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
  • 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
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular

Definitions

• the present invention relates to an aqueous dispersion and a method for producing a laminate obtained from the aqueous dispersion. More particularly, the present invention relates to an aqueous dispersion containing a tetrafluoroethylene-based polymer and a method for producing a laminate obtained from the aqueous dispersion.
• Tetrafluoroethylene-based polymers have excellent physical properties such as electrical insulation, water and oil repellency, chemical resistance, and heat resistance. Therefore, a dispersion liquid in which the particles are dispersed in water or an organic solvent is useful as a material for forming resists, adhesives, electrical insulating layers, lubricants, inks, paints, and the like.
• the tetrafluoroethylene-based polymer has a low surface energy, and its particles tend to agglomerate. Therefore, the development of low-viscosity dispersions with excellent dispersion stability is underway.
• Patent Document 1 discloses a non-aqueous dispersion containing fine particles of a tetrafluoroethylene-based polymer and a fluorine-based additive.
• an aqueous dispersion containing tetrafluoroethylene-based polymer particles in which water is used as a liquid dispersion medium is prone to foaming.
• the handleability was low when the dispersion was applied.
• the management of liquid physical properties such as pH and viscosity is complicated.
• the present inventors can obtain an aqueous dispersion that is excellent in dispersion stability, handleability during mixing and coating, and surface smoothness of the resulting coating film. We found that and completed the present invention.
• the present invention provides an aqueous dispersion excellent in dispersion stability, handleability during mixing and coating, and surface smoothness of the resulting coating film, and a method for producing a laminate obtained from the aqueous dispersion. .
• the present invention has the following aspects.
• the particles containing a tetrafluoroethylene-based polymer include particles containing a heat-melting tetrafluoroethylene-based polymer and particles containing a non-heat-melting tetrafluoroethylene-based polymer.
• a layer of the aqueous dispersion described in any one of [1] to [12] is formed on the substrate surface, and then water is removed from the aqueous dispersion layer by heating to form tetrafluoro on the substrate surface.
• the production method according to [13], wherein the layer containing the tetrafluoroethylene-based polymer formed by removing the water by heating is baked.
• an aqueous dispersion having excellent dispersion stability, handling properties during mixing with other materials and coating, and surface smoothness of the resulting coating film, and a laminate obtained from the aqueous dispersion A method of manufacturing a body is provided.
• Tetrafluoroethylene-based polymer is a polymer containing units (hereinafter also referred to as “TFE units”) based on tetrafluoroethylene (hereinafter also referred to as “TFE”), hereinafter simply referred to as "F polymer”. Also written.
• Tetrafluoroethylene-based polymer is the above-mentioned tetrafluoroethylene-based polymer, and is a melt-flowable polymer having a temperature at which the melt flow rate is 1 to 1000 g/10 minutes under a load of 49 N. means. Hereinafter, it is simply referred to as "heat-fusible F polymer".
• Polymer glass transition point (Tg) is a value measured by analyzing a polymer by dynamic viscoelasticity measurement (DMA).
• the “melting temperature (melting point) of a polymer” is the temperature corresponding to the maximum melting peak of the polymer measured by differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• D50 is the average particle diameter of the powder that is the particle aggregate, and is the volume-based cumulative 50% diameter of the powder determined by the laser diffraction/scattering method. That is, the particle size distribution of the powder is measured by a laser diffraction/scattering method, the cumulative curve is obtained with the total volume of the powder as 100%, and the particle diameter at the cumulative volume of 50% on the cumulative curve.
• D90 is the cumulative volume particle diameter of the powder, and is the volume-based cumulative 90% diameter of the powder determined in the same manner as "D50".
• a "unit based on a monomer” means an atomic group based on one molecule of the monomer formed by polymerization of the monomer. The units may be units directly formed by a polymerization reaction, or may be units in which some of said units have been converted to another structure by treatment of the polymer. Hereinafter, units based on monomer a are also simply referred to as “monomer a units”.
