CN116348534A - Composition comprising tetrafluoroethylene polymer powder particles, process for producing the same, and process for producing dispersion from the composition - Google Patents

Abstract

The present invention provides a high viscosity composition containing tetrafluoroethylene polymer powder particles 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, the composition comprising: derived from a specific surface area of 25m ² Particles of tetrafluoroethylene polymer powder of/g or less, liquid medium, and optionally other polymer dissolved in the liquid medium, wherein the viscosity is measured by a B-type viscometer at 25 ℃ and 30rpm8000-100000 mPa.s or a shearing speed of 1s according to a temperature of 25 DEG C ^‑1 The viscosity obtained by the capillary rheometry is 10000-100000 Pa.s. And a method for producing the composition, wherein a mixture of the components of the composition is kneaded and at least one of deaeration during or after the kneading and standing after the kneading is performed, and a method for producing a dispersion in which particles derived from the powder are dispersed in a liquid medium by diluting the composition with the liquid medium.

Description

Composition comprising tetrafluoroethylene polymer powder particles, process for producing the same, and process for producing dispersion from the composition

Technical Field

The present invention relates to a high-viscosity composition comprising tetrafluoroethylene polymer powder particles and a liquid medium, a method for producing the high-viscosity composition, and a method for producing a dispersion of tetrafluoroethylene polymer particles dispersed therein from the high-viscosity composition.

Background

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

For example, patent document 1 discloses a nonaqueous dispersion liquid using an additive from the viewpoint of improving the dispersibility of the dispersion liquid and adjusting the liquid properties thereof.

Prior art literature

Patent literature

Patent document 1: international publication No. 2016/15972

Disclosure of Invention

Technical problem to be solved by the invention

However, the dispersion described in patent document 1 is still insufficient in terms of dispersion stability.

In particular, in the case of tetrafluoroethylene polymer powder having a high fluorine content and a small specific surface area, foaming is intense when preparing a dispersion thereof, and dispersion stability may be lowered due to coagulation. Further, the surface smoothness of a coating film or a molded article obtained from such a dispersion may be lowered.

The present inventors have studied a method for producing a dispersion liquid excellent in dispersion stability of powder particles from tetrafluoroethylene polymer powder having a small specific surface area, and have completed the present invention.

Further, a dispersion liquid containing powder particles of a tetrafluoroethylene polymer and further containing other functional materials (an inorganic filler, a polymer or a resin different from the tetrafluoroethylene polymer, or the like) may impart physical properties of the other functional materials to a coating film or a molded article formed from the dispersion liquid.

However, the tetrafluoroethylene polymer has low affinity with other functional materials, and the dispersion stability of the tetrafluoroethylene polymer tends to be further lowered in the dispersion.

When a high shear is applied to disperse tetrafluoroethylene polymer powder when other functional materials are added, foaming or aggregation is likely to occur due to entrainment of air, deterioration of tetrafluoroethylene polymer, or the like.

As a result, the coating film or the molded article obtained from the dispersion liquid is liable to have a decrease in uniformity of component distribution or a decrease in water resistance due to the occurrence of voids.

The present invention provides a paste-like highly viscous composition containing tetrafluoroethylene polymer powder particles and a liquid medium as a dispersion precursor, and a method for producing the same.

The present invention also provides a composition having a higher viscosity such as a wet powder which is a dispersion precursor comprising a tetrafluoroethylene polymer powder particles, a polar polymer and a polar liquid medium, and a method for producing the composition.

Further, the present invention provides a dispersion liquid excellent in dispersion stability, which is a dispersion liquid obtained by dispersing the powder particles of the tetrafluoroethylene polymer by diluting the high viscosity composition with a liquid medium.

Technical proposal adopted for solving the technical problems

The present invention has the following technical matters.

[1]A composition comprising a material derived from a material having a specific surface area of 25m ² Particles of tetrafluoroethylene polymer powder per gram or less and a liquid medium, wherein the concentration of solid content is 40 mass% or more, and the viscosity of the tetrafluoroethylene polymer powder is 8000 to 100000 mPas measured by a B-type viscometer at a temperature of 25 ℃ and a rotation speed of 30 rpm.

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

[3]A composition comprising a material derived from a material having a specific surface area of 25m ² Particles of tetrafluoroethylene polymer powder of not more than/g, polar polymer or precursor thereof, and polar liquid medium capable of dissolving the polar polymer or precursor thereof, at 25 ℃ and shearing rate of 1s ^-1 The viscosity obtained by the capillary rheometry is 10000-100000 Pa.s.

[4] The composition according to [3], wherein the total of the content of the particles and the content of 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.

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

[6] The composition according to any one of [3] to [5], wherein the liquid medium having polarity is a liquid medium selected from the group consisting of water, amides, ketones and esters.

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

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

[9] The composition according to any one of [1] to [8], wherein the tetrafluoroethylene polymer has a melting temperature of 180 to 325 ℃.

[10] The composition according to any one of [1] to [9], wherein the particles constituting the tetrafluoroethylene polymer powder have an average particle diameter of 0.1 to 20. Mu.m.

[11] The composition of any one of [1] to [10], further comprising an inorganic filler.

[12]Manufacturing [1]]～[11]A method for producing a composition comprising a composition derived from the composition according to any one of the above, wherein the specific surface area is 25m ² Mixing a mixture of particles of tetrafluoroethylene polymer powder and a liquid medium, and at least one of deaeration during or after the mixing and standing after the mixing.

[13] The production method according to [12], wherein both of the deaeration and the standing are performed.

[14] A method for producing a dispersion, wherein the composition of any one of [1] to [11] is diluted with a 2 nd liquid medium to obtain a dispersion.

[15]A wet powder comprising: derived from a specific surface area of 25m ² Particles of tetrafluoroethylene polymer powder having carbonyl group-containing or hydroxyl group-containing, polar polymer having carbonyl group-containing or hydroxyl group-containing or precursor thereof, and at least 1 polar liquid medium selected from amide, ketone and ester.

Effects of the invention

By using the high-viscosity composition of the present invention, a dispersion liquid containing particles derived from tetrafluoroethylene polymer powder having a small specific surface area and having excellent dispersion stability can be produced. By using the dispersion obtained by this production method, the obtained coating film or molded article has an appearance excellent in surface smoothness.

Detailed Description

The following terms have the following meanings.

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

The "glass transition temperature (Tg) of a polymer" is a value determined by analyzing a polymer by the dynamic viscoelasticity measurement (DMA) method.

"melting temperature (melting point) of a polymer" means a temperature corresponding to the maximum value of a melting peak measured by a Differential Scanning Calorimeter (DSC) method.

The "D50" is the average particle diameter of particles constituting the object to be measured such as powder or inorganic filler, and is the cumulative 50% diameter of the volume of the particles constituting the object to be measured obtained by the laser diffraction/scattering method. That is, the particle size distribution of particles constituting the object to be measured is measured by a laser diffraction scattering method, and a cumulative curve is obtained with the total volume of the object to be measured being 100%, and the particle diameter at the point on the cumulative curve where the cumulative volume reaches 50%.

"D90" is the cumulative volume particle diameter of particles constituting the object to be measured, and is the cumulative 90% diameter based on the volume of particles obtained in the same manner as "D50".

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

The "viscosity measured by a type B viscometer" means a value measured at room temperature (25 ℃) and a rotation speed of 30rpm using a type B viscometer. The measurement was repeated 3 times, and the average of the 3 measured values was taken.

"thixotropic ratio" means the viscosity η measured using a B-type viscometer at room temperature (25 ℃) and at a rotation speed of 30rpm ₁ Divided by the viscosity eta measured at a speed of 60rpm ₂ The calculated value (eta ₁ /η ₂ )。

"monomer-based unit" in a polymer refers to an atomic group formed directly from 1 monomer molecule by polymerization and formed by treating the polymer such that a portion of the atomic group is converted to another structure. Hereinafter, the unit based on the monomer a is also simply referred to as "monomer a unit".

Hereinafter, the tetrafluoroethylene polymer of the present invention is also referred to as "F polymer". In addition, the specific surface area is 25m ² The F polymer powder of/g or less is also referred to as "present powder".

In the following, the liquid medium having a polarity is also referred to as "liquid polar medium".

One of the compositions of the present invention is the following: the powder contains particles derived from the powder and a liquid medium, has a solid content of 40 mass% or more, and has a viscosity (hereinafter, simply referred to as "viscosity measured by a B-type viscometer") of 8000 to 100000 mPas measured by a B-type viscometer at a temperature of 25 ℃ and a rotation speed of 30 rpm. Hereinafter, the composition of the present invention is referred to as "present composition (1)".

Another of the compositions of the present invention is the following: comprising particles derived from the present powder, a polar polymer or precursor thereof, and a liquid polar medium, which is passed through a shear rate of 1s ^-1 The viscosity obtained by capillary rheometry (hereinafter, simply referred to as "viscosity obtained by capillary rheometry") is 10000 to 100000pa·s. Hereinafter, the composition of the present invention is referred to as "present composition (2)".

The present composition (1) and the present composition (2) are also collectively referred to as "present composition".

The composition is suitable as an intermediate for obtaining a dispersion of particles derived from the powder dispersed in a liquid medium. The dispersion may be obtained by diluting the present composition with a liquid medium.

In addition, in order to distinguish from the 2 nd liquid medium used for dilution of the present composition, the liquid medium in the present composition is also referred to as "1 st liquid medium" as required.

Hereinafter, the F polymer, the present powder, the liquid medium, the polar polymer and the precursor thereof according to the present composition will be described first.

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

The fluorine content of the F polymer is preferably 70% by mass or more. Of the F polymers having a high fluorine content, F polymers are excellent in physical properties such as electric properties, but have significantly low affinity with a liquid medium. Therefore, the dispersibility of the particles of the F polymer is further reduced. According to the present composition, even in the dispersion of the F polymer particles obtained by using the composition, the physical properties of the whole F polymer are not impaired, and a dispersion excellent in dispersibility can be obtained.

