquid having a tetrafluoroethylene-based polymer powder-derived particle with a small specific surface area and excellent dispersion stability can be produced. By using the dispersion liquid obtained by the production method, a coating film or a molded article obtained therefrom has an appearance with excellent surface smoothness. DETAILED DESCRIPTION

[0037] The following terms have the following meanings.

[0038] The "tetrafluoroethylene-based polymer" is a polymer containing a unit based on tetrafluoroethylene (hereinafter also referred to as TFE unit).

[0039] The "glass transition temperature (Tg) of the polymer" is a value determined by dynamic viscoelasticity measurement (DMA) analysis of the polymer.

[0040] The "melting temperature (melting point) of the polymer" refers to the temperature corresponding to the maximum value of the melting peak determined by differential scanning calorimetry (DSC) measurement.

[0041] The "D50" is the average particle diameter of the particles constituting the measurement target such as a powder or an inorganic filler, and is the volume-based cumulative 50% diameter of the particles constituting the measurement target, which is obtained by laser diffraction / scattering method. That is, the particle size distribution of the particles constituting the measurement target is determined by laser diffraction scattering method, and the cumulative curve is obtained with the total volume of the measurement target being 100%, and the particle diameter at the point where the cumulative volume reaches 50% on the cumulative curve.

[0042] The "D90" is the cumulative volume particle diameter of the particles constituting the measurement target, and is the volume-based cumulative 90% diameter of the particles, which is obtained in the same manner as the "D50".

[0043] The "viscosity obtained by capillary rheometry" is the viscosity determined using a capillary having a capillary length of 10 mm and a capillary radius of 1 mm at a furnace body diameter of 9.55 mm and a load cell capacity of 2 t.

[0044] The "viscosity determined by a B-type viscometer" refers to the value determined at room temperature (25°C) and at a rotation speed of 30 rpm using a B-type viscometer. The determination is repeated 3 times, and the average of the 3 determined values is taken.

[0045] "Thixotropic ratio" means a value (η1 / η2) calculated by dividing the viscosity η1 measured at a rotation speed of 30 rpm at room temperature (25°C) using a B-type viscometer by the viscosity η2 measured at a rotation speed of 60 rpm.

[0046] "Monomer-based unit" in the polymer means an atomic group directly formed from one monomer molecule by polymerization and an atomic group formed by treating the polymer so that a part of the atomic group is converted into another structure. Hereinafter, the monomer-based unit based on monomer a is also simply referred to as "monomer a unit".

[0047] Hereinafter, the tetrafluoroethylene-based polymer of the present application is also referred to as "F polymer". In addition, the F polymer powder having a specific surface area of 25 m 2 / g or less is also referred to as "the present powder".

[0048] In addition, hereinafter, among the liquid medium, the liquid medium having polarity is also referred to as "liquid polar medium".

[0049] One of the compositions of the present application is a composition containing particles derived from the present powder and a liquid medium, having a solid content concentration of 40% by mass or more, and a viscosity (hereinafter, simply referred to as "viscosity measured by a B-type viscometer") measured at a temperature of 25°C and a rotation speed of 30 rpm using a B-type viscometer of 8000 to 100000 mPa-s. Hereinafter, the composition of the present application is referred to as "the present composition (1)".

[0050] Another of the compositions of the present application is a composition containing particles derived from the present powder, a polar polymer or a precursor thereof, and a liquid polar medium, having a viscosity (hereinafter, simply referred to as "viscosity measured by capillary rheometry") measured by capillary rheometry at a shear rate of 1 s -1 -1 of 10000 to 100000 Pa-s. Hereinafter, the composition of the present application is referred to as "the present composition (2)".

[0051] In addition, the above-mentioned present composition (1) and the present composition (2) are collectively referred to as "the present composition".

[0052] 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. The dispersion liquid can be obtained by diluting the present composition with a liquid medium.

[0053] In addition, in order to distinguish the second liquid medium used for dilution of the present composition, the liquid medium in the present composition is also referred to as "the first liquid medium" as needed.

[0054] Hereinafter, first, the F polymer, the present powder, the liquid medium, and the polar polymer and the precursor thereof involved in the present composition are described.

[0055] The F polymer of the present composition is a polymer containing a unit based on tetrafluoroethylene (hereinafter also referred to as "TFE") (hereinafter also referred to as "TFE unit").

[0056] The fluorine content of the F polymer is preferably 70% by mass or more. In the F polymer having a high fluorine content, the properties such as electrical properties of the F polymer are excellent, but the affinity with the liquid medium is significantly lower. Therefore, the dispersibility of the particles of the F polymer is further decreased. According to the present composition, even in the dispersion liquid of the F polymer particles obtained by using the same, the properties of the F polymer as a whole are not impaired, and a dispersion liquid having excellent dispersibility can be obtained.

[0057] The fluorine content of the F polymer is preferably 76% by mass or less.

[0058] The F polymer can be thermally fusible or non-thermally fusible.

[0059] The thermally fusible polymer refers to a polymer having a temperature at which the melt flow rate is 1 to 1000 g / 10 minutes under a load of 49 N.

[0060] The non-thermally fusible polymer refers to a polymer having no temperature at which the melt flow rate is 1 to 1000 g / 10 minutes under a load of 49 N.

[0061] The melting temperature of the thermally fusible F polymer is preferably 180°C or higher, more preferably 200°C or higher, and further preferably 260°C or higher. The melting temperature of the F polymer is preferably 325°C or lower, and more preferably 320°C or lower. The melting temperature of the F polymer is particularly preferably 180 to 325°C.

[0062] The glass transition temperature of the F polymer is preferably 50°C or higher, and more preferably 75°C or higher. The glass transition temperature of the F polymer is preferably 150°C or lower, and more preferably 125°C or lower.

[0063] As the F polymer, polytetrafluoroethylene (hereinafter also referred to as "PTFE"), a polymer containing a TFE unit and a unit based on perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE") (hereinafter also referred to as "PAVE unit") (hereinafter also referred to as "PFA"), or a copolymer containing TFE and a unit based on hexafluoropropylene (hereinafter also referred to as "FEP") are preferred, and PFA or FEP is more preferred, and PFA is further preferred. These polymers can further contain a unit based on other comonomer.

[0064] As the PAVE, CF2=CFOCF3, CF2=CFOCF2CF3, or CF2=CFOCF2CF2CF3 (hereinafter also referred to as PPVE) is preferred, and PPVE is more preferred.

[0065] The F polymer preferably has a polar functional group. In this case, the affinity of the present powder to the liquid medium is easily improved. The F polymer can have 2 or more polar functional groups.

[0066] As the polar functional group, a carbonyl group-containing group, a hydroxyl group-containing group, and a phosphoryl group-containing group are preferable, and the F polymer more preferably has a carbonyl group-containing group or a hydroxyl group-containing group from the viewpoint of easily improving the dispersibility and the like of the present powder.

[0067] The polar functional group can be contained in a monomer unit in the F polymer, or can be contained in a terminal group of the polymer main chain. As the latter, an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like can be exemplified.

[0068] In the case where 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 5,000 or less, and further preferably 50 or more and 2,000 or less, per 1 x 10 6 carbon atoms of the main chain. In this case, the affinity of the F polymer particles to the liquid medium is easily improved. Note that the number of carbonyl group-containing groups in the F polymer can be quantified according to the composition of the polymer or the method described in International Publication No. 2020 / 145133.

[0069] As the carbonyl group-containing group, a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH2), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)- and the like), and a carbonate group (-OC(O)O-) are preferable, and an acid anhydride residue is more preferable. As the hydroxyl group-containing group, an alcohol hydroxyl group-containing group is preferable, and -CF2CH2OH, -C(CF3)2OH, and a 1,2-diol group (-CH(OH)CH2OH) are more preferable.

[0070] As a preferable form of the F polymer, a polymer (1) having a carbonyl group-containing group or a hydroxyl group, which contains a TFE unit and a PAVE unit, or a polymer (2) having neither of the carbonyl group-containing group or the hydroxyl group, which contains a TFE unit and a PAVE unit and contains 2 to 5 mol% of the PAVE unit relative to the total monomer units, can be exemplified. Since these polymers form fine spherocrystals in a coating film or a molded article, the properties of the obtained coating film or molded article.

[0071] 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), a polymer containing 90 to 99 mol% of a TFE unit, 0.5 to 9.97 mol% of a PAVE unit, and 0.01 to 3 mol of a unit based on the above monomer, respectively, relative to the total units is more preferable.

[0072] In addition, as the monomer having the hydroxyl group-containing group or the carbonyl group-containing group, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride (alias: nadic anhydride; hereinafter also referred to as "NAH") are preferable.

[0073] As a specific example of the polymer (1), the polymer described in International Publication No. 2018 / 16644 can be cited.

[0074] As the polymer (2), a polymer composed only of TFE units and PAVE units and containing 95 to 98 mol% of TFE units and 2 to 5 mol% of PAVE units with respect to the total monomer units is preferable.

[0075] The content of the PAVE units in the above preferable polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more with respect to the total monomer units.

[0076] In addition, the polymer (2) does not have either of the carbonyl group-containing group and the hydroxyl group-containing group means that the number of the carbonyl group-containing groups or the hydroxyl group-containing groups possessed by the polymer is less than 500 with respect to the number of carbon atoms (1 x 10 6 The number of the carbonyl group-containing groups or the hydroxyl group-containing groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of the carbonyl group-containing groups or the hydroxyl group-containing groups is usually 0.

[0077] The polymer (2) can be produced using a polymerization initiator or a chain transfer agent, etc. that does not generate a polar functional group as a terminal group of a polymer chain, or can be produced by subjecting a polymer having a polar functional group at a terminal group of a polymer chain, etc. to a fluorination treatment.

[0078] As a method of the fluorination treatment, a method using fluorine gas can be cited (refer to Japanese Patent Kokai No. 2019-194314, etc.).

[0079] The present powder is composed of particles of the F polymer.

[0080] The specific surface area of the present powder is preferably 8 m 2 / g or less, more preferably 5 m 2 / g or less, particularly preferably 3 m 2 / g or less. The specific surface area of the present powder is preferably 1 m 2 / g or more.

[0081] The D50 of the present powder is preferably 20 μm or less, further preferably 8 μm or less. The D50 of the present powder is preferably 0.1 μm or more, more preferably 0.3 μm or more, further preferably 1 μm or more. In addition, the D90 of the present powder is preferably less than 100 μm, more preferably 90 μm or less. If the D50 and D90 of the present powder are within the range, the surface area becomes large, and the dispersibility of the present powder is easily further improved.