• the aqueous dispersion of the present invention (hereinafter also referred to as “this dispersion”) includes particles containing F polymer (hereinafter also referred to as “F particles”), polydimethylsiloxane compounds (hereinafter also referred to as “this siloxane” ), hydrophobic silica (hereinafter also referred to as “this silica”) and water.
• the method for producing a laminate of the present invention comprises forming a layer of the present dispersion on the surface of a substrate, and then removing water from the layer of the aqueous dispersion by heating.
• a method for producing a laminate (hereinafter also referred to as "this laminate”) having a layer containing an F polymer and a substrate, wherein the layer containing the F polymer is formed on the surface of a material.
• the F polymer is highly rigid and has extremely low affinity with other components. Therefore, an aqueous dispersion containing F particles, which uses water as a liquid dispersion medium, easily foams. In addition, the F particles have low wettability with water, and have low handling properties when preparing themselves, when mixing them with other components such as resin varnish, and when coating them.
• the present dispersion suppresses foaming and is excellent in dispersion stability, handleability and long-term storage stability.
• a laminate formed from the present dispersion has excellent physical properties based on the F polymer, such as electrical properties, and is also excellent in surface smoothness. Although the reason is not necessarily clear, it is considered as follows.
• the present siloxane easily covers the surface of the F particles and tends to enhance the interaction with the F particles.
• the present siloxane adheres to the F particles to a high degree, so that the dispersion stability of the F particles is selectively improved in the present dispersion liquid, and the deterioration of the liquid physical properties is suppressed.
• the hydrophobic silica cooperates with the siloxane to improve the dispersion stability of the F particles and suppress foaming in the liquid, so that the dispersion can be mixed and coated. It is thought that this improves the surface smoothness of moldings such as coating films.
• the F polymer used in the present invention may be hot-melt or non-hot-melt, preferably at least partially hot-melt.
• the heat-fusible polymer is as described above, and the non-heat-fusible polymer means a polymer that does not have a temperature at which the melt flow rate is 1 to 1000 g/10 minutes under a load of 49N.
• the F polymer When the F polymer is heat-meltable, its melting temperature is preferably 200°C or higher, more preferably 260°C or higher. When the F polymer is heat-meltable, the melting temperature is preferably 325° C. or lower, more preferably 320° C. or lower. In this case, the F particles are likely to interact with the present siloxane, and the present dispersion tends to be excellent in dispersion stability and handleability.
• the glass transition point of 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.
• the surface tension of the F polymer is preferably 16-26 mN/m.
• the surface tension of the F polymer can be measured by placing a droplet of a wetting index reagent (manufactured by Wako Pure Chemical Industries, Ltd.) on a flat plate made of the F polymer.
• F polymer with a high fluorine content is excellent in physical properties such as electrical properties, but on the other hand, it has low surface tension and tends to have low adhesiveness. This dispersion is easy to obtain.
• F polymer is polytetrafluoroethylene (hereinafter also referred to as "PTFE"), a polymer containing TFE units and ethylene units, a polymer containing TFE units and propylene units, TFE units and perfluoro(alkyl vinyl ether) (hereinafter referred to as “PAVE”. Also referred to as “FEP”) is preferred, PFA and FEP are more preferred, and PFA is even more preferred. These polymers may also contain units based on other comonomers.
• the hot-melt F polymer preferably has an oxygen-containing polar group, more preferably has a hydroxyl group-containing group or a carbonyl group-containing group, and further preferably has a carbonyl group-containing group.
• an oxygen-containing polar group more preferably has a hydroxyl group-containing group or a carbonyl group-containing group, and further preferably has a carbonyl group-containing group.
• the hydroxyl group-containing group a group containing an alcoholic hydroxyl group is preferable, and -CF 2 CH 2 OH and -C(CF 3 ) 2 OH are more preferable.
• carbonyl group-containing groups include carboxyl group, alkoxycarbonyl group, amide group, isocyanate group, carbamate group (-OC(O)NH 2 ), acid anhydride residue (-C(O)OC(O)-), Imido residues (-C(O)NHC(O)-, etc.) and carbonate groups (-OC(O)O-) are preferred, and acid anhydride residues are more preferred.
