Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives
  • C08L1/26—Cellulose ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

• the present invention relates to an aqueous dispersion containing particles of a tetrafluoroethylene-based polymer.
• aqueous dispersions have high versatility in the equipment required for their use and high selectivity for substrates to be coated, and improvement of the liquid properties by various additives has been studied.
• Patent Document 1 proposes an aqueous dispersion in which the pH at 25° C. and the solids concentration of the tetrafluoroethylene-based polymer are within a predetermined range, and the metal ion content is less than 100 ppm relative to the entire aqueous dispersion.
• Patent Document 2 proposes a dispersion containing polyvinylidene fluoride particles, a specific nonionic surfactant, a specific polymer surfactant, and a dispersion medium, and in which the contents of sodium ions, potassium ions, and ammonium ions are each equal to or less than a predetermined amount.
• Tetrafluoroethylene-based polymer particles have low water dispersibility, and their aqueous dispersions tend to foam, so that the handling properties of the aqueous dispersions, such as fluidity, are not sufficient.
• a viscosity regulator such as a water-soluble polymer
• the viscosity and thixotropy of the aqueous dispersion can be improved, but there is still room for improvement in terms of suppressing foaming.
• cations contained in the aqueous dispersion have been recognized as components that should be removed as much as possible, as they cause the coloration and decomposition of tetrafluoroethylene-based polymers and cause equipment contamination, as shown in Patent Document 1 or Patent Document 2 and other documents.
• an aqueous dispersion containing a tetrafluoroethylene-based polymer, a specific water-soluble polymer, and water, and in which the concentrations of alkali metal ions and alkaline earth metal ions in the liquid are controlled within a specific range, has excellent dispersion stability, is suppressed from foaming, and is easy to handle.
• a molded product such as a polymer layer formed from such a dispersion has excellent physical properties such as heat resistance and electrical properties (low linear expansion coefficient, low dielectric constant and low dielectric tangent) based on the tetrafluoroethylene-based polymer, and has excellent surface appearance, and have arrived at the present invention.
• An object of the present invention is to provide an aqueous dispersion containing a tetrafluoroethylene polymer, which is excellent in physical properties such as heat resistance and electrical properties (low linear expansion coefficient, low dielectric constant and low dielectric tangent), can form a molded product having excellent surface appearance, and has excellent dispersion stability and handleability.
• An aqueous dispersion comprising particles of a tetrafluoroethylene-based polymer, a water-soluble polymer having at least one polar functional group selected from the group consisting of a vinyl alcohol-based polymer, an acrylic polymer, polyvinylpyrrolidone, polypyrrole, polythiophene, polyethylene oxide, polyethyleneimine, and cellulose ether, and water, wherein the concentration of at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions is 0.1 to 1000 ppm.
• (6) The aqueous dispersion according to any one of (1) to (5), wherein the water-soluble polymer is a vinyl alcohol-based polymer.
• (7) The aqueous dispersion according to any one of (1) to (5), wherein the water-soluble polymer is a cellulose ether.
• a method for producing a laminate comprising placing the aqueous dispersion according to any one of (1) to (14) on a surface of a substrate and heating the surface to form a polymer layer containing the tetrafluoroethylene-based polymer, and obtaining a laminate having a substrate layer constituted by the substrate and the polymer layer in this order.
• the present invention provides an aqueous dispersion with excellent dispersion stability and ease of handling.
• a molded product such as a coating film (polymer layer) can be formed that has excellent physical properties based on the tetrafluoroethylene polymer, such as heat resistance and electrical properties (low linear expansion coefficient, low dielectric constant, and low dielectric tangent), and has excellent surface appearance.
• the "average particle size (D50)" is the volume-based cumulative 50% diameter of a particle or filler determined by a laser diffraction/scattering method. That is, the particle size distribution is measured by a laser diffraction/scattering method, a cumulative curve is calculated with the total volume of the particle group as 100%, and the average particle size (D50) is the particle size at the point on the cumulative curve where the cumulative volume is 50%.
• the D50 of a particle or filler can be determined by dispersing the particles in water and analyzing them by a laser diffraction/scattering method using a laser diffraction/scattering type particle size distribution measuring device (LA-920 measuring device, manufactured by Horiba, Ltd.).
• Average particle size (D90) is the volume-based cumulative 90% diameter of particles, which is determined in the same manner as D50.
• the specific surface area of a particle or filler is a value calculated by measuring the particle by a gas adsorption (constant volume method) BET multipoint method, and is determined using a gas adsorption type pore distribution measuring instrument (product name NOVA4200e, manufactured by Quantachrome Instruments).
• Melting temperature is the temperature corresponding to the maximum of the melting peak of a polymer as measured by differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• glass transition temperature (Tg)” is a value measured by analyzing a polymer using a dynamic mechanical analysis (DMA) method.
• the "viscosity” is determined by measuring the dispersion using a Brookfield viscometer at 25° C. and a rotation speed of 30 rpm. The measurement is repeated three times, and the average value of the three measured values is calculated.
• the "thixotropy ratio” is a value calculated by dividing the viscosity ⁇ 1 of the dispersion measured at a rotation speed of 30 rpm by the viscosity ⁇ 2 measured at a rotation speed of 60 rpm. Each viscosity measurement is repeated three times, and the average value of the three measured values is used.
• the "surface tension" of a solvent or solution is a value measured by the Wilhelmy method at 25°C using a surface tensiometer.
• the "degree of substitution” of cellulose ether is also called the degree of etherification, and represents the number (average value) of hydroxyl groups substituted with alkoxyl groups among the three hydroxyl groups on the glucose ring of cellulose. Theoretically, the degree of substitution can have a value between 0 and 3, and generally, the higher the substituent, the more hydrophilic the substance is.
• the degree of substitution is calculated by converting the value measured by the substitution degree analysis method for hydroxypropyl methylcellulose described in the 18th revised Japanese Pharmacopoeia.