[0082] The present powder can be a powder composed of particles composed of a mixture of two or more kinds of F polymers, or a powder composed of two or more kinds of particles composed of F polymers. The latter is a powder composed of particles composed of a certain F polymer and particles composed of a different F polymer from the former, and is usually a mixture of a certain F polymer powder and a different F polymer powder (i.e., a powder mixture).

[0083] As the powder mixture, a mixture of a hot-melt F polymer powder (a hot-melt F polymer powder having a carbonyl group-containing unit such as a TFE unit and a PAVE unit, etc.) and a non-hot-melt F polymer powder (a non-hot-melt PTFE powder, etc.) is preferable.

[0084] In the case where the present powder is a mixture of the above two kinds of powders, the proportion of the former particles (particles of the hot-melt F polymer) in the total amount of the present powder is preferably 50 mass% or less, more preferably 25 mass% or less. In addition, the above proportion is preferably 0.1 mass% or more, more preferably 1 mass% or more. In addition, it is preferable that the D50 of the former particles be 1 to 4 μm and the D50 of the latter particles (particles of the non-hot-melt F polymer) be 0.1 to 1 μm.

[0085] The particles constituting the present powder can also contain a polymer or a resin other than the F polymer or an inorganic substance. However, in this case, the polymer or the resin other than the F polymer or the inorganic substance is not dissolved in the liquid medium in the present composition.

[0086] As specific examples of the polymer or the resin other than the F polymer, there are mentioned polymers such as aromatic polyimide, aromatic maleimide, aromatic elastomer such as a styrene elastomer, and aromatic polyamide acid, or cured products of curable resins. However, among them, there are those which have solubility in the liquid medium depending on the liquid medium in the present composition but do not become components of the particles constituting the present powder, as in the case of the present composition (2) described later.

[0087] As specific examples of the inorganic substance, there are mentioned silicon oxide (silica), metal oxide (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, magnesium metasilicate (block talc).

[0088] As the present powder containing particles of the F polymer and a polymer or resin different from the F polymer or an inorganic substance, for example, there can be mentioned a powder composed of particles of a mixture of fine particles of the F polymer, a polymer or resin different from the F polymer, or an inorganic substance, and a present powder composed of particles of a core-shell structure having the F polymer as the core and fine particles of a polymer or resin different from the F polymer as the shell or having the F polymer as the shell and fine particles of a polymer or resin different from the F polymer as the core. As the latter present powder, there can be mentioned a powder obtained by impinging, agglomerating, or the like, a F polymer powder and a powder composed of fine particles of a polymer or resin different from the F polymer or an inorganic substance.

[0089] The liquid medium is an inert liquid which does not dissolve the particles of the F polymer (hereinafter also referred to as "present powder particles") constituting the present powder and is in a liquid state at 25°C. The liquid medium preferably has an affinity with the F polymer particles, and for example, a liquid polar medium generally has an affinity with the particles of the F polymer having a carbonyl group-containing group or a hydroxyl group-containing group. As the liquid medium in the present composition, it can be either a low viscosity liquid medium or a high viscosity liquid medium. As the liquid medium in the present composition, a low viscosity liquid medium is preferred.

[0090] Hereinafter, a low viscosity liquid medium refers to a liquid medium having a viscosity of 10 mPa-s or less at 25°C as measured with a B-type viscometer, and a high viscosity liquid medium refers to a liquid medium having a viscosity of more than 10 mPa-s at 25°C as measured with a B-type viscometer.

[0091] The low viscosity liquid medium preferably has a boiling point of 75°C or higher, more preferably 100°C or higher. The low viscosity liquid medium preferably has a boiling point of 300°C or lower, more preferably 250°C or lower.

[0092] The low viscosity liquid medium can be a liquid polar medium or a non-polar liquid medium such as a hydrocarbon liquid medium. The liquid polar medium is a liquid medium having a polar group, and refers to a liquid medium composed of an organic compound having an amide group, a carbonyl group, an oxidized carbonyl group, or the like, and a liquid medium composed of an inorganic compound having a polarity such as water. As the above organic compound having a polar group, an amide, a ketone, and an ester are preferred, and as the above inorganic compound having a polarity, water is preferred.

[0093] As the liquid polar medium in the present composition (2), a low viscosity liquid polar medium selected from water, an amide, a ketone, and an ester is preferred.

[0094] As specific examples of the amides as the low viscosity liquid medium, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-diethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone can be listed.

[0095] As specific examples of the ketones as the low viscosity liquid medium, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, cycloheptanone can be listed.

[0096] As specific examples of the esters as the low viscosity liquid medium, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, γ-butyrolactone, γ-valerolactone can be listed.

[0097] As the low viscosity liquid medium, water, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, cyclopentanone are preferred.

[0098] The high viscosity liquid medium preferably has a boiling point of 100°C or higher. The high viscosity liquid medium preferably has a boiling point of 350°C or lower, more preferably 300°C or lower.

[0099] As the high viscosity liquid medium, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ether or ester derivatives of the glycols, and the like can be listed. As the ether derivatives of the glycols, glycol monoalkyl ethers, glycol monoaryl ethers, glycol monoalkyl ether alkyl esters, glycol monoaryl ether alkyl esters, glycol dialkyl ethers are more preferred, and glycol monoalkyl ethers are further preferred.

[0100] As specific examples of the high viscosity liquid medium, 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, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate can be listed.

[0101] The present composition (1) can further contain a polymer or a resin other than the F polymer. The present composition (1) can contain a polymer or a resin other than the F polymer in the sense that it can be contained in a portion other than the particles constituting the powder. The polymer or the resin other than the F polymer in the present composition (1) can be dissolved in the liquid medium, can be contained as the same particles as the inorganic filler without being dissolved, or can be contained as particles swollen with the liquid medium.

[0102] The present composition (2) contains a polar polymer or a precursor thereof other than the F polymer.

[0103] Hereinafter, first, the polymer or resin other than the F polymer which can be contained in the present composition (1) will be described, and then the polar polymer and the precursor thereof which are contained in the present composition (2) will be described.

[0104] The polymer or resin other than the F polymer means a polymer or a precursor thereof (a low molecular compound or an oligomer which can become a polymer by polymerization or crosslinking, etc.) other than the F polymer, a combination of two or more compounds which can become a polymer by condensation or the like, etc. For example, a resin called a thermoplastic resin is generally a polymer, and a resin called a curable resin is generally a low molecular compound, an oligomer, or a combination of low molecular compounds which become a polymer by reaction. In addition, those which are called an elastomer or a rubber in correspondence with the physical properties of the polymer can also be included. Hereinafter, the polymer or resin other than the F polymer is collectively referred to as "other resin".

[0105] As the other resin, aromatic polyester, aromatic polyimide, aromatic polyamide acid, aromatic polyamide-imide, precursor of aromatic polyamide-imide, epoxy resin, maleimide resin, polyurethane resin, thermoplastic elastomer, polyamide-imide, polyphenylene ether, polyphenylene ether, liquid crystal polyester, polysaccharide, nylon, acrylic resin, methacrylic resin, butyral, cyanate resin, ABR rubber, cellulose, PVA acrylic methacrylic, polyalkylene ether, polyoxyethylene alkyl ether, fluorine-containing polymer other than the F polymer can be exemplified.

[0106] As the other resin, aromatic polyester, aromatic polyimide, aromatic polyamide acid, aromatic polyamide-imide, precursor of aromatic polyamide-imide, polyphenylene ether, epoxy resin, maleimide resin, and thermoplastic elastomer are preferable. The aromatic polyimide can be thermoplastic or thermosetting.

[0107] As specific examples of the aromatic polyimide, "Neopulim (registered trademark)" series (manufactured by Mitsubishi Gas Chemical Corporation), "SPIXAREA (registered trademark)" series (manufactured by Somaly Co., Ltd.), "Q-PILON (registered trademark)" series (manufactured by PI Technology Institute), "WINGO" series (manufactured by WINGO Technology Co., Ltd.), "Tohmide (registered trademark)" series (manufactured by T&K TOKA Co., Ltd.), "KPI-MX" series (manufactured by Kawamura Industry Co., Ltd.), "UPIA (registered trademark)-AT" series (manufactured by Ube Industries, Ltd.) can be exemplified.

[0108] As specific examples of the aromatic polyamide-imide and the precursor of the aromatic polyamide-imide, "HPC-1000", "HPC-2100D" (both manufactured by Showa Denko Materials Co., Ltd.) can be given.

[0109] As the styrene elastomer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer can be given.

[0110] As the polyurethane resin, for example, a polyurethane fine particle containing an acrylic component can be given, and it can be a homopolymer or a copolymer. Specifically, commercially available DYMIC BEADS CM (manufactured by Ouchi Shinko Co., Ltd.), ART PEARL (manufactured by Koonoh Industry Co., Ltd.), and GRAN PEARL (manufactured by Aica Kogyo Co., Ltd.) can be given.

[0111] As the polysaccharide, glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, levan, xanthan gum, guar gum, casein, gum arabic, gelatin, agar gum, arabinan, curdlan, callose, carboxymethyl starch, chitin, chitosan, quince seed, glucomannan, gellan gum, tamarind gum, dextran, pullulan, hyaluronic acid, ceramid, funoran, pectic acid, porphyran, laminaran, lichenin, carrageenan, alginic acid, tragacanth gum, alkali gum, locust bean gum can be given.

[0112] As the acrylic resin and the methacrylic resin, polyacrylate, polymethacrylate, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer can be given.

[0113] As the acrylic resin and the methacrylic resin, for example, among commercially available products, Neocryl series manufactured by Nishimura Chemical Co., Ltd. can be given.

[0114] As the nylon, nylon 6, nylon 11, and nylon 12 can be given.

[0115] As commercially available products of the butyral resin, there can be mentioned S-LEC (registered trademark) B series, K (KS) series, SV series manufactured by Sekisui Chemical Co., Ltd., and MOWITAL (registered trademark) series manufactured by Kuraray Co., Ltd.

[0116] As the cyanate ester resin, there can be mentioned bisphenol A type cyanate, bisphenol F type cyanate ester resin, 6F bisphenol A dicyanate resin, bisphenol E type dicyanate resin, tetramethyl bisphenol F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadiene bisphenol dicyanate resin, and cyanate novolak resin.