• the number of oxygen-containing polar groups in the F polymer is preferably 10 to 5,000, more preferably 100 to 3,000 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 WO2020/145133.
• 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, the former being preferred.
• Examples of the latter embodiment include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer obtained by subjecting the F polymer to plasma treatment or ionizing radiation treatment.
• the monomer having a carbonyl group-containing group itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH") are preferable, and NAH is more preferable.
• the F polymer is preferably a polymer having carbonyl-containing groups containing TFE units and PAVE units, comprising units based on monomers containing TFE units, PAVE units and carbonyl-containing groups, for all units: More preferably, the polymer contains 90 to 99 mol %, 0.99 to 9.97 mol %, and 0.01 to 3 mol % of these units in this order. Specific examples of such F polymers include the polymers described in WO2018/16644.
• D50 of F particles in the present invention is preferably 0.1 ⁇ m or more, more preferably more than 0.3 ⁇ m, and still more preferably 1 ⁇ m or more.
• D50 of the F particles is preferably 25 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less.
• the specific surface area of the F particles is preferably 1 to 25 m 2 /g.
• the present dispersion liquid may contain two or more kinds of F particles.
• the F particles are preferably particles of a heat-fusible F polymer and particles of a non-heat-fusible F polymer, containing TFE units and PAVE units, containing carbonyl groups Particles of heat-fusible F polymer having groups and particles of non-heat-fusible PTFE are more preferred.
• the present dispersion tends to be excellent in dispersion stability and handleability, and a molded article formed from the present dispersion tends to be excellent in electrical properties.
• the ratio of the heat-fusible F-polymer particles to the total amount of the heat-fusible F-polymer particles and the non-heat-fusible F-polymer particles is preferably 50% by mass or less, more preferably 25% by mass or less. Moreover, the ratio is preferably 0.1% by mass or more, more preferably 1% by mass or more.
• the D50 of the heat-fusible F-polymer particles is preferably 1-4 ⁇ m, and the D50 of the non-heat-fusible F-polymer particles is preferably 0.1-1 ⁇ m.
• the F particles are particles containing an F polymer, preferably particles composed of an F polymer.
• the F particles may contain a resin or an inorganic compound other than the F polymer, and may form a core-shell structure in which the F polymer is the core and the shell is a resin or inorganic compound other than the F polymer, and the F polymer may be may form a core-shell structure in which a resin or an inorganic compound other than the F polymer is used as a core.
• Resins other than the F polymer include aromatic polyesters, polyamideimides, polyimides, and maleimides.
• examples of inorganic compounds include silica and boron nitride.
• the content of F particles in the present dispersion is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more.
• the content of F particles is preferably 60% by mass or less, more preferably 40% by mass or less.
• This siloxane is an organopolysiloxane having dimethylsiloxane as a structural unit, and may have dimethylpolysiloxane units (-(CH 3 ) 2 SiO 2/2 -) in the main chain and dimethylpolysiloxane units in the side chains. It may have siloxane units, and may have dimethylpolysiloxane units in both the main chain and side chains.
• a linear polymer having dimethylpolysiloxane units in its main chain is preferred.
• This siloxane is preferably polyoxyalkylene-modified polydimethylsiloxane from the viewpoint of the dispersion stability of the present dispersion.
• Polyoxyalkylene-modified polydimethylsiloxane contains a dimethylsiloxane unit in the main chain and a polyoxyalkylene-modified polydimethylsiloxane having an oxyalkylene group in the side chain, or a dimethylsiloxane unit in the main chain and at the end of the main chain
• a polyoxyalkylene-modified polydimethylsiloxane having an oxyalkylene group can be mentioned.
• the former polyoxyalkylene-modified polydimethylsiloxane preferably contains a diorganosiloxane unit represented by the formula —(R 1 )(R 2 )SiO 2/2 — at the non-terminal portion of the main chain.