• the "cation concentration" of the aqueous dispersion is a value calculated from the content of cations contained in a measurement sample obtained by ashing the dried aqueous dispersion at 1000°C for 4 minutes, which is determined by frameless atomic absorption spectrometry, and the mass of the aqueous dispersion.
• a "unit" in a polymer means an atomic group based on a monomer formed by polymerization of the monomer.
• the unit may be a unit formed directly by a polymerization reaction, or may be a unit in which a part of the unit is converted into a different structure by processing the polymer.
• a unit based on monomer a is also simply referred to as a "monomer a unit.”
• the aqueous dispersion of the present invention contains particles (hereinafter also referred to as "F particles") of a tetrafluoroethylene-based polymer (hereinafter also referred to as "F polymer”), a water-soluble polymer having at least one polar functional group selected from the group consisting of a vinyl alcohol-based polymer, an acrylic polymer, polyvinylpyrrolidone, polypyrrole, polythiophene, polyethylene oxide, polyethyleneimine, and cellulose ether (hereinafter also referred to as "water-soluble polymer”), and water, and has a concentration of at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions (hereinafter also referred to as "cation concentration”) of 0.1 to 1000 ppm.
• F particles a tetrafluoroethylene-based polymer
• F polymer a water-soluble polymer having at least one polar functional group selected from the group consisting of a vinyl alcohol-
• This dispersion is excellent in dispersion stability and handling, and a molded product such as a coating film (polymer layer) formed from this dispersion is excellent in physical properties such as heat resistance and electrical properties (low linear expansion coefficient, low dielectric constant and low dielectric tangent) based on the tetrafluoroethylene polymer, and is excellent in surface appearance.
• excellent surface appearance includes both excellent surface smoothness such as “less surface roughness” and excellent appearance observed visually or with an analytical instrument such as "no streaks, cracks, defects, etc. on the surface.”
• the viscosity of the aqueous dispersion can be increased, and the liquid properties such as thixotropy (thixotropy) can be improved. It also acts as a binder for the F particles when forming a processed product such as a coating film from the aqueous dispersion.
• the aqueous dispersion tends to foam easily, making it difficult to handle, and the transparency of the molded product tends to decrease, making it difficult to select an appropriate water-soluble polymer.
• the cation concentration is controlled within a specific range of 0.1 to 1000 ppm.
• the concentration of at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions is 0.1 to 1000 ppm.
• the cation concentration is preferably 0.2 ppm or more, more preferably 0.5 ppm or more, and even more preferably more than 1 ppm.
• the cation concentration is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 5 ppm or less. In this case, the above-mentioned mechanism of action is likely to be significantly exhibited.
• the binder function of the water-soluble polymer contained in the present dispersion is further enhanced, and when the present dispersion is placed on the surface of a substrate and heated to form a polymer layer containing an F polymer, powder falling of the F particles is suppressed, and the occurrence of defects and the like is easily prevented to a high degree. Furthermore, the hue of the obtained polymer layer is easily maintained better.
• the cation include alkali metal ions such as lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion, and alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion. Among these, it is preferable that the cation is at least one of sodium ion and potassium ion.
• the above-mentioned cations can be contained in the present dispersion due to their origin in each of the constituent components.
• the above-mentioned cations include cations derived from the F polymer.
• Such cations include cations derived from metal hydroxides such as sodium hydroxide and potassium hydroxide used as pH adjusters in the post-treatment step in the polymerization to obtain the F polymer.
• the above-mentioned cations include cations derived from water-soluble polymers.
• cellulose ether is obtained by a manufacturing method in which refined pulp is contacted with an alkaline solution such as sodium hydroxide or potassium hydroxide, and then an etherifying agent is applied to convert the hydroxyl group contained in the cellulose into an ether, so that the cations may be derived from the alkaline solution.
• the vinyl alcohol polymer may include cations derived from metal hydroxides such as sodium hydroxide or potassium hydroxide used as a saponifying agent in the saponification step after polymerization of vinyl ester.
• cations may be contained as minerals.
• the amount of cations derived from each component constituting the present dispersion may be controlled in advance.
• desalting treatments include a method of previously washing the F polymer with water to control its cation concentration, a method of previously washing a water-soluble polymer with a washing solution to control its cation concentration, and a method of previously controlling the cation concentration of the water used.
• the dispersion after preparation may be treated with an ion exchange resin to control and adjust the cation concentration within the above range.
• the F polymer in the present invention is a polymer containing units based on tetrafluoroethylene (hereinafter also referred to as "TFE") (hereinafter also referred to as “TFE units”).
• the F polymer may be either heat-fusible or non-heat-fusible.
• a heat-fusible polymer means a polymer that has a temperature at which the melt flow rate is 1 to 1000 g/10 min under a load of 49 N.
• the melting temperature of the F polymer, which is heat-fusible is preferably 180° C. or higher, and more preferably 200° C. or higher.
• the melting temperature of the F polymer is preferably 325° C. or lower, and more preferably 320° C. or lower.
• a molded product such as a coating film (polymer layer) formed from the present dispersion tends to have excellent heat resistance.
• the glass transition point of the F polymer is preferably 50° C. or higher, more preferably 75° C. or higher.
• the glass transition point of the F polymer is preferably 150° C. or lower, more preferably 125° C. or lower.
• the fluorine content of the F polymer is preferably 70% by mass or more, more preferably 72 to 76% by mass.
• F polymer is preferably polytetrafluoroethylene (PTFE), the polymer that comprises TFE unit and ethylene-based unit (ETFE), the polymer that comprises TFE unit and propylene-based unit, the polymer that comprises TFE unit and perfluoro(alkyl vinyl ether) (PAVE)-based unit (PAVE unit) (PFA), the polymer that comprises TFE unit and hexafluoropropylene-based unit (FEP), more preferably PFA and FEP, and even more preferably PFA.
• PTFE include low molecular weight PTFE and modified PTFE.
• the number average molecular weight of the low molecular weight PTFE is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
• the number average molecular weight of the PTFE is preferably 10,000 or more.