[0117] As the epoxy resin, there can be mentioned bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, t-butyl- catechol type epoxy resin, naphthalene type epoxy resin, naphthalene ether type epoxy resin, glycidyl amine 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, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin.

[0118] As commercially available products of the thermoplastic elastomer, there can be mentioned TR series (styrene-butadiene thermoplastic elastomer, manufactured by JSR Co., Ltd.), RB series (polybutadiene-based thermoplastic elastomer, manufactured by JSR Co., Ltd.), JSR EXCELINK (olefin-based thermoplastic elastomer, manufactured by JSR Co., Ltd.), DYNARON (registered trademark) series (hydrogenated thermoplastic elastomer, manufactured by JSR Co., Ltd.), THERMORUN (registered trademark) (olefin-based thermoplastic elastomer, manufactured by Mitsubishi Chemical Corporation), ESPOLEX TPE series (olefin-based thermoplastic elastomer, manufactured by Sumitomo Chemical Co., Ltd.), SEPTON (registered trademark) series (hydrogenated styrene-based thermoplastic elastomer, manufactured by Kuraray Co., Ltd.), Tafetec (registered trademark) (hydrogenated styrene-based thermoplastic elastomer, manufactured by Asahi Kasei Corporation).

[0119] As the fluorine-containing polymer other than the F polymer, there can be mentioned polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, and the like.

[0120] As described above, the present composition (2) contains, as the other resin, a polar polymer or a precursor thereof.

[0121] 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 a precursor of the polar polymer is a precursor capable of being polymerized by heating or the like to become the polar polymer. The polar functional group is generally a hetero atom or a hetero atom-containing group. The hetero atom can be exemplified by oxygen, sulfur, nitrogen, and halogen atoms other than fluorine. The precursor of the polar polymer is a precursor having such a polar functional group or a group capable of becoming such a polar functional group by polymerization.

[0122] As the polymer having a polar functional group in the main chain, there can be exemplified a polymer having an ether bond, an ester bond, an amide bond, an imide bond, a thioether (thioether) bond, a sulfide (sulfide) bond, or a disulfide bond in the main chain.

[0123] As the polar functional group in the polymer having a polar functional group in the side chain, there can be exemplified the above-mentioned carbonyl group-containing group, the above-mentioned hydroxyl group-containing group, a mercapto group, a thioether group, a sulfonyl group, a sulfoxy group, an amino group, an amide group, and the like, with preference given to the carbonyl group-containing group and the hydroxyl group-containing group. In this case, the interaction of the F polymer with the polar polymer (or the precursor thereof) and the liquid medium is easily enhanced, and the above-mentioned mechanism of action is easily embodied.

[0124] The molecular weight of the polar polymer and the precursor thereof is preferably 3,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more. The molecular weight of the polar polymer and the precursor thereof is preferably 50,000 or less, and more preferably 30,000 or less. In this case, the polar polymer and the precursor thereof easily interact with the F polymer and the liquid polar medium, and the dispersing stability and the like of the present composition (2) are easily excellent.

[0125] The polar polymer and the precursor thereof are preferably soluble in the liquid polar medium.

[0126] As the polar polymer, there can be exemplified an ether-based polymer such as a polyalkylene oxide, a polyether ketone, a polyether ether ketone, a polyether sulfone, an ester-based polymer such as a polyalkylene terephthalate, a polyalkylene naphthalate, an amide-based polymer such as nylon, aramid, an imide-based polymer such as polyimide, polyamide-imide, a thioether-based polymer such as a polythiol, a polythioether, a polydisulfide, a sulfone-based polymer such as a polyether sulfone, a polyphenyl sulfone, a vinyl-based polymer such as a polyvinyl alcohol, a polyacrylate, a polymethacrylate, a polyvinylpyrrolidone, a polyvinyl acetate, a carboxyvinyl polymer, a polyhaloethylene other than the F polymer, a polyvinylidene halide, and a polysaccharide and a precursor thereof. In addition, as the polar polymer, there can be exemplified a polymer in which the above-mentioned polar functional group is introduced into a polyolefin. In addition, as the polysaccharide, there can be exemplified the above-mentioned polysaccharide exemplified as the other resin.

[0127] These polar polymers can be copolymers composed of a plurality of monomers.

[0128] As the polar polymer and its precursor, imide-based polymers, precursors of imide-based polymers, vinyl-based polymers, and polysaccharides are preferable.

[0129] As the preferable imide-based polymer and its precursor, polyimide, polyamide-imide, polyamide acid, polyamide-imide precursor, more preferably aromatic polyimide, aromatic polyamide-imide, aromatic polyamide acid, aromatic polyamide-imide precursor can be exemplified.

[0130] As the specific examples of the imide-based polymer, "Neopulim (registered trademark)" series (manufactured by Mitsubishi Gas Chemical Company, Inc.), "SPIXAREA (registered trademark)" series (manufactured by Somyo Corporation), "Q-PILON (registered trademark)" series (manufactured by PI Technology Institute), "WINGO" series (manufactured by WINGO Technology Co., Ltd.), "Tohmide (registered trademark)" series (manufactured by DIC Corporation), "KPI-MX" series (manufactured by Kawamura Industry Co., Ltd.), "UPIA (registered trademark)-AT" series (manufactured by Ube Industries, Ltd.), "HPC-1000", "HPC-2100D" (both manufactured by Showa Denko Materials Co., Ltd.) can be exemplified.

[0131] As the preferable vinyl-based polymer, vinyl alcohol-based polymers such as polyvinyl alcohol, vinyl pyrrolidone-based polymers such as polyvinyl pyrrolidone, acrylic acid-based polymers such as polyacrylic acid, carboxyvinyl polymers, and more preferably vinyl alcohol-based polymers can be exemplified.

[0132] As the vinyl alcohol-based polymer, polyvinyl alcohol, polyvinyl acetate, partially acetylated product of polyvinyl alcohol, partially acetalized product of polyvinyl alcohol, copolymer of vinyl alcohol, vinyl butyral, and vinyl acetate are preferable.

[0133] As the specific examples of the vinyl alcohol-based polymer, "S-LEC (registered trademark) B" series, "S-LEC (registered trademark) K (KS)" series, "S-LEC (registered trademark) SV" series (all manufactured by Sekisui Chemical Co., Ltd.), "MOWITAL (registered trademark)" series (manufactured by Kuraray Co., Ltd.) can be exemplified.

[0134] As the acrylic acid-based polymer, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, poly-α-halogen acrylate, poly-α-cyano acrylate, polyacrylic acid amide, sodium polyacrylate can be exemplified.

[0135] As the preferred polysaccharides, among the polysaccharides, glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, chitin can be exemplified. As the cellulose, carboxymethyl cellulose is preferred. The carboxymethyl cellulose can be carboxymethyl cellulose sodium, carboxymethyl cellulose ammonium and the like carboxymethyl cellulose salts.

[0136] In the case where the present composition contains other resins than the F polymer, the other resins in the present composition are preferably dissolved in the liquid medium or swelled by the liquid medium, and particularly preferred are polar polymers or precursors thereof which are dissolved in the liquid medium.

[0137] The other resins which are not dissolved in the liquid medium are preferably contained in the present composition as particles which are the same as the particles of the inorganic filler described below. As the particles which are the same as the particles of the inorganic filler, particles composed of the cured product of the curable resin are preferred.

[0138] The present composition can further contain particles of an inorganic filler.

[0139] The inorganic filler is used to improve the properties of the obtained coating film or molded article when the present composition or the dispersion liquid obtained by diluting the present composition is used to form various coating films or molded articles, and the kind thereof is appropriately selected depending on the purpose of the coating film or molded article.

[0140] For example, in the case where the purpose is to improve the dielectric constant of the coating film or molded article, as the inorganic filler, a perovskite-type high dielectric filler and a bismuth layer-structured perovskite-type high dielectric filler are preferred.

[0141] As the perovskite-type high dielectric, barium titanate, lead zirconate titanate, lead titanate, zirconia, titania can be exemplified. As the bismuth layer-structured perovskite-type high dielectric, bismuth strontium tantalate, bismuth strontium niobate, bismuth titanate can be exemplified.

[0142] For example, in the case where the purpose is to reduce the dielectric constant and dielectric loss tangent or linear expansion rate of the coating film or molded article, as the inorganic filler, a low dielectric constant, low dielectric loss tangent or low linear expansion rate inorganic filler is used.

[0143] As the inorganic filler, a boron nitride filler, a beryllium oxide filler (beryllium oxide filler), a silicon oxide filler (silicon dioxide filler), a wollastonite filler, and a magnesium metasilicate filler (block talc filler) are preferred.

[0144] For example, in the case where the purpose is to improve the thermal conductivity or scratch resistance of the coating film or molded article, as the inorganic filler, a filler of a metal oxide can be used.

[0145] As the metal oxide, aluminum oxide, lead oxide, iron oxide, tin oxide, magnesium oxide, titanium oxide, zinc oxide, antimony pentoxide, zirconium oxide, lanthanum oxide, neodymium oxide, cerium oxide and niobium oxide are preferred, and aluminum oxide is more preferred.

[0146] In addition, as the inorganic filler other than the above, a glass fiber filler or a carbon filler can be used.

[0147] As the carbon filler, carbon fiber, carbon black, graphene, graphene oxide, fullerene, graphite, and graphite oxide can be given. As the carbon fiber, polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, carbon nanotube (single-walled, double-walled, multi-walled, cup stack type, etc.) can be given.

[0148] From the viewpoint of dispersibility, as the inorganic filler, boron nitride filler, silica filler, and magnesium metasilicate filler are preferable, and the silica filler is more preferable. These fillers can be ceramic fillers after firing.

[0149] The shape of the inorganic filler particles (i.e., the particles constituting the inorganic filler) is appropriately selected depending on the purpose, and can be a blocky particle or a fibrous particle. If a filler composed of a blocky particle is used, the surface flatness of a coating film or a molded article is improved, the surface slip property thereof becomes good, and the scratch resistance is easily improved. On the other hand, if an inorganic filler composed of a fibrous particle is used, a part of the filler particles is exposed from the surface of a coating film or a molded article, and for example, the abrasion resistance and the scratch resistance of the surface of the article are easily improved.

[0150] In the case of an inorganic filler composed of a blocky particle, the average particle diameter (D50) thereof is preferably 0.02 to 200 μm. In the case of an inorganic filler composed of a fibrous particle, 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-mentioned shapes, the particles constituting the inorganic filler can have various shapes such as a plate shape, a hollow shape, a honeycomb shape, and the like.