• the latter polyoxyalkylene-modified polydimethylsiloxane preferably contains a triorganosiloxane terminal group represented by the formula (R 1 ) 2 (R 2 )SiO 2/2 — at the main chain terminal.
• R 1 in the formula represents an alkyl group, preferably a methyl group.
• R 2 in the formula represents a group having a polyoxyalkylene group and is represented by the formula -X 2 -O-(Y 2 ) n -Z 2 (wherein X 2 is an alkylene group, Y 2 is a polyoxyalkylene group, Z 2 is a hydrogen atom, an alkyl group or an acyl group, and n is an integer of 2 to 100).
• X2 includes an ethylene group, a propylene group, and a butylene group.
• Y2 includes an oxyethylene group and an oxypropylene group. Examples of the alkyl group or acyl group for Z2 include a methyl group and an acetyl group.
• the polyoxyalkylene group contained in the polyoxyalkylene-modified dimethylsiloxane may consist of two or more kinds of oxyalkylene groups. In the latter case, different oxyalkylene groups may be linked randomly or in blocks.
• the degree of polymerization of the oxyalkylene groups in the polyoxyalkylene-modified polydimethylsiloxane, that is, the number of repeating units of the oxyalkylene groups is preferably 2 or more.
• the degree of polymerization is preferably 100 or less, more preferably 50 or less, even more preferably 20 or less.
• the present siloxane is preferably a combination of hydrophilic polydimethylsiloxane (hereinafter also referred to as “hydrophilic siloxane”) and hydrophobic polydimethylsiloxane (hereinafter also referred to as “hydrophobic siloxane”).
• Hydrophilic siloxanes are siloxanes that are inherently hydrophilic.
• "essentially hydrophilic” means that even if some of the functional groups contain hydrophobic groups, the siloxane compound exhibits hydrophilicity.
• the hydrophilic siloxane has polyoxyethylene groups.
• the present dispersion tends to be excellent in dispersion stability and handleability.
• the hydrophilic siloxane include hydrophilic siloxanes among the polyoxyalkylene-modified polydimethylsiloxanes described above, and examples thereof include polyoxyalkylene-modified polydimethylsiloxanes having a structure represented by the following formula (I) or (II).
• R 1 and R 3 are each an alkyl group having 1 to 18 carbon atoms
• R 2 is a formula --R 4 --O(CH 2 CH 2 O) a --[CH 2 (CH 3 )CHO ] b —R 5
• x is an integer of 5-150
• y is an integer of 1-15.
• R 4 is an alkylene group having 2 to 6 carbon atoms
• R 5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acetyl group or an isocyanate group.
• a is an integer of 1 or more
• b is an integer of 0 or more
• the sum of a and b is 3 to 80, and the range of the value obtained by dividing a by b when b is not 0 is 0.25 to 4 is.
• Both R 1 and R 3 are preferably methyl groups, and R 3 may optionally be an alkyl group other than methyl groups.
• R 6 is an alkyl group having 1 to 18 carbon atoms
• R 7 is a group represented by the formula --R 8 --O(CH 2 CH 2 O) c --R 9
• c is 20 to 100 integers.
• R 8 is an alkylene group having 2 to 6 carbon atoms
• R 9 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acetyl group or an isocyanate group.
• R6 is a methyl group.
• Hydrophobic siloxanes are siloxanes that are hydrophobic in nature.
• "essentially hydrophobic” means that even if a part of the functional groups contain hydrophilic groups, the siloxane compound exhibits hydrophobicity.
• the viscosity of the hydrophobic siloxane at 25° C. measured by an Ostwald viscometer is preferably 10 to 100,000 mm 2 /s, more preferably 50 to 10,000 mm 2 /s, from the viewpoints of defoaming properties and handling properties.
• This silica may be either wet silica or dry silica.
• Examples of the present silica include precipitated silica, silica xerogel, fumed silica, etc. Specific examples include commercially available products such as Nipsil (manufactured by Tosoh Silica Co., Ltd.), Silysia (manufactured by Fuji Silysia Chemical Co., Ltd.), and Aerosil (manufactured by Nippon Aerosil Co., Ltd.). are mentioned.