The fluorine content of the F polymer is preferably 76 mass% or less.

The F polymer may be hot-melt or non-hot-melt.

The hot-melt polymer is a polymer having a melt flow rate of 1 to 1000g/10 minutes under a load of 49N.

The non-heat-fusible polymer is a polymer having a melt flow rate of 1 to 1000g/10 minutes under a load of 49N.

The melting temperature of the heat-fusible F polymer is preferably 180℃or higher, more preferably 200℃or higher, and still more preferably 260℃or higher. The melting temperature of the F polymer is preferably 325℃or less, more preferably 320℃or less. The melting temperature of the F polymer is particularly preferably 180 to 325 ℃.

The glass transition temperature of the F polymer is preferably 50℃or higher, more preferably 75℃or higher. The glass transition temperature of the F polymer is preferably 150℃or less, more preferably 125℃or less.

The F polymer is preferably polytetrafluoroethylene (hereinafter also referred to as "PTFE"), a polymer containing TFE units and units based on perfluoro (alkyl vinyl ether) (hereinafter also referred to as "PAVE units") (hereinafter also referred to as "PFA"), or a copolymer containing TFE and units based on hexafluoropropylene (hereinafter also referred to as "FEP"), more preferably PFA or FEP, and further preferably PFA. These polymers may also contain units based on other comonomers.

As PAVE, CF is preferred ₂ ＝CFOCF ₃ 、CF ₂ ＝CFOCF ₂ CF ₃ Or CF (CF) ₂ ＝CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as PPVE), more preferably PPVE.

The F polymer preferably has polar functional groups. In this case, the affinity of the present powder with the liquid medium is easily improved. The F polymer may have 2 or more polar functional groups.

The polar functional group is preferably a carbonyl group-containing group, a hydroxyl group-containing group, or a phosphoryl group-containing group, and the F polymer is more preferably a carbonyl group-containing or hydroxyl group-containing F polymer from the viewpoint of improving the physical properties such as dispersibility of the present powder.

The polar functional groups may be contained in the monomer units in the F polymer or may be contained in terminal groups of the polymer backbone. The latter form includes F polymers having polar functional groups as terminal groups derived from polymerization initiators, chain transfer agents, and the like.

In the case where the F polymer has carbonyl-containing groups, the number of carbonyl-containing groups in the F polymer is 1X 10 per unit ⁶ The number of main chain carbons is preferably 10 to 5000, more preferably 50 to 2000. In this case, the affinity of the particles of the F polymer with the liquid medium is easily improved. The number of carbonyl groups contained in the F polymer can be determined according to the composition of the polymer or the method described in International publication No. 2020/145133.

As the carbonyl group-containing group, preferred is a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH) ₂ ) Anhydride residues (-C (O) OC (O) -), imide residues (-C (O) NHC (O) -, etc.), and carbonate groups (-OC (O) O-), more preferably anhydride residues. As the hydroxyl group-containing group, an alcoholic hydroxyl group-containing group is preferable, and-CF is more preferable ₂ CH ₂ OH、-C(CF ₃ ) ₂ OH and 1, 2-diol (-CH (OH) CH) ₂ OH)。

Preferable examples of the F polymer include a polymer (1) having a carbonyl group or a hydroxyl group, which contains TFE units and PAVE units, and a polymer (2) having no carbonyl group or hydroxyl group, which contains TFE units and PAVE units and contains PAVE units in an amount of 2 to 5 mol% relative to the total monomer units. Since these polymers form fine spherulites in the coating film or the molded article, the properties of the obtained coating film or molded article are obtained.

As the polymer (1), a polymer containing TFE units, PAVE units and units based on a monomer having a hydroxyl group or a carbonyl group is preferable. The polymer (1) is more preferably a polymer containing 90 to 99 mol% of TFE units, 0.5 to 9.97 mol% of PAVE units, and 0.01 to 3 mol% of units based on the above monomers, respectively, based on the total units.

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

As a specific example of the polymer (1), there may be mentioned a polymer described in International publication No. 2018/16644.

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

The content of PAVE units in the above-mentioned preferred polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, relative to the total monomer units.

In addition, the absence of either the carbonyl group-containing group or the hydroxyl group-containing group in the polymer (2) means that the number of carbon atoms relative to the main chain of the polymer is 1X 10 ⁶ The number of carbonyl-containing groups or hydroxyl-containing groups in the polymer is less than 500. The number of carbonyl-containing groups or hydroxyl-containing groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of carbonyl-containing groups or hydroxyl-containing groups is usually 0.

The polymer (2) may be produced using a polymerization initiator, a chain transfer agent, or the like that does not generate a polar functional group as a terminal group of a polymer chain, or may be produced by fluorinating a polymer having a polar functional group such as a polymer having a polar functional group derived from a polymerization initiator at a terminal group of a polymer chain.

As a method of the fluorination treatment, a method using fluorine gas is exemplified (refer to japanese patent application laid-open No. 2019-194314, etc.).

The powder consists of particles of F polymer.

The specific surface area of the powder is preferably 8m ² Preferably less than or equal to/g, more preferably 5m ² Preferably less than or equal to/g, particularly preferably 3m ² And/g or less. The specific surface area of the powder is preferably1m ² And/g.

The D50 of the powder is preferably 20 μm or less, more preferably 8 μm or less. The D50 of the powder is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 1 μm or more. The D90 of the powder is preferably less than 100. Mu.m, more preferably 90. Mu.m or less. When the D50 and D90 of the powder are within this range, the surface area becomes large, and the dispersibility of the powder is easily improved further.

The powder may be composed of particles composed of a mixture of 2 or more kinds of F polymers, or may be composed of 2 or more kinds of particles composed of F polymers. The latter is a powder composed of particles of a certain F polymer and particles of a different F polymer, and is usually a mixture (i.e., powder mixture) of a certain F polymer powder and a different F polymer powder.

As the powder mixture, a mixture of a heat-fusible F polymer powder (a heat-fusible F polymer powder containing TFE units and PAVE units and having carbonyl groups, etc.) and a non-heat-fusible F polymer powder (a non-heat-fusible PTFE powder, etc.) is preferable.

When the present powder is a mixture of the above 2 kinds of powders, the proportion of the former particles (particles of the heat-fusible F polymer) in the total amount of the present powder is preferably 50 mass% or less, more preferably 25 mass% or less. The proportion is preferably 0.1% by mass or more, and more preferably 1% by mass or more. Further, it is preferable that the former particles have a D50 of 1 to 4 μm and the latter particles (particles of a non-heat-fusible F polymer) have a D50 of 0.1 to 1. Mu.m.

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

Specific examples of the polymer or resin different from the F polymer include cured products of polymers such as aromatic polyimide, aromatic maleimide, aromatic elastomer such as styrene elastomer, aromatic polyamic acid, and the like, and curable resins. However, as in the case of the present composition (2) described later, there are also those which have solubility in a liquid medium according to the liquid medium in the present composition but do not become components of particles constituting the present powder.

Specific examples of the inorganic substance include silicon oxide (silica), metal oxide (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite).

Examples of the present powder containing particles containing an F polymer and a polymer or resin different from the F polymer or an inorganic substance include: the powder is composed of particles composed of a mixture of particles of F polymer, a polymer or a resin or an inorganic substance different from the F polymer, and the powder is composed of particles having a core-shell structure in which the F polymer is used as a core and the polymer or the resin or the inorganic substance different from the F polymer is used as a shell or in which the F polymer is used as a shell and the polymer or the resin or the inorganic substance different from the F polymer is used as a core. The latter powder may be obtained by combining an F polymer powder with a powder composed of a polymer or resin powder different from the F polymer or inorganic fine particles by impact, coagulation or the like.

The liquid medium is an inert liquid which does not dissolve particles of the F polymer constituting the present powder (hereinafter also referred to as "present powder particles") and is liquid at 25 ℃. The liquid medium preferably has an affinity for the F polymer particles, e.g. the liquid polar medium typically has an affinity for particles having carbonyl-or hydroxyl-containing F polymers. The liquid medium in the composition may have a low viscosity or a high viscosity. As the liquid medium in the present composition, a low-viscosity liquid medium is preferable.

Hereinafter, the low-viscosity liquid medium means a liquid medium having a viscosity of 10 mPas or less as measured at 25℃by a type B viscometer, and the high-viscosity liquid medium means a liquid medium having a viscosity of more than 10 mPas as measured at 25℃by a type B viscometer.

The boiling point of the low viscosity liquid medium is preferably 75 ℃ or higher, more preferably 100 ℃ or higher. The boiling point of the low viscosity liquid medium is preferably 300 ℃ or less, more preferably 250 ℃ or less.

The low-viscosity liquid medium may be a liquid polar medium or a nonpolar liquid medium such as a hydrocarbon liquid medium. The liquid polar medium is a liquid medium having a polar group, and is composed of an organic compound having a polar group such as an amide group, a carbonyl group, or an oxycarbonyl group, and a liquid medium composed of an inorganic compound having a polarity such as water. The organic compound having a polar group is preferably an amide, a ketone or an ester, and the inorganic compound having a polar group is preferably water.

As the liquid polar medium in the present composition (2), a liquid polar medium selected from the group consisting of water, amides, ketones and esters is preferable as a low-viscosity liquid medium.

Specific examples of the amide which is a low viscosity liquid medium include N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-diethylformamide, hexamethylphosphoric triamide, and 1, 3-dimethyl-2-imidazolidinone.

Specific examples of ketones as low-viscosity liquid media include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentanone, methyl iso-pentanone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone.

Specific examples of the ester as the low-viscosity liquid medium include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, γ -butyrolactone, and γ -valerolactone.