• the number average molecular weight is a value calculated based on the following formula (1).
• Mn 2.1 ⁇ 1010 ⁇ Hc ⁇ 5.16 (1)
• Mn represents the number average molecular weight of the low-molecular-weight PTFE
• ⁇ Hc represents the heat of crystallization (cal/g) of the low-molecular-weight PTFE measured by differential scanning calorimetry.
• PAVE is preferably CF 2 ⁇ CFOCF 3 , CF 2 ⁇ CFOCF 2 CF 3 or CF 2 ⁇ CFOCF 2 CF 2 CF 3 (hereinafter also referred to as “PPVE”), and more preferably PPVE.
• the F polymer preferably has an oxygen-containing polar group, more preferably has a hydroxyl group-containing group or a carbonyl group-containing group, and even more preferably has a carbonyl group-containing group.
• the dispersion liquid is more likely to exhibit the above-mentioned mechanism of action associated with controlling the cation concentration within the range specified in the present invention, and is excellent in dispersion stability and handling.
• the molded product such as a coating film (polymer layer) formed from the dispersion liquid is excellent in physical properties such as heat resistance, electrical properties (low linear expansion coefficient, low dielectric constant and low dielectric loss tangent), and its surface appearance.
• the hydroxyl-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably --CF 2 CH 2 OH or --C(CF 3 ) 2 OH.
• the carbonyl group-containing group is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH 2 ), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.) or a carbonate group (-OC(O)O-), and more preferably an acid anhydride residue.
• the number of oxygen-containing polar groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, per 1 ⁇ 10 6 carbon atoms in the main chain.
• the number of oxygen-containing polar groups in the F polymer can be quantified by the composition of the polymer or the method described in WO 2020/145133.
• the oxygen-containing polar group may be contained in a unit based on a monomer in the F polymer, or may be contained in a terminal group of the main chain of the F polymer, with the former being preferred.
• Examples of the latter include F polymers having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and F polymers obtained by subjecting F polymers to plasma treatment or ionizing radiation treatment.
• the F polymer is preferably a polymer containing TFE units and PAVE units and units based on a monomer having a carbonyl group-containing group, more preferably a polymer containing TFE units, PAVE units and units based on a monomer having a carbonyl group-containing group, and more preferably a polymer containing these units in this order in an amount of 90 to 99 mol%, 0.99 to 9.97 mol%, and 0.01 to 3 mol% relative to the total units.
• Specific examples of such F polymers include the polymers described in WO 2018/16644.
• the monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride, or 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), and more preferably NAH.
• the D50 of the F particles is preferably 1 ⁇ m or more and less than 10 ⁇ m.
• the F particles may be solid particles or non-hollow particles.
• the F particles may be secondary particles formed from nanometer-order fine particles.
• the D50 of the F particles is preferably 1.0 ⁇ m or more, and more preferably 1.5 ⁇ m or more.
• the D50 of the F particles is preferably 6 ⁇ m or less, and more preferably 5 ⁇ m or less.
• D90 of the F particles is preferably 8 ⁇ m or less, and more preferably 6 ⁇ m or less.
• the specific surface area of the F particles is preferably from 1 to 25 m 2 /g, and more preferably from 6 to 15 m 2 /g.
• the F particles are particles containing an F polymer, and preferably consist of an F polymer.
• the F particles are more preferably particles of a heat-fusible F polymer having an oxygen-containing polar group and a melting temperature of 200 to 325° C. In this case, the above-mentioned mechanism of action is more effectively exerted and aggregation of the F particles is more easily suppressed.
• the F particles may contain a resin or an inorganic compound other than the F polymer, may form a core-shell structure with an F polymer as the core and a resin other than the F polymer or an inorganic compound as the shell, or may form a core-shell structure with an F polymer as the shell and a resin other than the F polymer or an inorganic compound as the core.
• examples of the resin other than the F polymer include aromatic polyester, polyamideimide, polyimide, and maleimide, and examples of the inorganic compound include silica and boron nitride.
• the F particles may be used alone or in combination of two or more kinds.
• the water-soluble polymer contained in the dispersion is at least one selected from the group consisting of vinyl alcohol polymers, acrylic polymers, polyvinylpyrrolidone, polypyrrole, polythiophene, polyethylene oxide, polyethyleneimine, and cellulose ether, and has a polar functional group.
• the term "water-soluble polymer” refers to a polymer having a solubility in water of 20 g/L or more.
• the polar functional group is preferably an ether bond, an ester bond, an amide bond, an imide bond, a thioether bond, a sulfide bond, a disulfide bond, a carbonyl group-containing group, a hydroxyl group-containing group, a thiol group, a sulfide group, a sulfonyl group, a sulfoxyl group, an amino group, or an amide group, more preferably a hydroxyl group-containing group, and even more preferably a nonionic hydroxyl group.
• the polar functional group may be present in either the main chain or the side chain of the polymer.
• polyvinylpyrrolidone, polypyrrole, polythiophene, polyethylene oxide, or polyethyleneimine further has a hydroxyl group, it is preferable that the hydroxyl group is present at the end of the main chain of the polymer.
• vinyl alcohol-based polymers examples include polyvinyl alcohol, polyvinyl acetate, partially acetylated or partially acetalized polyvinyl alcohol, and copolymers of vinyl alcohol, vinyl butyral, and vinyl acetate.
• Specific examples of vinyl alcohol-based polymers include the "S-LEC (registered trademark) B" series, the “S-LEC (registered trademark) K (KS)” series, and the “S-LEC (registered trademark) SV” series (all manufactured by Sekisui Chemical Co., Ltd.), and the "Mobital (registered trademark)” series (manufactured by Kuraray Co., Ltd.).