• the methanol wettability of the present silica is preferably 30-75, more preferably 40-75.
• Methanol wettability is measured by putting 5 mL of methanol aqueous solution and 0.2 g of hydrophobic silica in a test tube with an internal volume of 10 mL, turning it upside down 20 times, and allowing it to stand for 2 minutes. This is the lower limit of the methanol concentration (% by volume) of the aqueous methanol solution for dispersing to form a dispersion.
• the methanol wettability is sometimes referred to as the M value.
• the silica having such a methanol wettability balances the dispersed state and the sedimentation or floating state in the liquid, and in addition to the synergistic effect with the present siloxane, its foam breaking effect tends to increase, and the defoaming property of the present dispersion liquid. It is easy to improve the liquid physical properties of
• the primary particle size of the present silica is preferably 0.001 to 2.0 ⁇ m, more preferably 0.01 to 1.0 ⁇ m.
• the specific surface area of the silica according to the BET method is preferably 100 to 700 m 2 /g, more preferably 100 to 500 m 2 /g.
• the silica having at least one of the primary particle size and the specific surface area within the above range has a balanced state of dispersion and sedimentation or floating in the liquid, and in addition to the synergistic effect with the siloxane, the foam breaking effect is enhanced. It is easy to improve liquid physical properties such as defoaming properties of the present dispersion.
• the silica may be surface-treated.
• the surface treatment can be performed, for example, by using a mixing/dispersing device such as a Henschel mixer, a Loedige mixer, or a high speeder. It can be done by spraying siloxane. If necessary, heating and addition of an alkaline catalyst such as aqueous ammonia can also be carried out.
• the temperature is preferably room temperature to 100° C., more preferably 50 to 80° C., for 10 to 120 minutes, more preferably 15 to 60 minutes.
• the amount of the surface treatment agent such as organopolysiloxane to the silica varies depending on the specific surface area of the silica. 1 to 50 parts by mass is preferable, and 5 to 30 parts by mass is more preferable.
• the present dispersion liquid preferably contains 11 parts by mass or less of the present siloxane and 0.5 parts by mass or less of the present silica with respect to 100 parts by mass of the F particles.
• the present dispersion liquid contains more than 0 of the present siloxane and the present silica with respect to 100 parts by mass of the F particles, but from the viewpoint of the effect, it contains 0.1 parts by mass or more of the present siloxane and 0.01 parts by mass or more of the present silica. is preferred.
• the present dispersion When the present dispersion uses both the hydrophilic siloxane and the hydrophobic siloxane, the present dispersion contains 10 parts by mass or less of hydrophilic siloxane, 1 part by mass or less of hydrophobic siloxane, and 1 part by mass or less of hydrophobic siloxane with respect to 100 parts by mass of F particles. It preferably contains 0.5 parts by mass or less of silica.
• the present dispersion uses both the hydrophilic siloxane and the hydrophobic siloxane
• the present dispersion contains 0.1 parts by mass or more of hydrophilic siloxane and 0.1 part by mass of hydrophobic siloxane with respect to 100 parts by mass of F particles. part or more, preferably 0.01 part by mass or more of the present silica.
• the present dispersion may contain a polyether compound in addition to the present siloxane and the present silica.
• the polyether compound interacts with the F particles and also has an antifoaming action, so that the dispersion stability and handling properties of the present dispersion are likely to be improved.
• a polyether compound is a polyoxyalkylene compound represented by the following formula (III). R 10 O—(R 11 O) z —R 10 (III) However, in the above formula (III), R 10 is a hydrogen atom or a monovalent organic group. Two R 10 may be the same or different.
• the monovalent organic group includes alkyl groups such as methyl group, ethyl group, propyl group and butyl group, alkenyl groups such as vinyl group and allyl group, acetyl group and stearoyl group having 1 to 20 carbon atoms, preferably 1 ⁇ 18 monovalent organic groups are included.
• R 11 is an ethylene group or a propylene group. A plurality of R 11 may be two or more different groups.