As the low-viscosity liquid medium, water, N-methyl-2-pyrrolidone, gamma-butyrolactone, cyclohexanone, cyclopentanone are preferable.

The boiling point of the high viscosity liquid medium is preferably above 100 ℃. The boiling point of the high viscosity liquid medium is preferably 350 ℃ or less, more preferably 300 ℃ or less.

Examples of the high-viscosity liquid medium include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, and derivatives such as ethers and esters of the glycols. The ether derivative of the diol is more preferably a diol monoalkyl ether, a diol monoaryl ether, a diol monoalkyl ether alkyl ester, a diol monoaryl ether alkyl ester, or a diol dialkyl ether, and still more preferably a diol monoalkyl ether.

Specific examples of the high-viscosity liquid medium include ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

The present composition (1) may further comprise a polymer or resin other than the F polymer. Wherein the present composition (1) may be contained in a portion other than the particles constituting the present powder. The polymer or resin other than the F polymer in the present composition (1) may be dissolved in a liquid medium, may be contained as particles similar to the inorganic filler without being dissolved, or may be contained as particles swollen with a liquid medium.

And the present composition (2) comprises a polar polymer or a precursor thereof which is a polymer or a resin other than the F polymer.

Hereinafter, the polymer or resin other than the F polymer which may be contained in the present composition (1) is described first, and then the polar polymer and its precursor which are contained in the present composition (2) are described.

The polymer or resin other than the F polymer refers to a polymer or a precursor thereof (refers to a low molecular compound or oligomer which can be a polymer thereof by polymerization or crosslinking, etc.), a combination of 2 or more compounds which can be a polymer by a reaction such as condensation, etc., and the like. For example, resins called thermoplastic resins are generally polymers, and resins called curable resins are generally low-molecular compounds, oligomers, and combinations of low-molecular compounds that react to cure to polymers. Further, those called elastomers or rubbers may be used depending on the physical properties of the polymer. Hereinafter, polymers or resins other than the F polymer are collectively referred to as "other resins".

Examples of the other resin include aromatic polyesters, aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, precursors of aromatic polyamideimides, epoxy resins, maleimide resins, polyurethane resins, thermoplastic elastomers, polyamideimides, polyphenylene oxides, polyphenylene ethers, liquid crystal polyesters, polysaccharides, nylons, acrylic resins, methacrylic resins, butyrals, cyanate resins, ABR rubbers, celluloses, PVA acrylic methacrylic acid, polyalkylene ethers, polyoxyethylene alkyl ethers, and fluoropolymers other than F polymers.

As the other resin, aromatic polyesters, aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, precursors of aromatic polyamideimides, polyphenylene oxides, epoxy resins, maleimide resins, and thermoplastic elastomers are preferable. The aromatic polyimide may be thermoplastic or thermosetting.

As a specific example of the aromatic polyimide, examples thereof include "Neopulim (registered trademark)" series (Mitsubishi gas Chemicals, mitsubishi Chemie) "," SPIXARA (registered trademark) "series (Somadder Corp.)," Q-PILON (registered trademark) "series (Pi technical institute, inc.),)" WINGO "series (manufactured by WINGO technology Co., ltd.)," Tohmide (registered trademark) "series (manufactured by Kagaku Dikka Co., ltd.)," KPI-MX "series (manufactured by Hecun industry Co., ltd.)," UPIA (registered trademark) -AT "series (manufactured by Yu Kong Xing Co., ltd.)," manufactured by Yu Kong Co., ltd.), "and" Di Kong Co., ltd. ".

Specific examples of the aromatic polyamideimide and the precursor of the aromatic polyamideimide include "HPC-1000" and "HPC-2100D" (both made by Showa electric materials Co., ltd.).

Examples of the styrene elastomer include styrene-butadiene copolymers, hydrogenated styrene-isoprene copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated styrene-butadiene-styrene block copolymers, and hydrogenated styrene-isoprene-styrene block copolymers.

The urethane resin may be, for example, urethane fine particles containing an acrylic component, and may be a homopolymer or a copolymer. Specifically, commercially available DYMIC bead CM (dyi C M) (manufactured by dayc chemical industry Co., ltd.), ART PEARL (manufactured by root industry Co., ltd.), and GRANPEARL (manufactured by liku industry Co., ltd.).

Examples of polysaccharides include glycogen, amylose, agarose, pullulan, cellulose, dextrin, dextran, 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, aspergillus niger polysaccharide, hyaluronic acid, auricularia auricular, gloiopeltis, pectin, laver polysaccharide, laminarin, lichenin, carrageenan, alginic acid, tragacanth gum, alkali gum, locust bean gum.

Examples of the acrylic resin and the methacrylic resin include polyacrylate, polymethacrylate, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, and ethylene-vinyl acetate copolymer.

Examples of the acrylic resin and methacrylic resin include the Neocryl series manufactured by phoebe chemical company (phoebe chemical company), which are commercially available products.

Nylon 6, nylon 11, and nylon 12 are examples of nylon.

Examples of the commercial products of the butyral resins include S-LEC (registered trademark) B series, K (KS) series, SV series, and MOWITAL (registered trademark) series, which are manufactured by kuraray corporation, of the water chemical industry corporation.

Examples of the cyanate ester resin include 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 novolac cyanate resin.

Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, t-butyl catechol type epoxy resin, naphthalene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, and halogenated epoxy resin.

Examples of the commercial products of the thermoplastic elastomer include TR series (styrene-butadiene thermoplastic elastomer, JSR corporation), RB series (polybutadiene thermoplastic elastomer, JSR corporation), JSR EXCELINK (olefin thermoplastic elastomer, JSR corporation), DYNARON series (hydrogenated thermoplastic elastomer, JSR corporation), THERMORUN series (registered trademark) (olefin thermoplastic elastomer, mitsubishi chemical corporation), ESPOLEX TPE series (olefin thermoplastic elastomer, resident chemical corporation), SEPTON series (registered trademark) (hydrogenated styrene thermoplastic elastomer, koshi corporation), tafetec series (registered trademark) (hydrogenated styrene thermoplastic elastomer, asahi chemical corporation).

Examples of the fluorine-containing polymer other than the F polymer include polyvinyl fluoride, polyvinylidene fluoride, and polychlorotrifluoroethylene.

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

The polar polymer in the present composition (2) is a polymer having a polar functional group in the main chain or side chain of the polymer, and the precursor of the polar polymer is a precursor of the polar polymer which can be polymerized by heating or the like. The polar functional group is typically a heteroatom or heteroatom-containing radical. Examples of the hetero atom include 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.

Examples of the polymer having a polar functional group in the main chain include polymers having an ether bond, an ester bond, an amide bond, an imide bond, a thioether bond, or a disulfide bond in the main chain.

Examples of the polar functional group in the polymer having a polar functional group in a side chain of the polymer include the carbonyl group-containing group, the hydroxyl group-containing group, a mercapto group, a thioether group, a sulfonyl group, a sulfonyloxy group, an amino group, an amide group, and the like, and preferably a carbonyl group-containing group and a hydroxyl group-containing group. In this case, the interaction of the F polymer with the polar polymer (or its precursor) and the liquid medium is easily promoted, and the above mechanism of action is easily and remarkably exhibited.

The molecular weight of the polar polymer and its precursor is preferably 3000 or more, more preferably 5000 or more, and still more preferably 10000 or more. The molecular weight of the polar polymer and its precursor is preferably 50000 or less, more preferably 30000 or less. In this case, the polar polymer and its precursor easily interact with the F polymer and the liquid polar medium, and the present composition (2) is easily excellent in physical properties such as dispersion stability.

The polar polymer and its precursor are preferably dissolved in a liquid polar medium.

As the polar polymer, there may be mentioned: ether polymers such as polyacetal, polyalkylene glycol, polyether ketone, polyether ether ketone, polyether sulfone, ester polymers such as polyalkylene terephthalate and polyalkylene naphthalate, amide polymers such as nylon and aramid; imide polymers such as polyimide and polyamideimide, thioether polymers such as polythiol, polythioether and polydisulfide, sulfone polymers such as polyethersulfone and polyphenylsulfone, polyvinyl alcohol, polyacrylate, polymethacrylate, polyvinylpyrrolidone, polyvinyl acetate, carboxyvinyl polymer, polyvinyl halide other than F polymer, vinyl polymers such as polyvinylidene halide, polysaccharides and precursors thereof. The polar polymer may be a polymer obtained by introducing the polar functional group into a polyolefin. The polysaccharide may be a polysaccharide as exemplified as the other resin.

These polar polymers may be copolymers composed of a plurality of monomers.

As the polar polymer and the precursor thereof, imide-based polymers, imide-based polymer precursors, ethylene-based polymers, and polysaccharides are preferable.

Preferred imide polymers and their precursors include polyimide, polyamideimide, polyamic acid, and polyamideimide precursors, and more preferred are aromatic polyimide, aromatic polyamideimide, aromatic polyamic acid, and aromatic polyamideimide precursors.

Specific examples of the imide-based polymer include "Neoprim (registered trademark)" series (manufactured by Mitsubishi gas chemical Co., ltd.), "SPIXARA (registered trademark)" series (manufactured by Soulong corporation), "Q-PILON (registered trademark)" series (manufactured by PI technical research), "WINGO" series (manufactured by WINGO technology Co., ltd.), "Tohmide (registered trademark)" series (manufactured by Hevilla industry Co., ltd.), "UPIA (registered trademark) -AT" series (manufactured by Yu Kogyo Co., ltd.), "HPC-1000", "HPC-2100D" (manufactured by Showa electric materials Co., ltd.).

Preferable examples of the vinyl polymer include vinyl alcohol polymers such as polyvinyl alcohol, vinyl pyrrolidone polymers such as polyvinylpyrrolidone, acrylic polymers such as polyacrylic acid, and carboxyvinyl polymers such as carboxyvinyl polymer, and more preferable examples thereof.