• acrylic polymer examples include polyacrylic acid, salts of polyacrylic acid such as sodium polyacrylate, sodium acrylic acid/maleic acid copolymer, and sodium acrylic acid/sulfonic acid monomer copolymer, polyacrylates such as methyl polyacrylate and ethyl polyacrylate, poly- ⁇ -haloacrylate, poly- ⁇ -cyanoacrylate, and polyacrylamide.
• the cellulose ethers include alkyl celluloses, carboxyalkyl celluloses, hydroxyalkyl celluloses, or hydroxyalkyl alkyl celluloses.
• Examples of the carboxyalkyl cellulose include carboxymethyl cellulose.
• Examples of the hydroxyalkyl cellulose include hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
• Examples of the hydroxyalkyl alkyl cellulose include hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl ethyl methyl cellulose, etc. These may be used alone or in combination of two or more kinds. Among these, carboxyalkyl cellulose, hydroxyalkyl cellulose, or hydroxyalkyl alkyl cellulose is preferred, hydroxyalkyl cellulose is more preferred, and hydroxyethyl cellulose is even more preferred.
• the degree of substitution of the cellulose ether is preferably 1.4 or more, more preferably 1.9 or more, and even more preferably 2.1 or more.
• the degree of substitution of the cellulose ether is preferably 2.9 or less, and more preferably 2.7 or less.
• the weight average molecular weight of the cellulose ether is preferably 1,000 to 10,000.
• the weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a differential refractive index detector.
• GPC gel permeation chromatography
• Specific examples of cellulose ethers include the "Sunrose (registered trademark)” series (manufactured by Nippon Paper Industries Co., Ltd.), the “Metolose (registered trademark)” series (manufactured by Shin-Etsu Chemical Co., Ltd.), and "HEC CF Grade” (manufactured by Sumitomo Seika Chemicals Co., Ltd.).
• the water-soluble polymer is preferably at least one selected from the group consisting of vinyl alcohol polymers and cellulose ethers.
• the weight average molecular weight of the water-soluble polymer is preferably 1000 or more, more preferably 10000 or more, further preferably 100000 or more, and particularly preferably 300000 or more.
• the weight average molecular weight of the water-soluble polymer is preferably 1000000 or less, more preferably 500000 or less.
• the present dispersion may further contain a viscosity regulator other than the above-mentioned water-soluble polymer, from the viewpoint of adjusting the viscosity and thixotropy ratio.
• the water-soluble polymer is preferably at least one selected from the group consisting of vinyl alcohol-based polymers and cellulose ethers.
• the weight-average molecular weight of the water-soluble polymer is preferably 1,000 or more, more preferably 10,000 or more, even more preferably 100,000 or more, and particularly preferably 300,000 or more.
• the weight-average molecular weight of the water-soluble polymer is preferably 1,000,000 or less, more preferably 500,000 or less.
• the present dispersion may further contain a viscosity regulator other than the above-mentioned water-soluble polymer, from the viewpoint of adjusting the viscosity and thixotropy ratio.
• the dispersion may further contain a nonionic surfactant.
• nonionic surfactants include glycol-based surfactants, acetylene-based surfactants, silicone-based surfactants, and fluorine-based surfactants.
• One type of nonionic surfactant may be used, or two or more types may be used.
• silicone-based surfactants are preferred, and polyoxyalkylene-modified dimethylsiloxanes having a polyoxyalkylene structure as the hydrophilic portion and a polydimethylsiloxane structure as the hydrophobic portion are more preferred.
• the polyoxyalkylene-modified dimethylsiloxane may have a polydimethylsiloxane unit (-( CH3 ) 2SiO2 /2- ) in the main chain, may have a polydimethylsiloxane unit in the side chain, or may have a polydimethylsiloxane unit in both the main chain and the side chain.
• the polyoxyalkylene-modified polydimethylsiloxane is preferably a polyoxyalkylene-modified polydimethylsiloxane containing a dimethylsiloxane unit in the main chain and an oxyalkylene group in the side chain, or a polyoxyalkylene-modified polydimethylsiloxane containing a dimethylsiloxane unit in the main chain and an oxyalkylene group at a main chain terminal.
• the oxyalkylene group contained in the polyoxyalkylene-modified dimethylsiloxane may be composed of only one type of oxyalkylene group, or may be composed of two or more types of oxyalkylene groups. In the latter case, the different types of oxyalkylene groups may be linked randomly or in blocks.
• the HLB value of the silicone surfactant is preferably 10 or more.
• silicone surfactants include "BYK-347”, “BYK-349”, “BYK-378”, “BYK-3450”, “BYK-3451”, “BYK-3455”, “BYK-3456” (manufactured by BYK Japan), "KF-6011", and “KF-6043” (manufactured by Shin-Etsu Chemical Co., Ltd.).
• the dispersion further contains a nonionic surfactant, preferably a silicone surfactant, the content is preferably in the range of 1 to 15% by mass, more preferably 3 to 10% by mass, relative to the F particles in the dispersion.
• a nonionic surfactant preferably a silicone surfactant
• the dispersion may further contain an alcohol having 1 to 6 carbon atoms.
• an alcohol having 1 to 6 carbon atoms is a compound that is liquid at atmospheric pressure and 25°C, and preferably has a boiling point of 160°C or less, more preferably a compound with a boiling point of 120°C or less.
• Examples of the alcohol having 1 to 6 carbon atoms include methanol (23 mN/m), ethanol (23 mN/m), 1-propanol (24 mN/m), 2-propanol (22 mN/m), 1-butanol (25 mN/m), 2-butanol (24 mN/m), isobutanol (23 mN/m), 1-methoxy-2-propanol (26 mN/m), 2-propoxy-ethanol (27 mN/m), 1-propoxy-2-propanol (25 mN/m), 2-ethoxyethanol (26 mN/m), ethylene glycol (48 mN/m), propylene glycol (25 mN/m), and glycerin (63 mN/m).
• the numerical values in parentheses indicate the surface tension of each alcohol. These may be used alone or in combination of two or more. When two or more types of the alcohols are used, they are preferably compatible with each other.