[0151] At least a part of the surface of the inorganic filler particle is preferably subjected to surface treatment.

[0152] The inorganic filler is preferably composed of an inorganic filler particle subjected to surface treatment with a silane coupling agent. The affinity of this inorganic filler to the base powder is excellent, and the dispersibility of the base dispersion liquid is easily improved.

[0153] As the silane coupling agent, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-isocyanatepropyltriethoxysilane are preferable.

[0154] As a preferable specific example of the inorganic filler, there can be mentioned a silica filler ("admafin (registered trademark)" series manufactured by Admatechs Co., Ltd., etc.), a zinc oxide filler surface-treated with an ester such as didecyl ester propylene glycol ("FINEX (registered trademark)" series manufactured by Sakai Chemical Industry Co., Ltd., etc.), a spherical fused silica filler ("SFP (registered trademark)" series manufactured by Denki Kagaku Kogyo K.K., etc.), a zinc oxide filler coated with a polyol and an inorganic substance ("TIPAQUE (registered trademark)" series manufactured by Seido Chemical Industry Co., Ltd., etc.), a rutile titanium oxide filler surface-treated with an alkylsilane ("JMT (registered trademark)" series manufactured by Teika Co., Ltd., etc.), a hollow silica filler ("E-SPHERES" series manufactured by Pacific Cement Co., Ltd., "SILINA X" series manufactured by Nippon Steel Mining Co., Ltd., "Eccospheres" series manufactured by Emerson and Cuming, etc.), a talc filler ("SG" series manufactured by Nippon Talc Co., Ltd., etc.), a block talc filler ("BST" series manufactured by Nippon Talc Co., Ltd., etc.), and a boron nitride filler ("UHP" series manufactured by Showa Denko K.K., "HGP series", "GP series" manufactured by Denki Kagaku Kogyo K.K., etc.).

[0155] Further, the present composition can further contain an ingredient other than the present powder particles, the liquid medium, other resins, and the inorganic filler. As an example of the other ingredient, there can be mentioned a surfactant from the viewpoint of improving dispersion stability and handling properties.

[0156] The surfactant is preferably a nonionic surfactant.

[0157] The hydrophilic site of the surfactant preferably has an oxyalkylene group or an alcohol hydroxyl group.

[0158] The oxyalkylene group can be composed of one kind, or two or more kinds. In the latter case, the different kinds of oxyalkylene groups can be arranged in a random manner, or in a block manner.

[0159] As the oxyalkylene group, an oxyethylene group is preferable.

[0160] The hydrophobic site of the surfactant preferably has an ethynyl group, a polysiloxane group, a perfluoroalkyl group, or a perfluoroalkenyl group. In other words, the surfactant is preferably an ethynyl-based surfactant, a silicone-based surfactant, or a fluorine-based surfactant, and more preferably a silicone-based surfactant.

[0161] As the fluorine-based surfactant, a fluorine-based surfactant having a hydroxyl group, particularly an alcoholic hydroxyl group or an oxyalkylene group, a perfluoroalkyl group or a perfluoroalkenyl group is preferable.

[0162] As specific examples of the surfactant, the "FTERGENT" series (manufactured by Neos Corporation), the "SURFLON" series (manufactured by AGC Seimi Chemical Co., Ltd.), the "MEGAFACE" series (manufactured by DIC Corporation), the "UNIDYNE" series (manufactured by Daikin Industries, Ltd.), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (manufactured by BYK-Chemie Japan Ltd.), "KF-6011", "KF-6043" (manufactured by Shin-Etsu Chemical Co., Ltd.), the "Tergitol" series ("Tergitol TMN-100X" and the like manufactured by Dow Chemical), and the like can be given.

[0163] In the case where the present composition contains a surfactant (but the surfactant is the one attached to the surface of the inorganic filler in the case where the inorganic filler is previously treated with a surfactant), the amount thereof in the present dispersion liquid in the present dispersion liquid after the present composition is diluted with the second liquid medium is preferably 1 to 15 mass%. In this case, the affinity between the components increases, and the dispersion stability of the present dispersion liquid is easily further improved.

[0164] In addition to the above-mentioned components, the present composition can further contain a thixotropy imparting agent, a viscosity adjusting agent, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a coloring agent, a conductive agent, a mold releasing agent, a surface treatment agent, a flame retardant, various organic fillers, and the like additives.

[0165] The present composition (1) is a composition containing particles derived from F polymer powder and a liquid medium, having a solid content concentration of 40 mass% or more, and a viscosity of 8000 to 100000 mPa-s measured with a B-type viscometer. The present composition (1) is a composition in the form of a slurry, a paste, or a gum, and is preferably a high viscosity composition called a gum.

[0166] The solid content concentration of the present composition (1) is preferably 50 mass% or more. The solid content concentration of the present composition (1) is preferably 90 mass% or less, and more preferably 80 mass% or less.

[0167] The viscosity of the present composition (1) is preferably 10,000 mPa-s or more as measured with a B-type viscometer. The viscosity is preferably 80,000 mPa-s or less, more preferably 40,000 mPa-s or less, and further preferably 20,000 mPa-s or less.

[0168] The liquid medium in the present composition (1) is preferably a low viscosity liquid medium, and the present composition (1) can contain two or more kinds of liquid medium.

[0169] The present composition (1) can further contain other components such as other resins or inorganic fillers. In the case where the other resin is other than a polar polymer or a precursor thereof, the other resin is preferably dissolved in the liquid medium, and in this case, the liquid medium that dissolves the other resin can be a liquid medium other than the liquid polar medium.

[0170] The present composition (1) preferably has a foam volume ratio of 10% or less.

[0171] The foam volume ratio is a value obtained by measuring the volume (V N ) of the present composition (1) at a standard atmospheric pressure and 20°C and adding the volume (V V ) of the foam when it is depressurized to 0.003 MPa, and using the following calculation formula.

[0172] Foam volume ratio [%] = 100 x (V V - V N ) / V N

[0173] The present composition (1) can be obtained, for example, by mixing a mixture containing the F polymer powder and the liquid medium, and performing at least one of degassing during or after the mixing and standing after the mixing.

[0174] If the present composition (1) is produced by this method, the foam volume ratio can be made to be within the above range.

[0175] The content of the liquid medium in the present composition (1) is preferably 10% by mass or more. The content of the liquid medium is preferably 60% by mass or less, and more preferably 25% by mass or less. By this, each particle constituting the powder is always mixed with the liquid medium in a state of contact with the liquid medium, and the powder particles and the liquid medium are uniformly mixed.

[0176] By appropriately setting the amounts of the F polymer and the liquid medium, the solid content concentration of the present composition (1) can be made to be within the above range. In the case where other resins or inorganic fillers are contained, by the same appropriate setting, the solid content concentration in the present composition (1) can be made to be within the above range.

[0177] Further, by selecting the viscosity of the liquid medium, the viscosity of the present composition (1) can be made to be within the above range.

[0178] In the case where the present composition (1) contains other resins, the mass ratio of the present powder particles to the other resins is preferably 1 of the mass of the present powder particles and 0.01 to 0.5 of the mass of the other resins, more preferably 0.1 to 0.3.

[0179] In the case where the present composition (1) contains an inorganic filler, the content of the inorganic filler in the solid components is preferably 25 mass% or more, more preferably 50 mass% or more. Further, the inorganic filler is preferably 75 mass% or less, more preferably 60 mass% or less.

[0180] The foam volume ratio of the dispersion liquid obtained by diluting the present composition (1) with the second liquid medium is easily within the same range as the foam volume ratio of the present composition (1). Therefore, the uniformity of the component distribution or the voids of the coating film or the molded article obtained from the dispersion liquid can be inhibited from decreasing.

[0181] 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 of 10,000 to 100,000 Pa-s obtained by capillary rheometry. As the present composition (2), a high viscosity composition called wet powder is preferable.

[0182] The present composition (2) can further contain other components such as an inorganic filler, a surfactant, and the like.

[0183] In the present composition (2), the proportion of the total mass of the present powder particles and the polar polymer is preferably greater than 50 mass%, more preferably 60 mass% or more, and further preferably 80 mass% or more, based on 100 mass% of the total mass of the present composition (2). The proportion of the total mass is preferably 99 mass% or less, and more preferably 90 mass% or less.

[0184] In the present composition (2), the mass proportion of the liquid polar medium is preferably 40 mass% or less, and more preferably 20 mass% or less, based on 100 mass% of the total mass of the present composition (2). The mass proportion is preferably 1 mass% or more, and more preferably 5 mass% or more.

[0185] In the present composition (2), the ratio of the content of the polar polymer to the content of the present powder particles is preferably 0.001 or more and less than 0.5, based on 1 of the content of the present powder particles. The ratio is more preferably 0.005 or more, and further preferably 0.01 or more. Further, the ratio is more preferably 0.25 or less, and further preferably less than 0.1.

[0186] The viscosity of the present composition (2) obtained by capillary rheometry is more preferably 15,000 Pa-s or more. Furthermore, the viscosity of the present composition (2) is more preferably 50,000 Pa-s or less, and further preferably 30,000 Pa-s or less.

[0187] The state of the present composition (2) having the viscosity obtained by capillary rheometry within the range is a composition called wet powder which is a composition containing the present powder particles wetted with the liquid polar medium in which the polar polymer (or a precursor thereof) is sufficiently dissolved, in a mass or clay-like state. The present composition (2) is considered to be in a state in which the present powder particles in the present composition (2) are dispersed in a small amount of the liquid polar medium in which the polar polymer (or a precursor thereof) is dissolved, or in a state in which the present powder particles in the present composition (2) are in contact with each other and the liquid polar medium in which the polar polymer (or a precursor thereof) is dissolved is present in the interstices between the particles.

[0188] Furthermore, the present composition (2) preferably further contains a surfactant.

[0189] That is, as a specific example of the present composition (2), a wet powder containing particles of the F polymer powder having the carbonyl group-containing or hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, a polar polymer having a carbonyl group-containing or hydroxyl group-containing group or a precursor thereof, and a liquid polar medium selected from at least one of an amide, a ketone, and an ester.

[0190] The solid content concentration of the present composition (2) is preferably more than 50% by mass, and more preferably 60% by mass or more. The solid content concentration is preferably 99% by mass or less, and more preferably 95% by mass or less. In this case, the dispersibility of the present composition (2) with respect to the second liquid medium is excellent, and the dispersion stability of the obtained dispersion liquid is excellent.