As the vinyl alcohol polymer, polyvinyl alcohol, polyvinyl acetate, a partial acylate of polyvinyl alcohol, a partial acetal of polyvinyl alcohol, a copolymer of vinyl alcohol and vinyl butyral and vinyl acetate are preferable.

Specific examples of the vinyl alcohol polymer include "S-LEC (registered trademark) B" series, "S-LEC (registered trademark) K (KS)" series, "S-LEC (registered trademark) SV" series (manufactured by Nikka chemical Co., ltd., "MOWITAL (registered trademark)" series (manufactured by Coley Co., ltd.).

Examples of the acrylic polymer include polyacrylic acid, polymethyl acrylate, polyacrylic acid ethyl ester and other polyacrylates, poly- α -halogenated acrylate, poly- α -cyanoacrylate, polyacrylamide, and sodium polyacrylate.

Among the polysaccharides, preferred are glycogen, amylose, agarose, amylopectin, cellulose, dextrin, dextran, levan, and chitin. As the cellulose, carboxymethyl cellulose is preferable. The carboxymethyl cellulose may be carboxymethyl cellulose salt such as sodium carboxymethyl cellulose and ammonium carboxymethyl cellulose.

When the present composition contains a resin other than the F polymer, the resin other than the F polymer is preferably dissolved in a liquid medium or swelled by the liquid medium, and particularly preferably the polar polymer or a precursor thereof is dissolved in the liquid medium.

The other resin which is insoluble in the liquid medium is preferably contained in the present composition as the same particles as those of the inorganic filler described below. As the particles similar to those of the inorganic filler, particles composed of a cured product of a curable resin are preferable.

The present composition may also comprise particles of an inorganic filler.

The inorganic filler is used to improve the physical properties of the obtained coating film or molded article when the present composition or the dispersion 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.

For example, in the case of improving the dielectric constant of a coating film or a molded article, a perovskite type ferroelectric filler and a bismuth layered perovskite type ferroelectric filler are preferable as the inorganic filler.

Examples of the perovskite type ferroelectric material include barium titanate, lead zirconate titanate, lead titanate, zirconium oxide, and titanium oxide. Examples of the bismuth layered perovskite type ferroelectric material include bismuth strontium tantalate, bismuth strontium niobate, and bismuth titanate.

For example, in the case of lowering the dielectric constant and dielectric loss tangent or linear expansion coefficient of a coating film or a molded article, a low dielectric constant, low dielectric loss tangent or low linear expansion coefficient inorganic filler is used as the inorganic filler.

The inorganic filler is preferably a boron nitride filler, a beryllium oxide filler (beryllium oxide filler), a silicon oxide filler (silica filler), a wollastonite filler, or a magnesium metasilicate filler (steatite filler).

For example, in the case of improving the thermal conductivity or scratch resistance of a coating film or a molded article, a filler of a metal oxide can be used as the inorganic filler.

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

As the inorganic filler other than this, a glass fiber filler or a carbon filler may be used.

As the CARBON filler, CARBON FIBER (CARBON FIBER), CARBON black, graphene oxide, fullerene, graphite, and graphite oxide can be cited. Examples of the carbon fibers include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, vapor grown carbon fibers, and carbon nanotubes (single-wall, double-wall, multi-wall, cup-stacked, and the like).

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

The shape of the inorganic filler particles (i.e., particles constituting the inorganic filler) is appropriately selected according to the purpose, and may be either bulk particles or fibrous particles. When a filler composed of block particles is used, the surface flatness of the coating film or the molded article is improved, the surface slidability thereof is improved, and the scratch resistance is easily improved. On the other hand, when an inorganic filler composed of fibrous particles is used, a part of the filler particles is exposed from the surface of the coating film or the molded article, and for example, the abrasion resistance and scratch resistance of the product surface are easily improved.

In the case of an inorganic filler composed of bulk particles, the average particle diameter (D50) thereof is preferably 0.02 to 200. Mu.m. In the case of an inorganic filler composed of fibrous particles, the average fiber length is preferably 0.05 to 300. Mu.m. The average fiber diameter of the fibrous inorganic filler is preferably 0.01 to 15. Mu.m. In addition to the above-described shape, the particles constituting the inorganic filler may have various shapes such as a plate shape, a hollow shape, and a honeycomb shape.

The inorganic filler particles are preferably surface-treated at least in part on the surface thereof.

The inorganic filler is preferably composed of inorganic filler particles surface-treated with a silane coupling agent. The inorganic filler has excellent affinity with the present powder, and the dispersibility of the present dispersion liquid is easily improved.

As the silane coupling agent, 3-aminopropyl triethoxysilane, vinyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane and 3-isocyanatopropyl triethoxysilane are preferred.

As a preferable specific example of the inorganic filler, examples thereof include "admafin" (registered trademark) series made by ya Dou Ma corporation, admafin (registered trademark) series made by ya Dou Ma corporation, zinc oxide filler surface-treated with an ester such as propylene glycol dicaprate (FINEX (registered trademark) series made by Kagaku chemical industry Co., ltd., a company, etc.), a metal oxide film, a metal oxide, a metal nitride, a metal, etc., and the "made of" and the admetal (and admetal (self to "and admetal to" and adto "admetal spherical fused silica fillers (SFP (registered trademark) series, etc. made by Kagaku Co., ltd.), zinc oxide fillers (TIPAQUE (registered trademark) series, etc. made by Shichen Co., ltd. (Dan Yuan K.K.), which have been coated with a polyhydric alcohol and an inorganic substance, etc.) spherical fused silica filler (SFP (registered trademark) series, etc. made by Dendron Co., ltd.), a resin composition a zinc oxide filler coated with a polyhydric alcohol and an inorganic substance (TIPAQUE (registered trademark) series, etc. made by Shi Yuan Kagaku Co., ltd. (Dan Yuan, available from Shi Yuan Co., ltd.)) Talcum filler (BST series, etc. manufactured by Japanese Talcum Co., ltd., boron nitride filler (UHP series, HGP series, GP series, etc. manufactured by Showa electric Co., ltd.).

Further, the present composition may contain components other than the present powder particles, the liquid medium, the other resin and the inorganic filler. As examples of other components, surfactants are exemplified from the viewpoint of improving dispersion stability and handleability.

The surfactant is preferably a nonionic surfactant.

The hydrophilic part of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.

The oxyalkylene group may be composed of 1 kind or 2 or more kinds. In the latter case, the different kinds of oxyalkylene groups may be arranged in a random form or may be arranged in a block form.

As the oxyalkylene group, an oxyethylene group is preferable.

The hydrophobic portion 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 acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.

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

Specific examples of the surfactant include "FTERGENT" series (made by nikoku corporation), the "SURFLON" series (made by AGC bang corporation), the "MEGAFACE" series (made by DIC corporation), the "UNIDYNE" series (made by DIC corporation), the "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", the "BYK-3456" (made by dyke chemical japan corporation), the "KF-6011", the "KF-6043" series (made by singe chemical industry corporation), the "teku" series (made by singe chemical industry corporation), and the "teku-100", respectively.

In the case where the present composition contains a surfactant (except for a surfactant which is attached to the inorganic filler in the case of an inorganic filler which has been previously treated with a surfactant), the content thereof in the present dispersion obtained by diluting the present composition with the 2 nd liquid medium is preferably 1 to 15% by mass. In this case, the affinity between the components increases, and the dispersion stability of the present dispersion is more likely to be improved.

In addition to the above components, the present composition may further contain additives such as thixotropic agents, viscosity modifiers, antifoaming agents, silane coupling agents, dehydrating agents, plasticizers, weather-proofing agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface-treating agents, flame retardants, various organic fillers, and the like.

The composition (1) contains particles derived from an F polymer powder, a liquid medium, a solid content concentration of 40 mass% or more, and a viscosity of 8000-100000 mPas measured by a B-type viscometer. The present composition (1) is a pasty, pasty or gel-like composition, preferably a high viscosity composition called a gel.

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

The viscosity of the present composition (1) is preferably 10000 mPas or more as measured by a B-type viscometer. The viscosity is preferably 80000 mPas or less, more preferably 40000 mPas or less, and even more preferably 20000 mPas or less.

The liquid medium in the present composition (1) is preferably a low-viscosity liquid medium, and in addition, the present composition (1) may contain 2 or more liquid media.

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

The foam volume ratio of the present composition (1) is preferably 10% or less.

The foam volume ratio is determined as the volume (V) of the present composition (1) at standard atmospheric pressure and 20 DEG C _N ) And the volume of bubbles added when it was depressurized to 0.003MPa (V _V ) And a value obtained by the following calculation formula.

Foam volume ratio [%]＝100×(V _V -V _N )/V _N

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

When the present composition (1) is prepared by this method, the foam volume ratio can be made within the above range.

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 mass% or less, more preferably 25 mass% or less. Thus, each of the particles constituting the present powder is always kneaded with the liquid medium in a state of being in contact with the liquid medium, and the present powder particles and the liquid medium are uniformly mixed.

The concentration of the solid content of the present composition (1) can be made within the above range by appropriately setting the amounts of the F polymer and the liquid medium. When other resin or inorganic filler is contained, the solid content concentration in the present composition (1) can be set within the above range by the same appropriate setting.

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

When the present composition (1) contains another resin, the mass ratio of the present powder particles to the other resin is preferably a ratio of 1 mass of the present powder particles to 0.01 to 0.5 mass of the other resin, more preferably a ratio of 0.1 to 0.3 mass.

When the present composition (1) contains an inorganic filler, the content of the inorganic filler in the solid content is preferably 25 mass% or more, more preferably 50 mass% or more. The inorganic filler is preferably 75 mass% or less, more preferably 60 mass% or less.

The foam volume ratio of the dispersion liquid obtained by diluting the present composition (1) with the 2 nd liquid medium is easily within the same range as that of the present composition (1). Therefore, the decrease in uniformity of the component distribution and voids of the coating film or molded article obtained from the dispersion can be suppressed.