• the content is preferably 0.1% by mass or more, and more preferably 1% by mass or more, relative to the dispersion.
• the content of the alcohol having 1 to 6 carbon atoms is preferably 10% by mass or less, and more preferably 5% by mass or less.
• dispersion media may be used in this dispersion liquid as long as the effects of the present invention are not impaired. It is preferable that such other dispersion media are miscible with the above-mentioned alcohol and water.
• Examples of other dispersion media include amides such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone; and ketones such as acetone and methyl ethyl ketone.
• amides such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2
• the present dispersion may further contain an inorganic filler, in which case the formed product such as a coating film (polymer layer) formed from the present dispersion is likely to have excellent electrical properties and low linear expansion.
• the shape of the inorganic filler may be any of spherical, acicular (fibrous), and plate-like, and specifically may be spherical, scaly, lamellar, leaflet-like, apricot kernel-like, columnar, cockscomb-like, equiaxed, leaf-like, micaceous, block-like, flat, wedge-like, rosette-like, net-like, and prismatic.
• inorganic fillers include silicon compounds such as quartz powder, silica, wollastonite, talc, silicon nitride, silicon carbide, and mica; nitrogen compounds such as boron nitride and aluminum nitride; metal oxides such as aluminum oxide, zinc oxide, titanium oxide, cerium oxide, beryllium oxide, magnesium oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, and silver oxide; carbon fibers; carbon allotropes such as graphite, graphene, and carbon nanotubes; and metals such as silver and copper.
• the inorganic filler may be used alone or in combination of two or more kinds.
• the D50 of the inorganic filler is preferably 0.1 to 50 ⁇ m.
• the surface of the inorganic filler may be treated with a silane coupling agent.
• Suitable specific examples of the inorganic filler include silica fillers (Admafine (registered trademark) series (manufactured by Admatechs Co., Ltd.), SFP (registered trademark) series (manufactured by Denka Co., Ltd.), E-SPHERES series (manufactured by Taiheiyo Cement Corporation), etc.), zinc oxide fillers (FINEX (registered trademark) series (manufactured by Sakai Chemical Industry Co., Ltd.), etc.), titanium oxide fillers (Tipaque (registered trademark) series (manufactured by Ishihara Sangyo Kaisha, Ltd.), JMT (registered trademark) series (manufactured by Teika Co., Ltd.), etc.), talc fillers (SG series (manufactured by Nippon Talc Co., Ltd.), etc.), steatite fillers (BST series (manufactured by Nippon Talc Co., Ltd.
• the present dispersion may further contain another resin different from the F polymer.
• another resin may be contained in the present dispersion as non-hollow particles, or may be dissolved or dispersed in a liquid dispersion medium such as water constituting the present dispersion, or an alcohol having 1 to 6 carbon atoms or other dispersion medium contained as necessary (hereinafter, water, an alcohol having 1 to 6 carbon atoms, other dispersion medium, etc. are collectively referred to as "liquid dispersion medium").
• polyester resins such as liquid crystalline aromatic polyesters, polyimide resins, polyamideimide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, and polyphenylene sulfide resins.
• the other resin is preferably an aromatic polymer, more preferably at least one aromatic imide polymer selected from the group consisting of aromatic polyimide, aromatic polyamic acid, aromatic polyamideimide, and a precursor of aromatic polyamideimide.
• the aromatic polymer is preferably contained in the present dispersion as a varnish dissolved in a liquid dispersion medium.
• aromatic imide polymers include the "UPIA-AT” series (UBE), the “NEOPLIM (registered trademark)” series (Mitsubishi Gas Chemical Company, Inc.), the “SPIXELIA (registered trademark)” series (Somar), the “Q-PILON (registered trademark)” series (PI Technical Research Institute), the "WINGO” series (Wingo Technology Co., Ltd.), the “TOMAID (registered trademark)” series (T&K TOKA Corporation), the "KPI-MX” series (Kawamura Sangyo Co., Ltd.), “HPC-1000” and “HPC-2100D” (both manufactured by Showa Denko Materials K.K.).
• the content of the other resin relative to the F particles is preferably 1 to 25% by mass.
• the dispersion may further contain additives such as a thixotropic agent, an antifoaming agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a release agent, and a flame retardant.
• additives such as a thixotropic agent, an antifoaming agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a release agent, and a flame retardant.
• This dispersion liquid can be obtained by mixing F particles, a water-soluble polymer, water, and, if necessary, the above-mentioned silicone-based surfactant, an alcohol having 1 to 6 carbon atoms, other dispersion media, inorganic fillers, other resins, additives, etc.
• the dispersion may be obtained by mixing the F particles, the water-soluble polymer, and water all at once, or may be mixed separately and in sequence, or a master batch of these may be prepared in advance and then mixed with the remaining components. There is no particular restriction on the order of mixing, and the mixing method may be either mixing all at once or mixing in several separate batches.
• a cellulose ether used as the water-soluble polymer, it may be added as a powder or an aqueous solution thereof, or may be added in a state dispersed or dissolved in a liquid defoaming agent or the like.
• a silicone surfactant When a silicone surfactant is further mixed, it may be added as it is or in the form of an aqueous solution.
• the above-mentioned alcohol having 1 to 6 carbon atoms, other dispersion medium, inorganic filler, other resin, additive, etc. are further mixed as necessary, they may be mixed when the F particles and water are mixed, or they may be mixed when the mixture is added to water.
• Mixing equipment for obtaining this dispersion includes blade-equipped stirring equipment such as a Henschel mixer, pressure kneader, Banbury mixer, and planetary mixer, media-equipped grinding equipment such as a ball mill, attritor, basket mill, sand mill, sand grinder, Dyno Mill, Dispermat, SC Mill, spike mill, and agitator mill, and dispersing equipment equipped with other mechanisms such as a microfluidizer, nanomizer, 8%, ultrasonic homogenizer, dissolver, disperser, high-speed impeller, thin film swirling high-speed mixer, centrifugal mixer, and V-type mixer.