• the weight average molecular weight of the polyether compound measured by GPC is preferably 500 to 5,000, more preferably 1,000 to 4,000, from the viewpoint of dispersion stability and handling properties during coating.
• the dispersion contains the polyether compound, the dispersion contains 10 parts by mass or less of the siloxane, 0.5 parts by mass or less of the silica, and 1 part of the polyether compound per 100 parts by mass of the F particles. From the viewpoint of dispersion stability, it is preferable to include not more than parts by mass.
• the dispersion contains the polyether compound, the dispersion contains 0.1 parts by mass or more of the siloxane, 0.01 parts by mass or more of the silica, and the polyether It is preferable to contain 0.1 parts by mass or more of the compound.
• the present siloxane is preferably the hydrophilic siloxane.
• the present dispersion contains the F particles, the present siloxane, the present silica and water.
• the content of water in the present dispersion is preferably 40% by mass or more, more preferably 60% by mass or more.
• the water content is preferably 90% by mass or less, more preferably 80% by mass or less.
• the present dispersion may further contain a water-soluble liquid compound as a dispersion medium.
• Water-soluble liquid compounds include water-soluble alcohols and water-soluble amides.
• the viscosity of the present dispersion is preferably 10 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more.
• the viscosity of the present composition is preferably 10000 mPa ⁇ s or less, more preferably 3000 mPa ⁇ s or less.
• the viscosity of the dispersion is a value measured using a Brookfield viscometer under the conditions of 25° C. and 30 rpm. The measurement is repeated 3 times, and the average value of the 3 measurements is taken.
• the thixotropic ratio of this dispersion is preferably 1.0 to 3.0.
• the thixotropic ratio of the dispersion is a value calculated by dividing the viscosity ⁇ 1 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 measurements is calculated.
• the pH of the present dispersion is preferably higher than 7, more preferably 8-10.
• the present siloxane is difficult to decompose, and the present dispersion tends to be excellent in long-term storage stability.
• the dispersion may further contain a pH adjuster or pH buffer to adjust the pH.
• pH adjusters include amines, ammonia, citric acid, and the like.
• pH buffers include tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium hydrogencarbonate, ammonium carbonate, and ammonium acetate.
• This dispersion may contain a nonionic surfactant.
• Preferred nonionic surfactants are glycol-based surfactants, acetylene-based surfactants, silicone-based surfactants and fluorine-based surfactants, and more preferably silicone-based surfactants. Two or more kinds of nonionic surfactants may be used. When two types of nonionic surfactants are used, the nonionic surfactant is preferably a combination of a silicone surfactant and a glycol surfactant.
• nonionic surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafac” series (manufactured by DIC), “Unidyne” series (manufactured by DIC).
• the present dispersion contains a nonionic surfactant
• the content of the nonionic surfactant in the present dispersion is preferably 1 to 15% by mass.
• the dispersion may also contain a resin different from the F polymer.
• Resins other than the F polymer may be thermosetting or thermoplastic. Resins other than the F polymer may be dissolved or dispersed in the present dispersion. A resin other than the F polymer may be contained in the present dispersion as a precursor thereof.
• Resins other than F Polymer include polyester resins (liquid crystalline aromatic polyesters, etc.), imide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, polyphenylene sulfide resins, and fluoropolymers other than F Polymer. polymers.
• Aromatic polymers include aromatic polyimides, aromatic polyimide precursors that are polyamic acids or salts thereof, aromatic polyamideimides, aromatic polyamideimide precursors, aromatic polyetherimides and aromatic polyetherimide precursors. be done.
• the aromatic polymer is preferably water-soluble, more preferably water-soluble aromatic polyimide precursors and water-soluble polyamideimides or precursors thereof.
• water-soluble aromatic polyimide precursors include polyamic acids obtained by polymerizing tetracarboxylic dianhydrides and diamines and salts thereof.
• water-soluble aromatic polyamideimides or precursors thereof include polyamideimides or precursors thereof obtained by reacting at least one of diisocyanate and diamine with tribasic acid anhydride.