The composition (2) comprises particles derived from F polymer powder, a polar polymer or a precursor thereof, and a liquid polar medium, and has a viscosity of 10000 to 100000 Pa.s as measured by capillary rheometry. The present composition (2) is preferably a high-viscosity composition called wet powder.

The present composition (2) may further contain other components such as an inorganic filler and a surfactant.

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

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

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, with the content of the present powder particles being 1. The ratio is more preferably 0.005 or more, and still more preferably 0.01 or more. Further, the ratio is more preferably 0.25 or less, and still more preferably less than 0.1.

The viscosity of the composition (2) obtained by capillary rheometry is more preferably 15000 Pa.s or more. The viscosity of the present composition (2) is more preferably 50000pa·s or less, and still more preferably 30000pa·s or less.

The present composition (2) having the viscosity obtained by capillary rheometry in this range is in the form of a lump or clay-like composition called wet powder among compositions containing present powder particles wetted with a liquid polar medium in which a polar polymer (or a precursor thereof) is sufficiently dissolved. 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 a 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 connected to each other with the liquid polar medium in which the polar polymer (or a precursor thereof) is dissolved in the particle gaps thereof.

In addition, the present composition (2) preferably further comprises a surfactant.

Specifically, the composition (2) may include a specific composition derived from a specific surface area of 25m ² Particles of the F polymer powder containing carbonyl group or hydroxyl group, a polar polymer containing carbonyl group or hydroxyl group or a precursor thereof, and a liquid polar medium selected from at least 1 of amide, ketone and ester.

The solid content concentration of the present composition (2) is preferably more than 50 mass%, more preferably 60 mass% or more. The solid content concentration is preferably 99 mass% or less, more preferably 95 mass% or less. In this case, the present composition (2) is excellent in dispersibility in the 2 nd liquid medium, and the dispersion stability of the obtained dispersion is excellent.

The solid content in the present composition (2) means the total amount of solid-forming substances in a coating film or a molded article formed from the present composition (2) or the obtained dispersion. 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 in the present composition (2).

When the present composition (2) contains an inorganic filler, the mass ratio of the inorganic filler to the present powder particles is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably 0.7 to 1.

In the present composition (2), the content of the present powder particles in the solid content is preferably 25 mass% or more, more preferably 30 mass% or more. The content of the present powder particles is preferably 60 mass% or less, more preferably 50 mass% or less.

When the present composition (2) contains an inorganic filler, the content of the inorganic filler in the solid content is preferably 10 mass% or more, more preferably 25 mass% or more. The content of the inorganic filler is preferably 75 mass% or less, more preferably 60 mass% or less.

Since the F polymer is a polymer having a low surface tension and rigidity, the F polymer particles are easily aggregated with each other in a dispersion liquid in which the F polymer powder is dispersed in a liquid dispersion medium. Therefore, it is difficult to obtain a dispersion excellent in processability and dispersion stability. In a method of mixing the F polymer powder with the dispersion medium by applying shear, which is generally performed to improve dispersibility, foaming may be intensified at the time of preparing the dispersion, and the dispersion stability may be lowered by coagulation.

Further, due to the characteristics of the F polymer, the present powder is less likely to interact with other components in a dispersion containing powder particles thereof and other components. Therefore, in the method of mixing the two in the dispersion medium by applying shear, the interaction between the components is not necessarily improved, and the F polymer particles are aggregated, so that it is difficult to form a dense and uniform dispersion. This tendency is particularly pronounced in the case of homogeneous dispersions which are to be obtained by mixing the F polymer with the polar polymer.

In the present invention, by using the present composition, wetting of the present powder and interaction between components can be promoted, and a dispersion liquid free from the above problems can be obtained.

In addition, in the present composition (2), the polar polymer interacts with a liquid polar medium that also has polarity, at least a portion of which is dissolved. As a result, it is considered that the degree of freedom of molecular movement of the polar polymer increases, and interaction between the polar polymer and the present powder particles is promoted. Further, by this, it is considered that the interaction of the liquid polar medium dissolving the polar polymer and the present powder particles is also promoted, and the present powder particles become easily wetted. As a result, the present composition (2) is considered to be a composition having three components densely and uniformly mixed in a predetermined viscosity range.

Since the present powder particles, the polar polymer and the liquid polar medium highly interact in the present composition (2), it is considered that the dispersion stability of the dispersion liquid of the present composition (2) diluted with the 2 nd polar solvent is also improved.

Like the present composition (1), the present composition (2) is also preferably obtained by kneading a mixture comprising the F polymer powder and the liquid polar medium, and at least one of degassing during or after the kneading and standing after the kneading.

The present invention also includes a method for producing the present composition by kneading a mixture containing the present powder and a liquid medium (hereinafter also referred to as "present mixture"), and at least one of deaeration during or after the kneading and standing after the kneading. The present composition (2) can be produced by this method by using a polar polymer together with the present powder and using a liquid polar medium as a liquid medium.

The deaeration of the kneaded material during or after kneading promotes the effective removal of gases such as air present in the particle gaps of the present powder or the atmosphere gas carried in the preparation of the present composition, thereby improving the wettability of the present powder particles. Further, the standing of the kneaded material after kneading promotes penetration of the liquid medium between the powder particles, thereby promoting wetting of the powder particles.

It is preferable to perform both of the above-described degassing and standing.

The present mixture in the kneader may be obtained by introducing the present mixture obtained by mixing the components outside the kneader into the kneader, or may be obtained by introducing the mixture of the components or a part thereof into the kneader. In addition, a part of each component may be introduced into a kneader during kneading of each component. For example, a liquid medium may be further added to the kneaded material (including a liquid medium) during kneading.

In addition, a solution of a polar polymer dissolved in a liquid polar medium is preferably used to form the present mixture. Further, a liquid component such as a liquid medium is preferably used after deaeration before forming the present mixture.

In kneading the present mixture, it is preferable to knead the mixture so that the mass of the mixture does not substantially change, and it is preferable to knead the mixture in a closed system. In other words, it is preferable to conduct kneading so that the liquid components of the present mixture do not evaporate during kneading.

In kneading, a kneader having a stirring tank and one or more stirring blades is preferably used. In order to obtain a high kneading effect, the number of stirring blades is preferably two or more. The kneading method may be either batch type or continuous type.

The kneading machine used for batch kneading is preferably a henschel mixer, a pressure kneader, a banbury mixer, a rotation revolution mixer or a planetary mixer, and more preferably a planetary mixer. The planetary mixer has a structure in which mixing blades having 2 shafts rotating and revolving with each other are provided to mix the kneaded material in the mixing tank. Therefore, the dead angle which the stirring blade cannot reach in the stirring tank is less. The shape of the blade may be thickened to apply a high load, but may also be used as a conventional stirrer in which the stirring blade rotates in a stirring tank. Therefore, the dead angle of the stirring blade in the stirring tank is small, and the load of the blade can be reduced, so that the mixture can be highly kneaded.

The kneading of the present mixture is preferably performed while cooling. In this case, vaporization of the liquid medium is suppressed, the present mixture becomes viscous, and a load is applied to the stirring blade of the kneader, so that a shearing force on the present mixture increases. In particular, in the case of using a plurality of stirring blades, shearing force is more easily applied to the material between the stirring blades or between the stirring blades and the stirring tank. As a result, in the case where the present powder contains agglomerates of the F polymer particles, deagglomeration of the agglomerates proceeds efficiently, and the present powder is sufficiently mixed with the liquid medium.

The temperature of kneading is preferably not higher than the boiling point of the liquid medium, and preferably not higher than 30 ℃. The temperature of kneading is preferably 0℃or higher, more preferably 10℃or higher.

The kneading for obtaining the present composition (2) is preferably carried out at a temperature of 25℃and a shear rate of 1s ^-1 The measurement of the capillary rheology was performed until the viscosity fluctuation range of the kneaded material was + -5% or less. The fluctuation range is more preferably + -3% or less.

The range of viscosity fluctuation can be confirmed by sampling the kneaded material from the kneader at 10 minute intervals while kneading, and measuring the viscosity by capillary rheometry at the upper limit. The viscosity measured at the nth time is denoted as eta _n The viscosity measured at the (n+1) th time is denoted as eta _n+1 In this case, the nth fluctuation range r is obtained by the following formula (1) _n The above range is repeated 3 times.

(η _n+1 /η _n )×100＝r _n (1)

Since the load applied to the stirring blade decreases as the kneading proceeds, the consumed current of the kneader decreases, and thus the end point of kneading can be determined by monitoring the consumed current.

Further, the kneading may be controlled by using a value obtained by dividing the load current of the kneader by the shear rate of the kneader as the force and energy applied to the kneaded material. Specifically, it is preferable to increase the load current from the start of kneading and gradually decrease it.

As the continuous kneading machine, a biaxial extrusion kneading machine or a stone mill type kneading machine can be mentioned.

A twin screw extrusion kneader is a twin screw continuous kneader for kneading an object to be kneaded by shearing force between two screws arranged in parallel and in close proximity, for example.

The stone mill type kneading machine is a kneading machine having, for example, a cylindrical fixed portion having an internal space through which an object to be kneaded can pass, and a rotating portion disposed in the internal space of the fixed portion and configured to continuously knead the object to be kneaded passing through the internal space by rotating the rotating portion while conveying the object in a direction of a rotation axis.

The deaeration may be performed during the kneading, may be performed after the kneading, or may be performed alternately with the kneading a plurality of times. The degassing may be carried out continuously or batchwise.