[0191] In addition, the solid content in the present composition (2) refers to the total amount of the substances forming the solid content in the coating film or molded article formed from the present composition (2) or the obtained dispersion liquid. For example, in the case where the present composition (2) contains an F polymer, a polar polymer, and an inorganic filler, the total content of these components is the solid content content in the present composition (2).

[0192] In the case where the present composition (2) contains an inorganic filler, the mass ratio of the inorganic filler with respect to the present powder particles is preferably 0.5 to 2, more preferably 0.6 to 1.5, and further preferably 0.7 to 1.

[0193] In the present composition (2), the content of the present powder particles in the solid content is preferably 25% by mass or more, and more preferably 30% by mass or more. Furthermore, the content of the present powder particles is preferably 60% by mass or less, and more preferably 50% by mass or less.

[0194] In the case where the present composition (2) contains an inorganic filler, the content of the inorganic filler in the solid components 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.

[0195] Since the F polymer is a low-surface-tension and rigid polymer, F polymer particles easily coagulate in a dispersion liquid in which the powder of the F polymer is dispersed in a liquid dispersion medium. Therefore, it is difficult to obtain a dispersion liquid that is excellent in processability and dispersion stability. In a method in which F polymer powder and a dispersion medium are mixed by applying shear for the purpose of improving dispersibility, foaming can become intense and coagulation can cause a decrease in dispersion stability when the dispersion liquid is prepared.

[0196] Furthermore, due to the properties of the F polymer, in a dispersion liquid containing the powder particles of the F polymer and other components, the powder of the F polymer and the other components hardly interact with each other. Therefore, in a method in which the two are mixed in a dispersion medium by applying shear, the interaction between the components is not necessarily improved, F polymer particles coagulate, and it is difficult to form a dense and uniform dispersion liquid. This tendency is particularly significant in the case where the F polymer is intended to be mixed with a polar polymer to obtain a uniform dispersion liquid.

[0197] In the present application, by using the present composition, the wetting of the powder of the F polymer and the interaction between the components can be promoted, and a dispersion liquid that does not have the above-described problems can be obtained.

[0198] Furthermore, in the present composition (2), the polar polymer interacts with the liquid polar medium that also has polarity, and at least a part of the polar polymer dissolves. As a result, it is considered that the degree of freedom of the molecular motion of the polar polymer rises, and the interaction between the polar polymer and the powder particles of the F polymer is promoted. Also, by this, it is considered that the interaction between the liquid polar medium in which the polar polymer is dissolved and the powder particles of the F polymer is also promoted, and the powder particles of the F polymer become easy to wet. As a result, it is considered that a composition that is dense and uniform in which the three components are mixed, that is, the present composition (2) in a prescribed viscosity range is formed.

[0199] Since the powder particles of the F polymer, the polar polymer, and the liquid polar medium in the present composition (2) highly interact with each other, it is considered that the dispersion stability of a dispersion liquid obtained by diluting the present composition (2) with a second polar solvent is also improved.

[0200] As with the present composition (1), the present composition (2) is also preferably obtained by kneading a mixture containing the powder of the F polymer and the liquid polar medium, and performing at least one of degassing during the kneading or after the kneading or standing after the kneading.

[0201] The present application also includes a method for producing the present composition, which is a method for producing the present composition by kneading a mixture (hereinafter also referred to as "the present mixture") containing the present powder and a liquid medium, and at least one of degassing during or after the kneading and standing after the kneading. By using a polar polymer together with the present powder and using a liquid polar medium as the liquid medium, it is possible to produce the present composition (2) with this method.

[0202] Degassing of the kneaded product during or after the kneading promotes the effective removal of gas such as air present in the interstices of the particles of the present powder or atmospheric gas brought in during the formulation of the present composition, thereby improving the wettability of the particles of the present powder. Further, standing of the kneaded product after the kneading promotes the penetration of the liquid medium into the interstices of the particles of the present powder, thereby promoting the wetting of the particles of the present powder.

[0203] Both of the above-mentioned degassing and standing are preferably performed.

[0204] The present mixture in the kneader can be obtained by introducing the present mixture obtained by mixing the components outside the kneader into the kneader, or the present mixture can be produced in the kneader by introducing a mixture of the components or a part thereof into the kneader in the kneader. Further, a part of each component can be introduced into the kneader during the kneading of the components. For example, liquid medium can be further added to the kneaded product (containing the liquid medium) during the kneading.

[0205] Further, a solution of the polar polymer dissolved in the liquid polar medium is preferably used for forming the present mixture. Further, the liquid components such as the liquid medium are preferably used after degassing before the formation of the present mixture.

[0206] During the kneading of the present mixture, it is preferable to knead in such a manner that the mass of the present mixture does not substantially change, and it is preferable to perform the kneading in a closed system. In other words, it is preferable to perform the kneading in such a manner that the liquid components of the present mixture do not evaporate during the kneading.

[0207] During the kneading, it is preferable to use a kneader having a stirring tank and one or more shafts and stirring blades. In order to obtain a high kneading effect, the number of stirring blades is preferably two or more. The method of the kneading can be either of batch type or continuous type.

[0208] As the kneader used for batch kneading, a Henschel mixer, a pressurized kneader, a Banbury mixer, a rotary-tumbler mixer, or a planetary mixer is preferable, and a planetary mixer is more preferable. The planetary mixer has a structure in which stirring blades with two shafts that perform self-rotation and revolution with respect to each other stir and knead the kneaded material in a stirring tank. Therefore, dead angles in the stirring tank to which the stirring blades do not reach are small. The shape of the stirring blades can be thickened to apply a high load, but a conventional stirrer in which the stirring blades rotate in the stirring tank can also be used. Therefore, dead angles in the stirring tank to which the stirring blades do not reach are small, and the load on the stirring blades can be reduced, so that the present mixture is highly kneaded.

[0209] The kneading of the present mixture is preferably performed while being cooled. In this case, vaporization of the liquid medium is suppressed, the present mixture becomes viscous, a load is applied to the stirring blades of the kneader, and as a result, the shear force on the present mixture becomes large. In particular, in the case where a plurality of stirring blades are used, the stirring blades more easily apply a shear force to the material with respect to each other or between the stirring blades and the stirring tank. As a result, in the case where the present powder contains agglomerates of F polymer particles, the deagglomeration of the agglomerates is efficiently performed, and the present powder is sufficiently mixed with the liquid medium.

[0210] The temperature of the kneading is preferably below the boiling point of the liquid medium, and is preferably 30°C or lower. The temperature of the kneading is preferably 0°C or higher, and more preferably 10°C or higher.

[0211] The kneading for obtaining the present composition (2) is preferably performed until the temperature reaches 25°C and the shear rate reaches 1 s -1 The viscosity of the kneaded material is measured by a capillary rheometer at a temperature of 25°C and a shear rate of 1 s

[0212] The variation in the viscosity can be confirmed by sampling the kneaded material from the kneader every 10 minutes while the kneading is performed and measuring the viscosity by a capillary rheometer at the upper limit. The viscosity measured at the n-th time is denoted by η n , the viscosity measured at the (n+1)-th time is denoted by η n+1 , and the variation at the n-th time obtained from the following equation (1) is denoted by r n . The variation is within the above range for three consecutive times.

[0213] (η n+1 / η n ) x 100 = r n (1)

[0214] Since the load applied to the stirring blades becomes small and the consumption current of the kneader decreases as the kneading proceeds, the end point of the kneading can be determined by monitoring the consumption current.

[0215] Further, the mixing can be controlled by the value obtained by dividing the load current of the kneader by the shear rate of the kneader, as the force and energy imparted to the mixture. Specifically, it is preferable to increase the load current from the start of the mixing and gradually decrease it.

[0216] As the continuous kneader, a twin-screw type extrusion kneader or a stone mill type kneader can be exemplified.

[0217] The twin-screw type extrusion kneader refers to a twin-screw continuous kneader that kneads the mixture, for example, by the shearing force between two screws arranged in parallel and close to each other.

[0218] The stone mill type kneader refers to a kneader that has, for example, a cylindrical fixed portion having an internal space through which the mixture passes, and a rotating portion arranged in the internal space of the fixed portion and transporting the mixture passing through the internal space in the direction of the rotation axis while continuously kneading the mixture by rotation.

[0219] The degassing can be performed during the mixing, after the mixing, or multiple times alternately with the mixing. The degassing can be performed continuously or intermittently.

[0220] The degassing is preferably performed in such a manner that the mass of the present mixture does not substantially change. The method of degassing can be exemplified by a method of placing the liquid composition under reduced pressure, a method of placing the liquid composition under heating, a method of freezing the liquid composition, a method of irradiating the present mixture with ultrasonic waves, and a method combining these methods. Among these methods, the method of placing the present mixture under reduced pressure or the method of placing the present mixture under heating is preferable due to the ease of operation, and the method combining both is more preferable from the viewpoint of the degassing efficiency. Further, as described above, it is particularly preferable to perform the degassing while cooling.

[0221] In the case of placing the present mixture under reduced pressure or heating, the temperature and pressure at the time of degassing are appropriately set according to the present mixture in the liquid composition, and a pressure and temperature at which the present mixture does not boil are selected. For example, a pressure of about 0 Pa to about 0.01 MPa and a temperature of 100°C to 250°C lower than the boiling point of the liquid medium in the present mixture are preferable.

[0222] The time for degassing is not particularly limited, but since the effect of the degassing does not change much if the time for degassing is too long, it is usually 10 minutes to 6 hours.

[0223] At the time of degassing, stirring or the like can be performed in order to prevent the explosive boiling.

[0224] The standing of the kneaded product is usually performed after the kneading. The kneaded product after the kneading is left to stand in a container for a certain period of time. The standing is preferably performed in a manner that the mass of the kneaded product does not substantially change, and is preferably performed in a closed system such as a closed container.

[0225] The temperature and pressure of the atmosphere in which the kneaded product is left to stand are usually 10 to 30°C and about 1 atm, and are preferably in a constant temperature and humidity. Depending on the case, the kneaded product can be stirred during the standing to the extent that the aggregation and sedimentation of the particles of the present powder do not occur.

[0226] The time for the standing is preferably 24 hours or more, and more preferably 48 hours or more. The time for the standing is preferably 168 hours or less, since the effect obtained by the standing does not substantially change even if the time for the standing is longer.