• Tetracarboxylic dianhydrides include pyromellitic anhydride and biphenyltetracarboxylic anhydride.
• Diamines include phenylenediamine, 3,3'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl ether.
• Diisocyanates include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, and 3,3'-diphenylmethane diisocyanate.
• the aromatic polymer preferably has a number average molecular weight (Mn) of 5,000 to 50,000.
• the acid value of the aromatic polymer is preferably 20-100 mg/KOH.
• the acid value of the aromatic polymer was determined by adding 0.5 g of aromatic polymer, 0.15 g of 1,4-diazabicyclo[2.2.2]octane, 60 g of N-methyl-2-pyrrolidone and 1 mL of deionized water. It is determined by titrating the mixed solution with a potentiometric titrator using a 0.05 mol/L ethanolic potassium hydroxide solution.
• the acid value at the time of ring-opening an acid anhydride group be the acid value of an aromatic polymer.
• the content of the aromatic polymer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more.
• the content of the aromatic polymer is preferably 30% by mass or less, more preferably 10% by mass or less.
• Fluoropolymers other than the F polymer include polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride and the like.
• the content of the fluoropolymer other than the F polymer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more.
• the content of the aromatic polymer is preferably 30% by mass or less, more preferably 10% by mass or less.
• the present dispersion may further contain an inorganic filler other than hydrophobic silica.
• an inorganic filler other than hydrophobic silica.
• Two or more kinds of inorganic fillers may be used.
• the shape of the inorganic filler is preferably spherical, needle-like, fibrous or plate-like, preferably spherical, scale-like or layer-like, more preferably spherical or scale-like.
• the spherical inorganic filler is preferably substantially spherical.
• substantially spherical means that, when observing the inorganic filler with a scanning electron microscope (SEM), the proportion of the inorganic filler having a minor axis to major axis ratio of 0.7 or more is 95% or more.
• the aspect ratio of the non-spherical inorganic filler is preferably 2 or more, more preferably 5 or more. The aspect ratio is preferably 10000 or less.
• carbon fillers, inorganic nitride fillers and inorganic oxide fillers are preferable, and carbon fiber fillers, boron nitride fillers, aluminum nitride fillers, beryllia fillers, silica fillers other than hydrophobic silica, wollastonite fillers, and talc. More preferred are fillers, cerium oxide fillers, aluminum oxide fillers, magnesium oxide fillers, zinc oxide fillers and titanium oxide fillers, and more preferred are silica fillers other than boron nitride fillers and hydrophobic silica.
• Silica fillers other than hydrophobic silica are hydrophilic silica fillers, and are preferably not surface-treated or surface-treated with a hydrophilic surface treatment agent.
• D50 of the inorganic filler is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. D50 is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
• the specific surface area of the inorganic filler is preferably 1-20 m 2 /g.
• the surface of the inorganic filler may be surface-treated with a silane coupling agent.
• Silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanate.
• Silane coupling agents with functional groups such as propyltriethoxysilane are preferred.
• silica fillers other than hydrophobic silica include the "ADMAFINE” series (manufactured by Admatechs), the “SFP” series (manufactured by Denka), and the “E-SPHERES” series (manufactured by Taiheiyo Cement Co., Ltd.).
• Specific examples of zinc oxide fillers include the “FINEX” series (manufactured by Sakai Chemical Industry Co., Ltd.).
• titanium oxide fillers include the "Tipake” series (manufactured by Ishihara Sangyo Co., Ltd.) and the "JMT” series (manufactured by Tayca Corporation).
• talc filler examples include "SG” series (manufactured by Nippon Talc Co., Ltd.).
• a specific example of the steatite filler is the “BST” series (manufactured by Nippon Talc Co., Ltd.).
• Specific examples of the boron nitride filler include “UHP” series (manufactured by Showa Denko KK) and "GP” and “HGP” grades of the "Denka Boron Nitride” series (manufactured by Denka).
• the present dispersion contains an inorganic filler other than hydrophobic silica, the content of such inorganic filler in the present dispersion is preferably 10 to 40% by mass.