The degassing is preferably carried out in such a way that the mass of the mixture does not substantially change. Examples of the method of deaeration include a method of bringing the liquid composition into a reduced pressure state, a method of bringing the liquid composition into a heated state, a method of freezing the liquid composition, a method of irradiating the present mixture with ultrasonic waves, and a method of combining these methods. Among these methods, the method of bringing the present mixture into a reduced pressure state or the method of bringing the present mixture into a heated state is preferable because of easiness of handling, and the method of combining both is more preferable from the viewpoint of degassing efficiency. Further, as described above, it is particularly preferable to perform cooling.

When the present mixture is subjected to reduced pressure or heated, the temperature and pressure at the time of deaeration are appropriately set according to the present mixture in the liquid composition, and the pressure and temperature at which the present mixture does not boil are selected. For example, a pressure of about 0Pa to 0.01MPa is preferable, and the temperature is 100℃to 250℃lower than the boiling point of the liquid medium in the present mixture.

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

In the deaeration, stirring or the like may be performed in order to prevent bumping.

The mixing is usually carried out after the mixing. The kneaded mixture after kneading is left to stand in the vessel for a certain period of time. The standing is preferably performed so that the mass of the kneaded material does not substantially change, and is preferably performed in a closed system such as a closed vessel.

The temperature and pressure of the atmosphere in which the kneaded product is left to stand are usually about 10 to 30℃and about 1 atm, and preferably at constant temperature and humidity. In some cases, the powder particles in the kneaded material may be stirred during the standing period to such an extent that the powder particles do not agglomerate and settle.

The time for the standing is preferably 24 hours or more, more preferably 48 hours or more. Since the effect obtained by the long standing time is not greatly changed, the standing time is preferably 168 hours or less.

The viscosity of the kneaded material when left to stand to obtain the present composition (1) is preferably 40000mpa·s or less, more preferably 20000mpa·s or less. The viscosity is preferably 8000 mPas or more. In this case, penetration of the liquid medium into the powder particles is further promoted, and the above mechanism of action is easily enhanced. The viscosity of the kneaded material can be adjusted depending on the temperature thereof or a liquid medium such as a liquid polar medium added to the kneaded material upon standing.

In the present method, either the deaeration or the standing may be performed, but both are preferably performed from the viewpoint of dispersion stability of a dispersion liquid obtained by diluting the present composition.

Examples of the mode of performing both may include: continuously or intermittently degassing the mixture after kneading, and then standing the mixture without degassing; mixing the mixture while continuously or intermittently degassing, and standing the obtained mixed material; mixing the mixture while continuously or intermittently degassing, standing the obtained mixed material, and further degassing after standing; mixing the mixture, standing the mixture while degassing the mixture after mixing the mixture, and standing the mixture without degassing the mixture; the liquid composition is kneaded, allowed to stand after kneading, and continuously or intermittently deaerated after standing. These multiple forms may be combined or one form may be repeated.

By performing at least one of the deaeration and the standing at any stage between the kneading and the mixing, aggregation of the present powder particles can be suppressed, and foaming at the time of mixing the present composition with the 2 nd liquid medium can be suppressed. As a result, the obtained coating film or molded article has excellent surface smoothness.

The present composition is preferably diluted with the 2 nd liquid medium and used as a dispersion of lower viscosity than the present composition. In addition, the present compositions may also be used for other purposes.

The dispersion liquid (hereinafter also referred to as "the present dispersion liquid") obtained by diluting the present composition with the 2 nd liquid medium is suitable for applications such as coating agents and paints.

The 2 nd liquid medium is a liquid medium compatible with the 1 st liquid medium, and may be the same liquid medium as the 1 st liquid medium. The 2 nd liquid medium is a liquid medium in which the insoluble components such as the present powder particles and the inorganic filler in the present composition are not dissolved when the present composition is diluted, and is preferably a liquid medium in which the components dissolved in the 1 st liquid medium are not precipitated. However, in the case where the present composition contains a component whose entire amount is not sufficiently soluble in the 1 st liquid medium because the amount of the 1 st liquid medium is small, for example, in the case where the polar polymer is not in a dissolved state even if swollen in the present composition (2), the state where the entire amount of the component is dissolved can be achieved by dilution with the 2 nd liquid medium. The 2 nd liquid medium is particularly preferably the same liquid medium as the 1 st liquid medium in the diluted present composition.

As the 2 nd liquid medium, there may be mentioned a liquid medium which can be used as the 1 st liquid medium, and among them, a low-viscosity liquid medium is preferable.

When the present composition is mixed with the 2 nd liquid medium for dilution with the 2 nd liquid medium, for example, a dispersing machine is preferably used for mixing from the viewpoints of dispersibility and dispersion stability of the obtained dispersion. Examples of the dispersing machine using the medium include an ultrasonic homogenizer, a ball mill, a pulverizer, a basket mill, a sand mill, a DYNO mill, a DISPERMAT dispersing machine, an SC mill, a nail pulverizer, and a stirring mill. Examples of the dispersing machine that does not use a medium include an ultrasonic homogenizer, a nano homogenizer, a vertical type dispersing machine, a high pressure impact type dispersing machine, a rotation and revolution mixer, and a thin film rotary type high-speed mixer. Among them, a dispersing machine using a medium is preferable because of its high dispersing ability.

Further, since dispersion stability is improved when mixing is performed using an impact type dispersing machine, mixing with the 2 nd liquid medium is preferably performed using an impact type dispersing machine.

The impact type dispersing machine is a dispersing machine which disperses the impact force or the like at the time of impact of a liquid medium pressurized once by a high pressure pump. Impact dispensers can be broadly classified into 2 categories depending on the impact object. That is, the liquid medium is made to collide with each other and the impact object is made to collide with the liquid medium. Examples of the means for causing the liquid media to collide with each other include a nano homogenizer, a plus PY, a super-homogenizer, aqua, and a micro-jet homogenizer. Examples of the method of causing the liquid medium to impact the impact target include a homogenizer and the like.

In addition to mixing by using the above-mentioned dispersing machine, examples of the method of mixing the present composition with the 2 nd liquid medium include a method of mixing the present composition with the 2 nd liquid medium in a mixer having a stirring tank and stirring blades for the above-mentioned kneading, a method of mixing the present composition with the 2 nd liquid medium by a different mixer, and the like. The mixer may be the same disperser as the batch mixer or the continuous mixer.

In the production of the present dispersion, other resins, inorganic fillers, surfactants, and the like may be added as necessary. In the case where both the other resin and the inorganic filler are added, the other resin and the inorganic filler may be added separately or together, or a master batch obtained by mixing the other resin and the inorganic filler may be prepared in advance and then the master batch may be added.

The solid content concentration in the present dispersion is preferably 40% by mass or more, more preferably 50% by mass or more. From the viewpoint of dispersibility of the present dispersion liquid, the solid content concentration is preferably 90 mass% or less, more preferably 75 mass% or less. The solid content of the dispersion means a component of the dispersion from which all the liquid medium is removed, and generally means the total amount of a substance forming a solid content in a coating film or a molded article formed from the dispersion.

From the viewpoint of dispersion stability of the dispersion liquid, the content of the powder particles in the dispersion liquid is preferably 20 mass% or more, more preferably 30 mass% or more, based on the amount of the solid component. The content of the present powder particles is preferably 70 mass% or less, more preferably 50 mass% or less.

The viscosity of the dispersion liquid measured by a B-type viscometer is preferably 50 mPas or more, more preferably 75 mPas or more, and still more preferably 100 mPas or more. The viscosity is preferably less than 8000 mPas, more preferably 5000 mPas or less, and even more preferably 1000 mPas or less. The dispersion having this viscosity is excellent in coatability.

The thixotropic ratio of the present dispersion is preferably 1 to 10.

From the viewpoint of a decrease in the uniformity of the component distribution of the coating film or the formed article obtained from the present dispersion or void suppression, the foam volume ratio in the dispersion is preferably less than 10%, more preferably less than 5%. The foam volume ratio is preferably 0% or more.

By the above mechanism of action, a dispersion excellent in the physical properties of the liquid can be easily obtained by the present method.

When the dispersion is applied to the surface of a substrate and heated to form a layer made of an F polymer (hereinafter also referred to as "F layer"), a laminate having the substrate and the F layer can be produced. The dispersion may be further left to stand when it is used.

Examples of suitable forms of the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof.

The metal foil of the metal-clad laminate is preferably copper foil. The metal-clad laminate is particularly useful as a printed substrate material.

The resin film of the multilayer film is preferably a polyimide film. The multilayer film can be used as wire coating material or printed circuit board material.

In the production of the laminate, the F layer may be formed on at least one surface of the substrate, and the F layer may be formed on only one surface of the substrate, or may be formed on both surfaces of the substrate. The surface of the substrate may be surface-treated with a silane coupling agent or the like. In the application of the dispersion, coating methods such as spray coating, roll coating, spin coating, gravure coating, micro gravure coating, doctor blading, touch coating, bar coating, die coating, jet meyer rod coating, slit die coating, and dip coating may be used.

The F layer is preferably formed by removing the liquid medium from the dispersion by heating and then firing the polymer by heating. The removal temperature of the liquid medium is preferably as low as possible, preferably a temperature 50 to 150 ℃ 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 ℃, it is preferably heated at 180℃or less, preferably 100 to 150 ℃. Purge air is preferred in the step of removing the liquid medium.

After removal of the liquid medium, the substrate is preferably heated to a temperature region where the polymer is fired to form, preferably the polymer is fired, for example, in the range of 300 to 400 ℃. The F layer preferably comprises a fired product of F polymer.

The F layer is formed by the steps of coating, drying and firing the dispersion. These steps may be performed 1 time or 2 or more times. For example, the step of forming a film by applying the dispersion on the surface of a substrate and heating to remove the liquid medium may be repeated 2 times, and the film having an increased thickness may be heated to sinter the F polymer, thereby forming the F layer. The step of applying and drying the dispersion may be performed 2 times or more from the viewpoint of easily obtaining a thick F layer excellent in smoothness.