• blade-equipped stirring equipment such as a Henschel mixer, pressure kneader, Banbury mixer, and planetary mixer
• media-equipped grinding equipment such as a ball mill, attritor, basket mill, sand mill, sand grinder, Dyno Mill, Dispermat, SC Mill, spike mill, and agitator mill
• the content of F particles in this dispersion is preferably 25% by mass or more, and more preferably 35% by mass or more.
• the content of F particles is preferably 75% by mass or less, and more preferably 60% by mass or less.
• the content of the water-soluble polymer in the present dispersion is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, based on the total mass of the present dispersion.
• the content of the water-soluble polymer is preferably 1% by mass or less, more preferably 0.1% by mass or less, based on the total mass of the present dispersion.
• the ratio of the content of the water-soluble polymer to the content of the F particles in the present dispersion is preferably 0.001 or more, more preferably 0.003 or more. This ratio is preferably 0.05 or less, more preferably 0.03 or less, and even more preferably 0.01 or less.
• the water content in this dispersion is preferably 25% by mass or more, and more preferably 40% by mass or more.
• the water content is preferably less than 70% by mass, and more preferably 65% by mass or less.
• the water content in this dispersion is preferably 60 to 180% by mass relative to the F particle content.
• the viscosity of the present dispersion is preferably 500 mPa ⁇ s or more, more preferably 1000 mPa ⁇ s or more.
• the viscosity of the present dispersion is preferably 10000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less.
• the present dispersion has excellent coatability and is easy to form a molded product such as a coating film (polymer layer) having a desired thickness.
• the present dispersion having a viscosity in this range is easy to highly express the physical properties of the F polymer in a molded product formed therefrom.
• the thixotropy ratio of the present dispersion is preferably 1.0 to 2.5, in which case the present dispersion has excellent coatability and homogeneity, and is likely to produce a denser molded product.
• the pH of the present dispersion is preferably 8 or more, more preferably more than 8, and even more preferably 8.1 or more.
• the pH of the present dispersion is preferably 11 or less, more preferably 10 or less.
• the above-mentioned mechanism of action is easily manifested.
• the present dispersion in which the water-soluble polymer is a vinyl alcohol-based polymer or cellulose ether and is in such a pH range is easily promoted to moderately promote the denaturation of the water-soluble polymer in the liquid, and the liquid properties such as the foamability of the liquid are easily improved.
• the pH of the present dispersion can be adjusted with a pH adjuster (an amine such as ethanolamine, ammonia, citric acid, etc.) or a pH buffer (tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium hydrogen carbonate, ammonium carbonate, ammonium acetate, etc.).
• a pH adjuster an amine such as ethanolamine, ammonia, citric acid, etc.
• a pH buffer tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium hydrogen carbonate, ammonium carbonate, ammonium acetate, etc.
• the dielectric constant of the molded product formed from this dispersion is preferably 2.4 or less, more preferably 2.0 or less.
• the dielectric constant is preferably greater than 1.0.
• the dielectric tangent of the molded product is preferably 0.0022 or less, more preferably 0.0020 or less.
• the dielectric tangent is preferably greater than 0.0010.
• the thermal conductivity of the molded product is preferably 1 W/m ⁇ K or more, more preferably 3 W/m ⁇ K or more.
• a molded product such as a sheet containing the F polymer can be formed.
• the sheet obtained by extrusion may be further cast by press molding, calendar molding, etc.
• the sheet is preferably further heated to remove the liquid dispersion medium and to bake the F polymer.
• the thickness of the sheet formed from the present dispersion is preferably 1 to 1000 ⁇ m.
• the suitable ranges of the dielectric constant, dielectric dissipation factor and thermal conductivity of the sheet are the same as those of the above-mentioned molded product.
• the thermal conductivity of the sheet means the thermal conductivity in the in-plane direction of the sheet.
• the linear expansion coefficient of the sheet is preferably 100 ppm/° C. or less, more preferably 80 ppm/° C. or less.
• the lower limit of the linear expansion coefficient of the sheet is 30 ppm/° C.
• the linear expansion coefficient means a value obtained by measuring the linear expansion coefficient of a test piece in the range of 25° C. to 260° C. according to the measurement method specified in JIS C 6471:1995.
• Such a sheet can be laminated on a substrate to form a laminate.
• methods for producing a laminate include a method of extruding the present dispersion onto the substrate, and a method of thermocompression bonding the sheet and the substrate.
• the substrate include metal substrates such as metal foils of copper, nickel, aluminum, titanium, alloys thereof, etc.; films of heat-resistant resins such as polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyaryl ether ketone, polyamideimide, liquid crystalline polyester, and tetrafluoroethylene polymers; prepreg substrates (precursors of fiber-reinforced resin substrates), ceramic substrates such as silicon carbide, aluminum nitride, and silicon nitride; and glass substrates.
• the shape of the substrate may be flat, curved, or uneven, and may be any of a foil, plate, film, and fiber shape.
• the ten-point average roughness of the surface of the substrate is preferably 0.01 to 0.05 ⁇ m.
• the surface of the substrate may be surface-treated with a silane coupling agent or plasma-treated.
• a silane coupling agent having a functional group such as 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, or 3-isocyanatepropyltriethoxysilane is preferable.
• the peel strength between the sheet and the substrate is preferably 10 to 100 N/cm.
• the dispersion is placed on the surface of a substrate and heated to form a polymer layer containing an F polymer (hereinafter also referred to as an "F layer")
• a laminate having, in this order, a substrate layer composed of the substrate and an F layer can be obtained.
• the F layer is preferably formed by disposing the dispersion on the surface of a substrate, heating to remove the liquid dispersion medium, and further heating to bake the F polymer. By separating the substrate from such a laminate, a sheet containing the F polymer is obtained.
• the substrate may be the same as the substrate that can be laminated with the above-mentioned sheet, and the preferred embodiments thereof are also the same.