[0227] The viscosity of the kneaded product at the time of the standing for obtaining 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 8,000 mPa-s or more. In this case, the penetration of the liquid medium into the particles of the present powder is further promoted, and the above-described mechanism is easily enhanced. The viscosity of the kneaded product at the time of the standing can be adjusted depending on the temperature thereof or the liquid medium such as the liquid polar medium added to the kneaded product.

[0228] In the present method, either one of the degassing and the standing can be performed, but both are preferably performed from the viewpoint of the dispersion stability of the dispersion liquid obtained by diluting the present composition.

[0229] As the form in which both are performed, there can be mentioned: a form in which the present mixture is kneaded and then continuously or intermittently degassed, and then left to stand without degassing; a form in which the present mixture is continuously or intermittently degassed while being kneaded, and the obtained kneaded product is left to stand; a form in which the present mixture is continuously or intermittently degassed while being kneaded, and the obtained kneaded product is left to stand, and then further degassed after the standing; a form in which the present mixture is kneaded, and then degassed while being left to stand after the kneading, and then left to stand without degassing; and a form in which the present mixture is kneaded, and then left to stand after the kneading, and then continuously or intermittently degassed after the standing. These multiple forms can be combined, and one form can be repeated.

[0230] By performing at least one of the degassing and the standing at any stage between the kneading and the mixing, the aggregation of the particles of the present powder can be inhibited, and the foaming at the time of mixing the present composition with a second liquid medium can be inhibited. As a result, the surface smoothness of the obtained coating film or molded product is excellent.

[0231] The present composition is preferably diluted with a second liquid medium and used as a dispersion liquid having a lower viscosity than the present composition. In addition, the present composition can also be used for other purposes.

[0232] The dispersion liquid (hereinafter also referred to as "the present dispersion liquid") obtained by diluting the present composition with the second liquid medium is suitable for use in a coating agent or a paint, etc.

[0233] The second liquid medium is a liquid medium that is compatible with the first liquid medium, and can also be the same liquid medium as the first liquid medium. Furthermore, the second liquid medium is a liquid medium that does not dissolve the non-dissolved components such as the present powder particles or inorganic fillers in the present composition when diluting the present composition, and is preferably a liquid medium that does not cause the components dissolved in the first liquid medium to come out of solution. However, in the case where the amount of the first liquid medium in the present composition is small and the entire amount of the components cannot be sufficiently dissolved in the first liquid medium, for example, in the case where the polar polymer in the present composition (2) is not in a dissolved state even if it swells, it is possible to achieve a state in which the entire amount of the components is dissolved by dilution using the second liquid medium. As the second liquid medium, it is particularly preferable to use the same liquid medium as the first liquid medium in the diluted present composition.

[0234] As the second liquid medium, it is possible to use a liquid medium that can be used as the first liquid medium, and a low-viscosity liquid medium is preferable.

[0235] When mixing the present composition with the second liquid medium in order to dilute the present composition with the second liquid medium, it is preferable to use a disperser, for example, from the viewpoint of the dispersibility and dispersion stability of the dispersion liquid obtained. As the disperser using a medium, it is possible to use an ultrasonic homogenizer, a ball mill, a pulverizer, a basket mill, a sand mill, a sand grinder, a DYNO mill, a DISPERMAT disperser, an SC mill, a pin mill, a stirring mill, etc. As the disperser not using a medium, it is possible to use an ultrasonic homogenizer, a nano-homogenizer, a vertical disperser, a disperser, a high-pressure impact disperser, a self-rotation and revolution stirrer, a thin-film rotary high-speed mixer, etc. Among these, the disperser using a medium is preferable because of the high dispersing ability.

[0236] Furthermore, since the dispersion stability is improved when mixing using an impact disperser, it is preferable to mix using an impact disperser for mixing with the second liquid medium.

[0237] The impact disperser refers to a disperser that disperses by the impact force, etc. when a liquid medium pressurized once with a high-pressure pump collides. The impact disperser can be roughly classified into two types according to the impact object. That is, a method in which liquid media collide with each other and a method in which a liquid medium collides with an impact object. As an example of the method in which liquid media collide with each other, it is possible to cite a nano-homogenizer, Genus PY, an ultrasonic homogenizer, Aqua, a micro-fluidizer, etc. As an example of the method in which a liquid medium collides with an impact object, it is possible to cite a homogenizer, etc.

[0238] Further, as a method for mixing the present composition with the second liquid medium, in addition to the mixing using the disperser described above, there can be mentioned a method in which the present composition is mixed with the second liquid medium in a kneader having a stirring tank and stirring blades for the above-mentioned kneading, a method in which the present composition is mixed with the second liquid medium by different kneaders, and the like. The kneader can be the same disperser as the above-mentioned batch and continuous kneaders.

[0239] In the production of the present dispersion, other resins, inorganic fillers, surfactants, and the like can be added as needed. In the case where both other resins and inorganic fillers are added, the other resins and inorganic fillers can be added separately, can be added together, or can be added after being prepared as a master batch of the other resins and inorganic fillers mixed together.

[0240] The solid content concentration in the present dispersion is preferably 40% by mass or more, and more preferably 50% by mass or more. From the viewpoint of the dispersibility of the present dispersion, the solid content concentration is preferably 90% by mass or less, and more preferably 75% by mass or less. Further, the solid content of the present dispersion refers to the content after all the liquid medium is removed from the present dispersion, and generally refers to the total amount of the solid-forming substances in the coating film or molded article formed from the present dispersion.

[0241] From the viewpoint of the dispersion stability of the present dispersion, the content of the present powder particles with respect to the amount of the solid content in the present dispersion is preferably 20% by mass or more, and more preferably 30% by mass or more. The content of the present powder particles is preferably 70% by mass or less, and more preferably 50% by mass or less.

[0242] The viscosity of the present dispersion, as measured by a B-type viscometer, is preferably 50 mPa-s or more, more preferably 75 mPa-s or more, and further preferably 100 mPa-s or more. The above-mentioned viscosity is preferably less than 8000 mPa-s, more preferably 5000 mPa-s or less, and further preferably 1000 mPa-s or less. The coating properties of the dispersion having such a viscosity are excellent.

[0243] Further, the thixotropy ratio of the present dispersion is preferably 1 to 10.

[0244] From the viewpoint of the reduction in the uniformity of the component distribution or the inhibition of voids in the coating film or molded article obtained from the present dispersion, the foam volume ratio in the dispersion is preferably less than 10%, and more preferably less than 5%. The foam volume ratio is preferably 0% or more.

[0245] By the above-mentioned mechanism of action, the dispersion having excellent liquid properties can be easily obtained according to the present method.

[0246] If the present dispersion is coated on the surface of a substrate and heated to form a layer composed of the F polymer (hereinafter also referred to as "F layer"), a laminate having a substrate and an F layer can be produced. The dispersion can be further left to stand at the time of use thereof.

[0247] As a suitable form of the laminate, 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.

[0248] The metal foil of the metal-clad laminate is preferably a copper foil. The metal-clad laminate is particularly useful as a printed board material.

[0249] The resin film of the multilayer film is preferably a polyimide film. The multilayer film is useful as a wire coating material, a printed board material.

[0250] In the production of the above-described laminate, the F layer can be formed on only one surface of the substrate, or on both surfaces of the substrate, as long as the F layer is formed on at least one surface of the substrate. The surface of the substrate can be subjected to surface treatment with a silane coupling agent or the like. In coating the present dispersion, a coating method such as a spray method, a roll coating method, a spin coating method, a gravure coating method, a microgravure coating method, a gravure offset coating method, a blade coating method, a kiss coating method, a bar coating method, a die coating method, a fountain Meyer bar coating method, a slit die coating method, or a dip coating method can be used.

[0251] The F layer is preferably formed by further baking the polymer by heating after removing the liquid medium from the present dispersion by heating. The removal temperature of the liquid medium is preferably as low a temperature as possible, and is preferably a temperature 50 to 150°C lower than the boiling point of the liquid medium. For example, in the case of using N-methyl-2-pyrrolidone having a boiling point of about 200°C, it is preferably heated at 180°C or lower, and preferably at 100 to 150°C. Air is preferably blown during the process of removing the liquid medium.

[0252] After the removal of the liquid medium, the substrate is preferably heated to a temperature range in which the polymer is baked to form, and the polymer is preferably baked, for example, in the range of 300 to 400°C. The F layer preferably contains a baked product of the F polymer.

[0253] The F layer is formed by the processes of coating, drying, and baking of the present dispersion as described above. These processes can be performed once or two or more times. For example, the processes of coating the present dispersion on the surface of the substrate, heating to remove the liquid medium to form a film can be repeated twice, and the film having an increased thickness is heated to bake the F polymer to form the F layer. From the viewpoint of easily obtaining a thick F layer having excellent smoothness, the processes of coating and drying of the present dispersion can be performed two or more times.

[0254] The thickness of the F layer is preferably 0.1 μm or more, more preferably 1 μm or more. The upper limit of the thickness is 100 μm. Within this range, the F layer having excellent crack resistance can be easily formed. The peel strength of the F layer from 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. If the present dispersion liquid is used, the properties of the F polymer in the F layer are not impaired, and the layered body can be easily formed.

[0255] The void fraction of the F layer is preferably 5% or less, more preferably 4% or less. The void fraction is preferably 0.01% or more, more preferably 0.1% or more. In addition, the void fraction is the area ratio (%) of the void portion in the cross section of the coating film or the molded product observed using a scanning electron microscope (SEM).

[0256] As the material of the base material, a metal substrate (a metal foil such as copper, nickel, aluminum, titanium, and an alloy thereof), a resin film (a film of polyimide, polyacrylate, polysulfone, polyarylsulfone, polyamide, polyether amide, polyphenylene sulfide, polyarylether ketone, polyamide-imide, liquid crystalline polyester, liquid crystalline polyester amide, and the like), a prepreg (a precursor of a fiber-reinforced resin substrate), a ceramic substrate, and a glass substrate can be given. As the shape of the base material, a planar shape, a curved shape, a concave-convex shape, and further any one of a foil shape, a plate shape, a film shape, and a fiber shape can be given.

[0257] The ten-point average roughness of the surface of the base material is preferably 0.01 to 0.05 μm.

[0258] As the suitable form of the layered body, a metal-clad layered body 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 given.

[0259] The metal foil of the metal-clad layered body is preferably a copper foil. The metal-clad layered body is particularly useful as a printed board material.

[0260] The resin film of the multilayer film is preferably a polyimide film. The multilayer film is useful as a wire coating material and a printed board material.