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. Mu.m. Within this range, an F layer excellent in crack resistance can be easily formed. The peel strength of the F layer to the base material layer is preferably 10N/cm or more, more preferably 15N/cm or more. The peel strength is preferably 100N/cm or less. When the dispersion liquid is used, the physical properties of the F polymer in the F layer are not impaired, and the laminate can be easily formed.

The void ratio of the F layer is preferably 5% or less, more preferably 4% or less. The void ratio is preferably 0.01% or more, more preferably 0.1% or more. The void ratio is the area ratio (%) of the void portion in the cross section of the coating film or the molded article observed by a Scanning Electron Microscope (SEM).

Examples of the material of the base material include a metal substrate (metal foil such as copper, nickel, aluminum, titanium, or an alloy thereof), a resin film (film of polyimide, polyacrylate, polysulfone, polyarylsulfone, polyamide, polyether amide, polyphenylene sulfide, polyaryletherketone, polyamide imide, liquid crystalline polyester, or liquid crystalline polyester amide), a prepreg (precursor of a fiber-reinforced resin substrate), a ceramic substrate, and a glass substrate. The shape of the substrate may be a planar shape, a curved shape, or a concave-convex shape, and may be any of a foil shape, a plate shape, a film shape, and a fiber shape.

The ten-point average roughness of the substrate surface is preferably 0.01 to 0.05. Mu.m.

Examples of suitable forms of the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof.

The metal foil of the metal-clad laminate is preferably copper foil. The metal laminate is particularly useful as a printed substrate material.

The resin film of the multilayer film is preferably a polyimide film. The multilayer film can be used as wire coating material or printed circuit board material.

Specific examples of the polyimide film include "Kapton 50EN-S" (manufactured by dolpont corporation, by lodydupont corporation), "Kapton100 EN" (manufactured by dolpont corporation), "Kapton 100H" (manufactured by dolpont corporation), "Kapton100 KJ" (manufactured by dolpont corporation), and "Kapton100 JP" (manufactured by dolpont corporation, miyao corporation), and "Kapton100LK" (manufactured by dolpont corporation, east).

The printed board includes a flexible printed board and a rigid printed board.

The side of the F layer opposite the substrate may be further laminated with other substrates to form a multilayer laminate. Lamination may be performed by, for example, thermocompression bonding.

Examples of the structure of the multilayer laminate include 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. Glass cloth or filler may also be included in each layer.

The laminate is useful as antenna parts, printed boards, aircraft parts, automotive parts, sports equipment, food industry products, paints, cosmetics, etc., and is particularly useful as: wire coating materials such as electric wires for aircraft, electrically insulating tapes, insulating tapes for oil drilling, materials for printed circuit boards, separation membranes such as microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, electrode adhesives such as lithium secondary batteries, fuel cells, etc., copy rolls, furniture, covers for motor vehicle dashboards, household appliances, etc., sliding members such as load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, food conveyor belts, etc., tools such as spades, files, awls, saws, etc., boilers, hoppers, pipes, ovens, baking molds, chute, molds, toilets, container coating materials, and demolding films.

When the dispersion liquid is impregnated into a woven fabric and dried by heating, an impregnated woven fabric in which the F polymer is impregnated into the woven fabric can be obtained. The impregnated fabric may be said to be a coated fabric in which the fabric is coated with an F layer. The woven fabric is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric, more preferably a glass fiber woven fabric or a carbon fiber woven fabric. From the viewpoint of improving the adhesion with the F layer, the woven fabric may be treated with a silane coupling agent.

The content of the F polymer in the impregnated fabric is preferably 30 to 80 mass%. Examples of the method of impregnating the dispersion into the fabric include a method of impregnating the fabric with the dispersion and a method of applying the dispersion to the fabric.

The F polymer may be baked after the fabric is dried. The method of firing the F polymer includes a method of passing the woven fabric through a through-air drying oven at 300 to 400 ℃. In addition, the drying of the woven cloth and the firing of the polymer may be performed in one step. The woven fabric thus obtained is excellent in properties such as high adhesion or adhesiveness between the F layer and the woven fabric, high surface smoothness, and less deformation. When the woven fabric is thermally bonded to the metal foil, a metal-clad laminate having high peel strength and less warpage can be obtained, and the metal-clad laminate can be suitably used as a printed board material.

In the production of the impregnated fabric, the fabric impregnated with the dispersion may be arranged by being adhered to the surface of the base material or the like, and dried by heating, thereby forming an impregnated fabric layer containing the F polymer and the fabric, and a laminate in which the base material and the impregnated fabric layer are laminated in this order may be produced. The form is not particularly limited, and for example, when a woven fabric impregnated with the dispersion is disposed 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, a layer of the impregnated woven fabric 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 lining method for the inner wall surface of a member such as a tank, a pipe, or a container.

As described above, the dispersion liquid is excellent in dispersion stability and can be effectively impregnated into a porous or fibrous material. The porous or fibrous material may be a material other than the woven fabric, and specifically, a plate-like, columnar or fibrous material may be used. These materials may be pretreated with a curable resin, a silane coupling agent, or the like, or may be further filled with an inorganic filler, other resin, or the like. In addition, these materials may be twisted into filaments, cables, wires. An interposer made of another polymer such as polyethylene may be disposed during twisting. As a form of producing a molded article by impregnating the material with the dispersion liquid, a form of impregnating a fibrous material carrying a curable resin or a cured product thereof with the dispersion liquid can be mentioned.

The fibrous material may be a high-strength and low-elongation fiber such as a carbon fiber, an aramid fiber, or a silicon carbide fiber. As the curable resin, a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, and a polyurethane resin is preferable. Specific examples of this form include a composite cable formed by impregnating a cable formed by twisting carbon fibers supporting a thermosetting resin with a dispersion liquid and further heating and firing an F polymer. The composite cable can be used as a cable for large structures, ground anchoring, oil excavation, cranes, cableways, elevators, agriculture, forestry, aquatic products and slings.

As described above, by diluting the present composition, the present dispersion liquid excellent in dispersibility and dispersion stability can be obtained. The aggregation of F polymer particles in the dispersion is suppressed, and foaming at the time of production and use of the dispersion is suppressed. As a result, the obtained coating film or molded article has excellent surface smoothness.

The present composition, the method for producing the present composition, and the method for producing the present dispersion from the present composition have been described above, but the present invention is not limited to the configuration of the above embodiment.

For example, in the constitution of the above embodiment, any other step may be added to the composition or the preparation method of the present composition or the present dispersion, and any step having the same function may be substituted for the composition or the preparation method of the present dispersion. The composition and the dispersion liquid according to the present invention may be added to the above-described embodiments, or may be replaced with any composition that exhibits the same function.

Examples

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1

1-1 preparation of the ingredients

[ powder ]

Powder 11: from each 1X 10 unit comprising 97.9 mol%, 0.1 mol%, 2.0 mol% of TFE unit, NAH unit and PPVE unit in this order ⁶ Powder (D50: 2.0 μm, specific surface area: 3 m) composed of 1000 carbonyl group-containing polymers (fluorine content: 76 mass%) having a main chain carbon number ² /g)

Powder 12: every 1X 10 unit consisting of TFE units and PPVE units ⁶ Powder (D50:2.4 μm, specific surface area: 4 m) composed of polymer having 40 carbonyl groups in the main chain carbon number (fluorine content: 76 mass%) ² /g)

[ aromatic Polymer ]

Varnish 1: varnish of thermoplastic aromatic polyimide (PI 1) dissolved in NMP

[ surfactant ]

Surfactant 1: CH (CH) ₂ ＝C(CH ₃ )C(O)OCH ₂ CH ₂ (CF ₂ ) ₆ F and CH ₂ ＝C(CH ₃ )C(O)(OCH ₂ CH ₂ ) ₂₃ OH copolymer having a fluorine content of 35% by mass

[ liquid Medium ]

NMP: n-methyl-2-pyrrolidone

[ viscosity ]

The viscosity in example 1 below refers to the viscosity measured by a type B viscometer at a temperature of 25℃and a rotation speed of 30 rpm.

1-2 preparation of Dispersion

Examples 1 to 1

A liquid composition containing powder 11 (70 parts by mass), PI1 (1.8 parts by mass), surfactant 1 (3.5 parts by mass) and NMP (30 parts by mass) obtained by mixing powder 11, varnish 1, surfactant 1 and NMP was charged into a planetary mixer, the liquid composition was kneaded while maintaining the inside of the planetary mixer under reduced pressure and degassing, and NMP was added to adjust the viscosity to obtain a paste composition 1 having a viscosity of 10000mpa·s. After the composition 1 was allowed to stand at 25℃for 48 hours under atmospheric pressure, NMP was added to the composition 1 in portions so that the total amount of NMP was 70 parts by mass, and the mixture was stirred and mixed to obtain a dispersion 11 having a viscosity of 1000 mPas.

Examples 1-2 to 1-6

Paste compositions 2 to 6 were obtained in the same manner as in example 1-1, except that the powder type, the presence or absence of degassing or standing, and the viscosity at standing (i.e., the presence or absence of additional addition of NMP at the time of producing a paste composition) were changed to those 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 "stationary" in Table 1 represent the stationary time (unit: hr).

The foam volume ratio of the composition 1, the composition 3, the dispersion 11, and the dispersion 13 is 0% or more and less than 5%, and the foam volume ratio of the composition 2, the composition 4, the composition 6, the dispersion 12, the dispersion 14, and the dispersion 16 is more than 5% and less than 10%. The foam volume ratio of the composition 5 and the dispersion 15 is 10% or more.

1-3 evaluation of the Dispersion

The diluted dispersion was sandwiched between 2 pieces of quartz glass, and a light transmission image was observed in a light transmission mode of an optical microscope, and the dispersion state of the powder in the dispersion was evaluated according to the following evaluation criteria. The light-transmitting image shows higher fluidity and dispersibility of the dispersion as the contrast and the moire pattern are not present.