• Methods for applying the present dispersion include coating, droplet discharging, and immersion methods, and roll coating, knife coating, bar coating, die coating, and spraying are preferred.
• the heating for removing the liquid dispersion medium is preferably performed at 100 to 200° C. for 0.1 to 30 minutes. In this heating, the liquid dispersion medium does not need to be completely removed, but only needs to be removed to the extent that the layer formed by the packing of the F particles can maintain a self-supporting film. In addition, when heating, air may be blown onto the surface to promote the removal of the liquid dispersion medium by air drying.
• the heating for baking the F polymer is preferably carried out at a temperature equal to or higher than the melting temperature of the F polymer, more preferably at 360 to 400° C. for 0.1 to 30 minutes.
• the heating device for each heating may be an oven or a ventilated drying furnace.
• the heat source in the device may be a contact type heat source (hot air, hot plate, etc.) or a non-contact type heat source (infrared rays, etc.).
• the heating may be carried out under normal pressure or under reduced pressure.
• the atmosphere in each heating step may be either an air atmosphere or an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.).
• the F layer is formed through the steps of disposing the present dispersion and heating. These steps may be performed once each, or may be repeated two or more times.
• the present dispersion may be disposed on the surface of a substrate and heated to form an F layer, and the present dispersion may be disposed on the surface of the F layer and heated to form a second F layer.
• the present dispersion may be disposed on the surface of the substrate and heated to form an F layer.
• the dispersion may be disposed on only one surface of the substrate, or on both surfaces of the substrate.
• a laminate having a substrate layer and an F layer on one surface of the substrate layer is obtained, and in the latter case, a laminate having a substrate layer and an F layer on both surfaces of the substrate layer is obtained.
• the thickness of the F layer varies depending on the application of the laminate, but is preferably in the range of 1 to 1000 ⁇ m.
• Suitable specific examples of the laminate include a metal-clad laminate having a metal foil and an F layer on at least one surface of the metal foil, and a multilayer film having a polyimide film and an F layer on both surfaces of the polyimide film.
• the preferred ranges of the thickness, dielectric constant, dielectric tangent, thermal conductivity, linear expansion coefficient, and peel strength between the F layer and the substrate layer of the F layer are the same as the preferred ranges of the thickness, dielectric constant, dielectric tangent, thermal conductivity, linear expansion coefficient, and peel strength between the sheet and the substrate of the sheet formed from the above-mentioned dispersion.
• the dispersion is useful as a material for imparting insulating properties, heat resistance, corrosion resistance, chemical resistance, water resistance, impact resistance, and thermal conductivity.
• the present dispersion can be used in printed wiring boards, thermal interface materials, substrates for power modules, coils used in power devices such as motors, in-vehicle engines, heat exchangers, vials, syringes, ampoules, medical wires, secondary batteries such as lithium ion batteries, primary batteries such as lithium batteries, radical batteries, solar cells, fuel cells, lithium ion capacitors, hybrid capacitors, capacitors (aluminum electrolytic capacitors, tantalum electrolytic capacitors, etc.), electrochromic elements, electrochemical switching elements, electrode binders, electrode separators, and electrodes (positive electrodes, negative electrodes).
• the dispersion is also useful as an adhesive for bonding parts.
• the dispersion can be used for bonding ceramic parts, metal parts, electronic parts such as IC chips, resistors, and capacitors on substrates of semiconductor elements and module parts, bonding circuit boards and heat sinks, and bonding LED chips to substrates.
• Molded articles such as sheets and laminates formed from the present dispersion are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, heat dissipation parts, and the like.
• these include electric wire coating materials (aircraft electric wires, etc.), enameled wire coating materials used in motors for electric vehicles, etc., electrical insulating tape, insulating tape for oil drilling, oil transport hoses, hydrogen tanks, materials for printed circuit boards, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrode binders (for lithium secondary batteries, for fuel cells, etc.), copy rolls, furniture, automobile dashboards, covers for home appliances, etc., sliding parts (load bearings, yaw bearings, sliding shafts, valves, bearings, bushings, seals, thrust washers, wear rings, etc.), and other applications.
• tension ropes tension ropes, wear pads, wear strips, tube lamps, test sockets, wafer guides, wear parts of centrifugal pumps, chemical and water supply pumps, tools (shovels, files, hacksaws, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, racket strings, dies, toilets, container coating materials, heat dissipation boards mounted for power devices, heat dissipation members for wireless communication devices, transistors, thyristors, rectifiers, transformers, power MOS FETs, CPUs, heat dissipation fins, metal heat sinks, blades for windmills, wind power generation equipment, aircraft, etc., housings for personal computers and displays, electronic device materials, interior and exterior parts of automobiles, processing machines and vacuum ovens that perform heat treatment under low oxygen conditions, sealing materials for plasma treatment devices, heat dissipation parts in treatment units for sputtering and various dry etching devices, and electromagnetic wave shields.
• Sheets and other molded articles and laminates formed from this dispersion are useful as electronic substrate materials such as flexible printed wiring boards and rigid printed wiring boards, as protective films and heat dissipation substrates, particularly heat dissipation substrates for automobiles.
• the dispersions can also be used as coatings for coating F polymers on feedthroughs through battery or capacitor housings made of light metals such as aluminum, magnesium, titanium, silicon carbide, and alloys thereof.
• feedthroughs include those in which the housing has an opening with a conductor passing through a glass material that seals the opening.
• the glass material may be a glass ceramic material, and specific examples thereof include the materials described in JP-A-2018-502417.
• the conductor may be a material suitable for an electrode material of a battery or a capacitor, for example, copper or a copper alloy for a cathode of a battery.
• the conductor may be made of different materials on the inside and outside of the housing.
• the F polymer in this dispersion particularly the heat-fusible F polymer containing oxygen-containing polar groups, has excellent adhesion, so when used to cover such feedthroughs, it can bond the glass material and the housing to a high degree.
• the F polymer has excellent chemical resistance, so it can highly inhibit corrosion of the glass material.