[0261] As specific examples of the polyimide film, "Kapton 50EN-S" (manufactured by Teijin DuPont), "Kapton 100EN" (manufactured by Teijin DuPont), "Kapton 100H" (manufactured by Teijin DuPont), "Kapton 100KJ" (manufactured by DuPont), "Kapton 100JP" (manufactured by DuPont, USA), and "Kapton 100LK" (manufactured by Teijin DuPont) can be given.

[0262] In addition, the printed board includes a flexible printed board, a rigid printed board.

[0263] The side of the F layer opposite the substrate can be further laminated with other substrates to form a multilayer laminate. The lamination can be performed, for example, by heat pressure bonding.

[0264] As a configuration of the multilayer laminate, there can be mentioned a substrate / F layer / other substrate / F layer / substrate, a metal substrate layer / other substrate layer / F layer / other substrate layer / metal substrate layer, and the like. Each layer can further include a glass cloth or a filler.

[0265] The laminate can be used as an antenna member, a printed board, a member for an airplane, a member for an automobile, sports equipment, a food industry product, a paint, a cosmetic, and the like, and specifically, as a wire covering material such as a wire for an airplane, an electrically insulating tape, an insulating tape for oil drilling, a material for a printed board, a separation membrane such as a precision filtration membrane, an ultrafiltration membrane, a reverse osmosis membrane, an ion exchange membrane, a dialysis membrane, a gas separation membrane, an electrode adhesive for a lithium secondary battery, a fuel cell, and the like, a copying roller, furniture, an instrument panel for a motor vehicle, a cover for a household appliance, a sliding member such as a load bearing, a sliding shaft, a valve, a bearing, a gear, a cam, a belt conveyor, a food conveyor belt, a tool such as a shovel, a file, a awl, a saw, a boiler, a hopper, a pipe, an oven, a baking mold, a chute, a mold, a toilet, a container covering material, a release film.

[0266] If the present dispersion liquid is impregnated in a woven fabric 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 referred to as a coated woven fabric in which the woven fabric is coated with the 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 can be treated with a silane coupling agent from the viewpoint of improving the adhesion between the F layer.

[0267] In the impregnated woven fabric, the content of the F polymer is preferably 30 to 80 mass%. The method of impregnating the dispersion liquid in the woven fabric can include a method in which the woven fabric is immersed in the dispersion liquid, and a method in which the dispersion liquid is applied to the woven fabric.

[0268] The F polymer can also be burned after drying the woven fabric. The method of burning the F polymer can include a method in which the woven fabric is passed through a ventilated drying oven at 300 to 400°C. In addition, the drying of the woven fabric and the burning of the polymer can be performed in one step. The woven fabric thus obtained is excellent in the adhesion or the adhesion between the F layer and the woven fabric, the surface smoothness, the deformation, and the like. If the woven fabric is heat pressure-bonded with a metal foil, a metal-clad laminate having high peel strength and being less likely to be warped can be obtained, which can be suitably used as a printed board material.

[0269] Further, in the production of the impregnated fabric, the fabric impregnated with the dispersion liquid can be arranged by being attached to the surface of a substrate or the like, and dried by heating, whereby an impregnated fabric layer containing the F polymer and the fabric is formed, and a laminate in which the substrate and the impregnated fabric layer are sequentially layered is produced. The form is not particularly limited, and for example, if the fabric impregnated with the dispersion liquid is arranged on a part or the whole of the inner wall surface of a member such as a tank, a pipe, or a container, and the member is heated while being rotated, an impregnated fabric layer can be formed on a part or the whole of the inner wall surface of the member. This production method is also used as a method of lining the inner wall surface of a member such as a tank, a pipe, or a container.

[0270] As described above, the present dispersion liquid has excellent dispersion stability, and can be effectively impregnated in a porous or fibrous material. As the porous or fibrous material, a material other than the above-described fabric can be exemplified, and specifically, a plate-like, columnar, or fibrous material can be exemplified. These materials can be pretreated with a curable resin, a silane coupling agent, or the like, and can be further filled with an inorganic filler or another resin, or the like. Further, these materials can be twisted into a yarn, a cable, or a wire. At the time of twisting, an intermediate layer composed of another polymer such as polyethylene can be arranged. As a form in which the dispersion liquid is impregnated in the material to produce a shaped article, a form in which the dispersion liquid is impregnated in a fibrous material on which a curable resin or a cured product thereof is supported can be exemplified.

[0271] As the fibrous material, a fiber having high strength and low elongation such as a carbon fiber, an aramid fiber, or a silicon carbide fiber can be exemplified. As the curable resin, a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, or a polyurethane resin is preferred. As a specific example of this form, a composite cable in which a cable twisted from a carbon fiber on which a thermosetting resin is supported is impregnated with the dispersion liquid and further heated to burn the F polymer can be exemplified. This composite cable can be used as a cable for large-scale structures, ground anchoring, oil excavation, cranes, ropeways, elevators, agriculture, forestry, and fishery, or a sling cable.

[0272] As described above, the present dispersion liquid having excellent dispersibility and dispersion stability can be obtained by diluting the present composition. Agglomeration of F polymer particles in the present dispersion liquid is suppressed, and foaming at the time of production and use of the present dispersion liquid is suppressed. As a result, the surface smoothness of the obtained coating film or shaped article is excellent.

[0273] The present composition, the production method of the present composition, and the production method of the present dispersion liquid from the present composition have been described above, but the present application is not limited to the configuration of the above-described embodiments.

[0274] For example, the production method of the present composition or the present dispersion liquid in the above-described embodiments can add other arbitrary processes or can replace them with arbitrary processes that have the same function. In addition, the present composition and the present dispersion liquid in the above-described embodiments can add other arbitrary configurations or can replace them with arbitrary configurations that have the same function.

[0275] Examples

[0276] Hereinafter, the present application will be described in detail by examples, but the present application is not limited to them.

[0277] [Example 1]

[0278] 1-1. Preparation of each component

[0279] [Polymer]

[0280] Powder 11: A powder composed of a polymer having 1000 carbonyl group-containing groups per 1 x 10 6 main chain carbons (fluorine content: 76 mass%) composed of TFE units, NAH units, and PPVE units in this order (D50: 2.0 μm, specific surface area: 3 m 2 / g)

[0281] Powder 12: A powder composed of a polymer having 40 carbonyl group-containing groups per 1 x 10 6 main chain carbons (fluorine content: 76 mass%) composed of TFE units and PPVE units (D50: 2.4 μm, specific surface area: 4 m 2 / g)

[0282] [Aromatic polymer]

[0283] Clearcoat 1: A clearcoat in which a thermoplastic aromatic polyimide (PI1) is dissolved in NMP

[0284] [Surfactant]

[0285] Surfactant 1: A copolymer of CH2=C(CH3)C(O)OCH2CH2(CF2)6F and CH2=C(CH3)C(O)(OCH2CH2) 23 OH, and the fluorine content is 35 mass%

[0286] [Liquid medium]

[0287] NMP: N-methyl-2-pyrrolidone

[0288] [Viscosity]

[0289] The viscosity in Example 1 below means the viscosity measured with a B-type viscometer at a temperature of 25°C and a rotation speed of 30 rpm.

[0290] 1-2. Examples of production of dispersions

[0291] [Example 1-1]

[0292] A liquid composition containing the powder 11 (70 parts by mass), PIl (1.8 parts by mass), the surfactant 1 (3.5 parts by mass), and NMP (30 parts by mass) was obtained by charging the powder 11, the varnish 1, the surfactant 1, and NMP into a planetary mixer, keeping the planetary mixer under reduced pressure, and kneading the liquid composition while degassing. NMP was added to adjust the viscosity to obtain a paste-like composition 1 having a viscosity of 10,000 mPa-s. After the composition 1 was left to stand at 25°C for 48 hours under atmospheric pressure, NMP was added to the composition 1 in portions so that the total amount of NMP reached 70 parts by mass, and the mixture was stirred to obtain a dispersion 11 having a viscosity of 1,000 mPa-s.

[0293] [Examples 1-2 to 1-6]

[0294] Paste-like compositions 2 to 6 were obtained in the same manner as in Example 1-1, except that the type of powder, degassing or not, and viscosity adjustment during standing (i.e., addition of NMP during production of the paste-like composition) were changed as shown in Table 1. Using the obtained pastes 2 to 6, dispersions 12 to 16 were obtained in the same manner as in Example 1-1. In addition, the values in parentheses in the column of "standing" in Table 1 represent the standing time (unit: hr).

[0295] In addition, the foam volume ratio of the composition 1, the composition 3, the dispersion 11, and the dispersion 13 was 0% or more and less than 5%, the foam volume ratio of the composition 2, the composition 4, the composition 6, the dispersion 12, the dispersion 14, and the dispersion 16 was more than 5% and less than 10%, and the foam volume ratio of the composition 5 and the dispersion 15 was 10% or more.

[0296] 1-3. Evaluation of dispersions

[0297] The diluted dispersion was sandwiched between two pieces of quartz glass, and the transmitted light image was observed in the transmitted light mode of an optical microscope. The dispersion state of the powder in the dispersion was evaluated in accordance with the following evaluation criteria. In addition, the higher the absence of contrast or mesh-like patterns in the transmitted light image, the higher the flowability and dispersibility of the dispersion.

[0298] <Evaluation Criteria>

[0299] O: The transmitted light image had no contrast and mesh-like patterns.

[0300] Δ: The transmitted light image had contrast but no mesh-like patterns.

[0301] X: The transmitted light image had contrast and mesh-like patterns.

[0302] [Table 1]

[0303]

[0304] 1-4. Examples of production of laminates

[0305] [Layered body 1]

[0306] The dispersion liquid 11 was applied to the surface of a long copper foil having a thickness of 18 μm by a bar coating method to form a wet film. Thereafter, the metal foil on which the wet film was formed was passed through a drying furnace at 110°C for 5 minutes to dry by heating, and a dry film was obtained. Thereafter, the dry film was heated at 380°C for 3 minutes in a nitrogen furnace. By this, a laminate 11 having a metal foil, and a polymer layer of a formed product having a thickness of 20 μm of a fusion-burnt product of the powder 11 and the PI 1 on the surface of the metal foil was produced.

[0307] [Layered bodies 2 to 6]

[0308] In the production of the laminate 1, the dispersion liquid 11 was changed to the dispersion liquids 12 to 16, and the laminates were produced in the same manner to obtain the laminates 2 to 6, respectively.