< evaluation criterion >

And (2) the following steps: the light-transmitting image has no contrast and no mesh pattern.

Delta: the light-transmitting image has contrast but no mesh pattern.

X: the light-transmitting image has contrast and a mesh pattern.

TABLE 1

1-4 production examples of laminate

Laminate 1

The dispersion 11 was applied by a bar coating method to the surface of a long copper foil having a thickness of 18 μm to form a wet film. Thereafter, the metal foil having the wet film formed thereon was passed through a drying oven at 110 ℃ for 5 minutes, and dried by heating to obtain a dry film. Thereafter, the dry film was heated at 380℃for 3 minutes in a nitrogen furnace. Thereby, a laminate 11 having a metal foil, and a polymer layer having a thickness of 20 μm as a molded product, which contains a melt-burned product of the powder 11 and PI1 on its surface, was produced.

[ layered bodies 2 to 6]

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

1-5 evaluation of laminate

The obtained laminates 1 to 6 were evaluated for coating unevenness and dielectric loss tangent according to the following criteria.

The results are shown in Table 2.

1-5-1 evaluation of coating unevenness of laminate

< evaluation criterion >

And (2) the following steps: no pits were identified on the surface of the polymer layer, and the surface was also smooth overall.

Delta: the pocks were identified by a portion of the polymer layer, but the surface was smooth overall.

X: the pits are recognized on the whole surface of the polymer layer, and the whole surface is provided with concave-convex.

1-5-2 evaluation of dielectric loss tangent of laminate

For each laminate, copper foil of the laminate was removed by etching with an aqueous ferrous chloride solution to prepare individual polymer layers, and dielectric loss tangent of the polymer layers was measured at a measurement frequency of 10GHz by the SPDR (separation medium resonance) method, and evaluated according to the following criteria.

< evaluation criterion >

O: the dielectric loss tangent of which is less than 0.0010.

Delta: the dielectric loss tangent is not less than 0.0010 and not more than 0.0025.

X: the dielectric loss tangent is more than 0.0025.

TABLE 2

Example 2

2-1 preparation of the ingredients

[ powder ]

Powder 21: each 1X 10 unit comprising 97.9 mol%, 0.1 mol%, 2.0 mol% of TFE unit, NAH unit and PPVE unit in this order ⁶ Powder of a polymer having 1000 carbonyl groups in the main chain carbon number and a melting temperature of 300 ℃ (D50:2.1 μm)

[ polar Polymer ]

Polar polymer 1: aromatic polyimide (U-varnish manufactured by Yu Seisaku Co., ltd.)

Polar polymer 2: carboxymethyl cellulose (manufactured by japan paper corporation (japan manufacturing)

Social) SUNROSE MAC series 200HC

Polar polymer 3: polyvinyl alcohol (S-LEC BL-1 manufactured by Water chemical industry Co., ltd.)

[ inorganic filler ]

Inorganic filler 1: aminosilane coupling agent surface-treated silica filler (D50: 0.2 μm)

[ liquid Medium ]

NMP: n-methyl-2-pyrrolidone

[ viscosity ]

The viscosity of the composition in example 2 below means the shear rate at 25℃for 1s ^-1 The viscosity of the dispersion obtained by capillary rheometry at a temperature of 25℃and a rotation speed of 30rpm was referred to as BViscosity measured by a type viscometer.

2-2. Preparation of composition

[ example 2-1]

The varnish of the polar polymer 1 (solvent: NMP) and NMP were put into a pot and mixed. Further, a powder mixture of the powder 21 and the inorganic filler 1 is charged into a tank and mixed to prepare a mixture. This mixture was kneaded in a planetary mixer and taken out to obtain a composition 21 containing powder 21 (50 parts by mass), inorganic filler 1 (40 parts by mass), polar polymer 1 (10 parts by mass), and NMP (30 parts by mass). Composition 21 is a wet powder in the form of a lump and a clay.

At a temperature of 25℃and a shear rate of 1s ^-1 When the capillary rheology is measured below, the viscosity of the composition 21 is 18000 Pa.s, and the range of viscosity variation is within.+ -. 3% even if the composition 21 is further kneaded.

NMP was added to the composition 21 in portions, and the mixture was stirred while deaerating at 2000rpm by a rotation/revolution stirrer. Further, 80 parts by mass of NMP was added to the composition 21 as a whole while stirring while adding NMP in portions, and a dispersion was prepared to obtain a dispersion 21. The viscosity of the dispersion 21 was 300 mPas.

[ examples 2-2]

A composition 22 and a dispersion 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 is 20000 Pa.s, and the range of variation in the viscosity is within + -3% even if the composition 22 is further kneaded. The viscosity of the dispersion 22 was 400 mPas.

Examples 2 to 3

A composition 23 and a dispersion 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 the range of variation in the viscosity was within.+ -. 3% even if the composition 23 was further kneaded. The viscosity of the dispersion 23 was 400 mPas.

Examples 2 to 4

Composition 24 and dispersion 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 when the composition 24 was further kneaded, the viscosity varied by more than.+ -. 5%. The viscosity of the dispersion 24 was 800 mPas.

Examples 2 to 5

A composition 25 and a 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 mPas.

Examples 2 to 6

A composition 26 and a 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 the range of variation in the viscosity was within.+ -. 3% even if the composition 26 was further kneaded. The viscosity of the dispersion 26 was 3000 mPas.

2-3. Evaluation

2-3-1 evaluation of Dispersion stability of Dispersion

After storing each dispersion in a container at 25℃for a long period of time, the dispersibility was visually confirmed, and the dispersion stability was evaluated according to the following criteria.

[ evaluation criterion ]

And (2) the following steps: no aggregates were identified.

Delta: the adhesion of fine aggregates was recognized at the side wall of the container. If gently stirred, the dispersion was again uniform.

X: agglutinate precipitation was also identified at the bottom of the vessel. The redispersion requires strong shear agitation.

2-3-2 evaluation of thixotropic stability of the Dispersion

The respective dispersions were stored in a container at 25℃for 30 days, and the range of variation in the thixotropic ratio before and after storage was measured, and the thixotropic stability was evaluated according to the following criteria.

[ evaluation criterion ]

O: the absolute value of the fluctuation range of the thixotropic ratio is less than 1

Delta: the absolute value of the fluctuation range of the thixotropic ratio is more than 1 and less than 3

X: the absolute value of the fluctuation range of the thixotropic ratio is more than 3

The evaluation results are summarized in table 3 below.

TABLE 3

	Dispersion stability	Thixotropic stability
			Dispersion 21	○	○
Dispersion 22	○	○
			Dispersion 23	○	○
Dispersion 24	△	△
			Dispersion 25	△	△
Dispersion 26	×	×

Industrial applicability

From the above results, it is clear that the dispersion prepared by the present method is excellent in dispersibility, dispersion stability, and thixotropic stability, and therefore the laminate obtained by using the dispersion obtained by the present method is excellent in uniformity of component distribution and various physical properties.

Further, the entire contents of the specification, claims and abstract of Japanese patent application No. 2021-051437, which are filed by Japanese patent application No. 2020-181771 and Japanese patent application No. 2021-051437 filed by No. 25 and No. 2021-03 are incorporated herein by reference as if set forth in the specification of the present invention.

Claims (15)

1. A composition comprising a material derived from a material having a specific surface area of 25m ² Particles of tetrafluoroethylene polymer powder per gram or less and a liquid medium, wherein the concentration of solid content is 40 mass% or more, and the viscosity of the tetrafluoroethylene polymer powder is 8000 to 100000 mPas measured by a B-type viscometer at a temperature of 25 ℃ and a rotation speed of 30 rpm.

2. The composition of claim 1, further comprising a polymer or resin other than the tetrafluoroethylene-based polymer that is soluble in the liquid medium.

3. A composition comprising a material derived from a material having a specific surface area of 25m ² Particles of tetrafluoroethylene polymer powder of not more than/g, polar polymer or precursor thereof, and polar liquid medium capable of dissolving the polar polymer or precursor thereof, at 25 ℃ and shearing rate of 1s ^-1 The viscosity obtained by the capillary rheometry is 10000-100000 Pa.s.

4. A composition according to claim 3, wherein the total of the content of the particles and the content of 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.

5. The composition according to claim 3 or 4, wherein the polar polymer or a precursor thereof is an imide polymer, a precursor of an imide polymer, an ethylene polymer or a polysaccharide.

6. The composition according to any one of claims 3 to 5, wherein the liquid medium having polarity is a liquid medium selected from the group consisting of water, amides, ketones and esters.

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

8. The composition according to any one of claims 1 to 7, wherein the tetrafluoroethylene polymer has a fluorine content of 70 mass% or more.

9. The composition of any one of claims 1 to 8, wherein the tetrafluoroethylene polymer has a melting temperature of 180 to 325 ℃.

10. The composition according to any one of claims 1 to 9, wherein the particles constituting the tetrafluoroethylene polymer powder have an average particle diameter of 0.1 to 20. Mu.m.

11. The composition of any one of claims 1-10, further comprising an inorganic filler.

12. A method for producing a composition comprising a composition having a specific surface area of 25m ² The composition according to any one of claims 1 to 11 is produced by kneading a mixture of particles of tetrafluoroethylene polymer powder and a liquid medium, and at least one of deaeration during or after the kneading and standing after the kneading.

13. The production method according to claim 12, wherein both of the degassing and the standing are performed.

14. A method of producing a dispersion by diluting the composition of any one of claims 1 to 11 with a 2 nd liquid medium.

15. A wet powder comprising: derived from a specific surface area of 25m ² Particles of tetrafluoroethylene polymer powder having carbonyl group-containing or hydroxyl group-containing, polar polymer having carbonyl group-containing or hydroxyl group-containing or precursor thereof, and liquid medium having polarity selected from at least 1 of amide, ketone and ester.