• a battery that uses an electrolyte containing lithium fluoride salt and has a feedthrough covered with the F polymer from this dispersion not only has excellent airtightness, but also has excellent durability because erosion of the glass material in the feedthrough due to the generation of hydrofluoric acid is inhibited.
• F Particle 1 Particles of a tetrafluoroethylene polymer (melting temperature: 300° C.) containing 97.9 mol %, 0.1 mol %, and 2.0 mol % of TFE units, NAH units, and PPVE units, in that order, and having 1,000 carbonyl group-containing groups per 1 ⁇ 10 6 main chain carbon atoms (D50: 2.0 ⁇ m, specific surface area: 7 m 2 /g).
• F Particles 2 Particles made of a polymer (melting temperature 305° C.) containing 97.5 mol % TFE units and 2.5 mol % PPVE units, in that order, and having no oxygen-containing polar group (D50: 1.8 ⁇ m, specific surface area: 9 m 2 /g).
• the pot was rolled at 150 rpm for 1 hour to obtain a dispersion 1 (viscosity: 1000 mPa s, pH: 8.4) containing F particles 1 (35 parts by mass), hydroxyethyl cellulose (0.1 parts by mass), silicone surfactant (5 parts by mass), water (50 parts by mass), ethanol (10 parts by mass), and ethanolamine, and having a cation concentration of 2 ppm.
• the cation concentration is the total concentration of sodium ions and potassium ions (hereinafter the same).
• Dispersion liquid 2 (viscosity: 2000 mPa s) containing F particles 1 (35 parts by mass), hydroxyethyl cellulose (0.1 parts by mass), a silicone-based surfactant (5 parts by mass), and water (60 parts by mass) and having a cation concentration of 1 ppm was obtained in the same manner as in Example 1, except that ethanol was not added.
• Example 3 Dispersion 3 (viscosity: 2000 mPa s) containing F particles 1 (35 parts by mass), hydroxyethyl cellulose (0.1 parts by mass), a silicone-based surfactant (5 parts by mass), and water (60 parts by mass) and having a cation concentration of 1100 ppm was obtained in the same manner as in Example 1, except that ethanol was not added and the salt content of each component was not adjusted.
• Example 4 After each component was desalted and the salt content of each component was adjusted, F particles 2, polyvinyl alcohol, and water were added to the pot, and zirconia balls were then added. The pot was then rolled at 150 rpm for 1 hour to obtain dispersion liquid 4 containing F particles 2 (35 parts by mass), polyvinyl alcohol (0.1 parts by mass), and water (64.9 parts by mass) and having a cation concentration of 3 ppm.
• Example 5 In the same manner as in Example 4, dispersion 5 containing F particles 2 (35 parts by mass), polyvinyl alcohol (0.1 parts by mass), a silicone surfactant (5 parts by mass), and water (59.9 parts by mass) and having a cation concentration of 0.04 ppm was obtained.
• Example 6 Dispersion liquid 6 containing F particles 2 (35 parts by mass), polyvinyl alcohol (0.1 parts by mass), a silicone-based surfactant (5 parts by mass), and water (59.9 parts by mass) and having a cation concentration of 2000 ppm was obtained in the same manner as in Example 4, except that the salt content of each component was not adjusted.
• Example 7 Dispersion 7 (viscosity: 950 mPa ⁇ s, pH: 7.7) having a cation concentration of 2 ppm was obtained in the same manner as in Example 1, except for adjusting the amount of ethanolamine used.
• Example 8 Dispersion 8 (viscosity: 1100 mPa ⁇ s, pH: 11.1) having a cation concentration of 2 ppm was obtained in the same manner as in Example 1, except that ethanolamine was not used.
• Dispersibility of Dispersions Containing Inorganic Filler Dispersions 4 to 6 were each used to evaluate the behavior when preparing a dispersion further containing an inorganic filler, and the dispersibility of the resulting dispersion. Specifically, 100 parts by mass of Dispersion 4 and 50 parts by mass of silica filler (D50: 0.6 ⁇ m) were put into a pot, and zirconia balls were then put in. The pot was then rolled at 150 rpm for 1 hour to prepare Dispersion 4′ containing silica filler, and the state was visually evaluated after leaving it to stand, and it was found to be well dispersed without any sedimentation or the like. Dispersion 5' prepared in the same manner as above using Dispersion 5 contained some sediment and had poor dispersibility. Dispersion 6' prepared in the same manner as above using dispersion 6 was significantly thickened and gelation occurred in some parts.
• a laminate was produced using each of the dispersions 1 to 3, and the handleability and the polymer layer formed were evaluated. Specifically, by a roll-to-roll process, each dispersion was applied to one surface of a substrate (polyimide film (PI Advanced Materials'"FG-100": thickness 25 ⁇ m) by a small-diameter gravure reverse method to form a coating layer, and the substrate was passed through a ventilation drying oven (oven temperature 150 ° C.) for 3 minutes to remove water and form a dry film. Similarly, each dispersion was applied to the other surface of the substrate to form a coating layer, and the substrate was dried to form a dry film.
• PI Advanced Materials' PI Advanced Materials'
• FG-100 thickness 25 ⁇ m
• Dispersion 1 gave a transparent, smooth polymer layer without bubbles on the surface of the coating layer and without defects or streaks on the surface.
• Dispersion 2 some bubbles were observed on the surface of the coating layer, and the obtained polymer layer was slightly less transparent due to coloring.
• Dispersion 3 had foaming on the surface of the coating layer, discoloration of the polymer layer, and surface defects.
• Dispersion 1 gave a transparent, smooth polymer layer without bubbles on the surface of the coating layer and without defects or streaks on the surface.
• Dispersions 7 and 8 some bubbles were observed on the surface of the coating layer, and the obtained polymer layer had slightly poor transparency.
• the dispersion of the present invention has excellent dispersion stability and ease of handling.

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• 2023
  • 2023-09-27 JP JP2024555751A patent/JPWO2024075609A1/ja active Pending
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