[0309] 1-5. Evaluation of laminates

[0310] The coating unevenness and the dielectric loss tangent of the obtained laminates 1 to 6 were evaluated in accordance with the following criteria.

[0311] The results are shown in Table 2.

[0312] 1-5-1. Evaluation of coating unevenness of laminates

[0313] <Criteria for evaluation>

[0314] O: No pitting was recognized on the surface of the polymer layer, and the entire surface was smooth.

[0315] Δ: Pitting was recognized on a part of the polymer layer, but the entire surface was smooth.

[0316] X: Pitting was recognized on the entire surface of the polymer layer, and the entire surface had unevenness.

[0317] 1-5-2. Evaluation of dielectric loss tangent of laminates

[0318] For each laminate, the copper foil of the laminate was removed by etching with an aqueous ferrous chloride solution to prepare a separate polymer layer, the dielectric loss tangent of the polymer layer was measured at a measurement frequency of 10 GHz by an SPDR (split post dielectric resonator) method, and the evaluation was performed in accordance with the following criteria.

[0319] <Criteria for evaluation>

[0320] ○: Its dielectric loss tangent is less than 0.0010.

[0321] △: Its dielectric loss tangent is above 0.0010 and below 0.0025.

[0322] ×: Its dielectric loss tangent is greater than 0.0025.

[0323] [Table 2]

[0324]

[0325] [Example 2]

[0326] 2-1. Preparation of each component

[0327] [powder]

[0328] Powder 21: Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units per 1 × 10⁻⁶ units. 6 Powder composed of a polymer with 1000 carbonyl groups in its main chain and a melting temperature of 300°C (D50: 2.1 μm).

[0329] [Polar Polymers]

[0330] Polar polymer 1: Aromatic polyimide (U-varnish manufactured by Ube Industries, Ltd.)

[0331] Polar polymer 2: Carboxymethyl cellulose (Nippon Paper Corporation (Japan)) (The "SUNROSE MAC Series 200HC" manufactured by the company)

[0332] Polar polymer 3: Polyvinyl alcohol ("S-LEC BL-1" manufactured by Sekisui Chemicals Co., Ltd.)

[0333] [Inorganic packing]

[0334] Inorganic filler 1: Silica filler with aminosilane coupling agent surface treatment (D50: 0.2μm)

[0335] [Liquid medium]

[0336] NMP: N-methyl-2-pyrrolidone

[0337] [Viscosity]

[0338] In Example 2 below, the viscosity of the composition refers to the viscosity at a temperature of 25°C and a shear rate of 1 second. -1 The viscosity obtained by capillary rheology measurement is the viscosity of the dispersion measured using a type B viscometer at a temperature of 25°C and a rotation speed of 30 rpm.

[0339] 2-2. Manufacturing Example of the Composition

[0340] [Example 2-1]

[0341] Into a tank, a varnish of the polar polymer 1 (solvent: NMP) and NMP were put and mixed. Further, into the tank, a powder mixture of the powder 21 and the inorganic filler 1 were put and mixed, and a mixture was prepared. After the mixture was kneaded in a planetary mixer, it was taken out, and a composition 21 containing the powder 21 (50 parts by mass), the inorganic filler 1 (40 parts by mass), and the polar polymer 1 (10 parts by mass), NMP (30 parts by mass) was obtained. The composition 21 was in a lump and clay-like, and was a wet powder.

[0342] The viscosity of the composition 21 was 18000 Pa-s at a temperature of 25°C and a shear rate of 1 s -1 The viscosity of the composition 21 was 18000 Pa-s at a temperature of 25°C and a shear rate of 1 s

[0343] Into the composition 21, NMP was added in portions while stirring with a self-rotation and revolution agitator at 2000 rpm with degassing. Further, while adding NMP in portions, 80 parts by mass of NMP was added in total to the composition 21, and a dispersion liquid was prepared, and a dispersion liquid 21 was obtained. The viscosity of the dispersion liquid 21 was 300 mPa-s.

[0344] [Example 2-2]

[0345] 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 if the composition 22 was further kneaded, the variation of the viscosity was within ±3%. The viscosity of the dispersion liquid 22 was 400 mPa-s.

[0346] [Example 2-3]

[0347] 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 if the composition 23 was further kneaded, the variation of the viscosity was within ±3%. The viscosity of the dispersion liquid 23 was 400 mPa-s.

[0348] [Example 2-4]

[0349] 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 60000 Pa-s, and if the composition 24 was further kneaded, the variation of the viscosity exceeded ±5%. The viscosity of the dispersion liquid 24 was 800 mPa-s.

[0350] [Example 2-5]

[0351] The composition 25 and the dispersion 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 25 was 400 mPa-s.

[0352] [Example 2-6]

[0353] The composition 26 and the dispersion 26 were obtained in the same manner as in Example 2-1, except that NMP was changed to n-decane. The viscosity of the composition 26 was 80000 Pa-s, and even if the composition 26 was further kneaded, the variation range of the viscosity was within ±3%. The viscosity of the dispersion 26 was 3000 mPa-s.

[0354] 2-3. Evaluation

[0355] 2-3-1. Evaluation of dispersion stability of dispersion

[0356] After each dispersion was stored for a long period of time at 25°C in a container, the dispersion stability was evaluated by visually confirming the dispersibility in accordance with the following criteria.

[0357] [Criteria for evaluation]

[0358] O: No agglomerates were recognized.

[0359] Δ: Adhesion of fine agglomerates was recognized on the side wall of the container. If gently stirred, it was uniformly redispersed.

[0360] X: Agglomerates were recognized to be precipitated also on the bottom of the container. Strong shear stirring was required for redispersion.

[0361] 2-3-2. Evaluation of thixotropic stability of dispersion

[0362] Each dispersion was stored for 30 days at 25°C in a container, and the variation range of the thixotropic ratio before and after the storage was measured, and the thixotropic stability was evaluated in accordance with the following criteria.

[0363] [Criteria for evaluation]

[0364] O: The absolute value of the variation range of the thixotropic ratio was less than 1

[0365] Δ: The absolute value of the variation range of the thixotropic ratio was 1 or more and less than 3

[0366] X: The absolute value of the variation range of the thixotropic ratio was more than 3

[0367] The evaluation results are collectively shown in Table 3 below.

[0368] [Table 3]

[0369] dispersion stability thixotropic stability dispersion 21 ○ ○ dispersion 22 ○ ○ dispersion 23 ○ ○ dispersion 24 △ △ dispersion 25 △ △ dispersion 26 × ×

[0370] Possibility of use in industry

[0371] From the above results, it is clear that the dispersibility, dispersion stability, and thixotropic stability of the dispersion liquid produced by the present method are excellent, and therefore the uniformity of the composition distribution of the laminate obtained using the dispersion liquid obtained by the present method is excellent, and various physical properties are excellent.

[0372] In addition, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2020-181771 filed on October 29, 2020 and Japanese Patent Application No. 2021-051437 filed on March 25, 2021 are hereby incorporated by reference as a disclosure of the present application.

Claims

1. A blocky or clay-like composition comprising components derived from substances with a specific surface area of ​​25 m². 2 The following are included: particles of tetrafluoroethylene polymer powder containing carbonyl or hydroxyl groups (with a weight of less than 1 g); polar polymers or precursors containing carbonyl or hydroxyl groups; and polar liquid media selected from at least one of amides, ketones, and esters capable of dissolving the polar polymers or precursors. The content of the particles and the content of the polar polymer or precursor thereof are greater than 50 mass%, the content of the liquid medium having polarity is 40 mass% or less, the ratio of the content of the polar polymer or precursor thereof to the content of the particles is 0.001 or more and less than 0.5, and the viscosity obtained by capillary rheometry at a temperature of 25°C and a shear rate of 1 s -1 -1 is 10,000 to 50,000 Pa-s.

2. The composition of claim 1, wherein, The polar polymer or the precursor thereof is an imide-based polymer, a precursor of an imide-based polymer, an ethylene-based polymer, or a polysaccharide.

3. The composition of claim 1 or 2, wherein, The liquid medium having polarity is a liquid medium selected from water, amides, ketones, and esters.

4. The composition of claim 1, wherein, The tetrafluoroethylene-based polymer is a polymer having a carbonyl group-containing group or a hydroxyl group-containing group.

5. The composition of claim 1, wherein, The tetrafluoroethylene-based polymer has a fluorine content of 70% by mass or more.

6. The composition of claim 1, wherein, The tetrafluoroethylene-based polymer has a melting temperature of 180 to 325°C.

7. The composition of claim 1, wherein, The average particle diameter of the particles constituting the tetrafluoroethylene-based polymer powder is 0.1 to 20 μm.

8. The composition according to claim 1, further comprising an inorganic filler.

9. A method for producing a composition by mixing a mixture comprising particles of a tetrafluoroethylene-based polymer powder having a specific surface area of 25 m2 / g or less and having a carbonyl group-containing or hydroxyl group-containing group, a polar polymer having a carbonyl group-containing or hydroxyl group-containing group or a precursor thereof, and a liquid medium having a polarity selected from at least one of an amide, a ketone and an ester capable of dissolving the polar polymer or the precursor thereof, and performing at least one of degassing during or after the mixing and standing after the mixing, to produce the composition according to any one of claims 1 to 8. 2 The total content of the particles and the polar polymer or the precursor thereof is more than 50% by mass, the content of the liquid medium having polarity is 40% by mass or less, and the ratio of the content of the polar polymer or the precursor thereof to the content of the particles is 0.001 or more and less than 0.

5. ​ 10. The production method as claimed in claim 9, wherein, Both the degassing and the standing are performed.

11. A method for producing a dispersion liquid by diluting the composition according to any one of claims 1 to 8 with a second liquid medium to obtain a dispersion liquid.

12. A wet powder comprising: a powder derived from a specific surface area of ​​25 m² / g. 2 The composition includes particles of tetrafluoroethylene-based polymer powder containing carbonyl or hydroxyl groups (with a weight of less than 1 g), polar polymers or precursors containing carbonyl or hydroxyl groups, and a polar liquid medium selected from at least one of amides, ketones, and esters, wherein... The content of the particles and the content of the polar polymer or precursor thereof are greater than 50 mass%, the content of the liquid medium having polarity is 40 mass% or less, the ratio of the content of the polar polymer or precursor thereof to the content of the particles is 0.001 or more and less than 0.5, and the viscosity obtained by capillary rheometry at a temperature of 25°C and a shear rate of 1 s -1 -1 is 10,000 to 50,000 Pa-s.

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