• the present dispersion may further contain a polyhydric alcohol other than the polyether compound.
• a polyhydric alcohol is a compound other than the polyoxyalkylene compound represented by the formula (III) and having two or more alcoholic hydroxyl groups, and is hereinafter simply referred to as polyhydric alcohol.
• polyhydric alcohol an aliphatic polyhydric alcohol containing two or three alcoholic hydroxyl groups and containing no nitrogen atoms and having a boiling point of 100° C. or higher is preferred.
• the boiling point of the polyhydric alcohol is preferably 150°C or higher, more preferably 200°C or higher.
• the boiling point is preferably 340°C or lower.
• the polyhydric alcohol is preferably one that is miscible with water.
• Polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- pentanediol, 2-butene-1,4-diol, glycerin, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol. Glycerin is preferred as the polyhydric alcohol. In this case, the dispersibility of the F particles in the present dispersion liquid is further improved, and the present dispersion liquid tends to be excellent in dispersion stability and handleability. Polyhydric alcohols may be used singly or in combination of two or more.
• the mass ratio of the polyhydric alcohol to water is preferably 0.2 or more, more preferably 0.5 or more.
• Such content mass ratio is preferably 10 or less, more preferably 5 or less.
• the polyhydric alcohol exhibits a well-balanced aggregation-inhibiting action and rheology-adjusting action, and the present dispersion tends to be excellent in dispersion stability.
• this dispersion may optionally contain a thixotropic agent, a viscosity modifier, an antifoaming agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, and an antistatic agent. , brighteners, coloring agents, conductive agents, release agents, surface treatment agents, flame retardants, various fillers, and other additives.
• the present dispersion is prepared by collectively adding the F particles, the present siloxane, the present silica, and, if necessary, other components such as the polyether compound, inorganic filler, resin different from the F polymer, additives, etc., to water and mixing. a method of sequentially adding F particles and other components to water and mixing them; a method of pre-mixing F particles with water and other components with water before mixing; mixing F particles with other components It is preferable to manufacture by a method of mixing with water after drying. Mixing of these may be performed in a batch system or in a continuous system.
• Mixing devices include blade-equipped stirring devices such as Henschel mixers, pressure kneaders, Banbury mixers and planetary mixers, ball mills, attritors, basket mills, sand mills, sand grinders, dyno mills, dispermats, SC mills, and spike mills. Or equipped with other mechanisms such as grinding equipment with media such as agitator mill, microfluidizer, nanomizer, agitzer, ultrasonic homogenizer, desolver, disper, high speed impeller, rotation or revolution stirrer or thin film swirling high speed mixer A dispersing device may be mentioned.
• blade-equipped stirring devices such as Henschel mixers, pressure kneaders, Banbury mixers and planetary mixers, ball mills, attritors, basket mills, sand mills, sand grinders, dyno mills, dispermats, SC mills, and spike mills. Or equipped with other mechanisms such as grinding equipment with media such as agitator
• the F particles and a part of water are kneaded in advance to obtain a kneaded material, and the kneaded material is further added to the remaining water to obtain a dispersion liquid.
• the present dispersion liquid further contains other components such as polyether compounds, inorganic fillers and other resins, the other components may be mixed during kneading or may be mixed during addition.
• the kneaded product obtained by kneading may be in the form of paste or wet powder.
• a paste is a paste or the like having a viscosity of 1000 to 100000 mPa ⁇ s.
• wet powder refers to wet powder or the like having a viscosity of 10,000 to 100,000 Pa ⁇ s as measured by a capillograph.
• the viscosity measured by the capillograph is defined by using a capillary with a capillary length of 10 mm and a capillary radius of 1 mm, a furnace body diameter of 9.55 mm, a load cell capacity of 2 t, a temperature of 25 ° C., and a shear rate of It is a value measured as 1s ⁇ 1 .
• a planetary mixer is a stirring device having two stirring blades that rotate and revolve with each other.
• Mixing in the addition is preferably carried out using a thin-film rotating high-speed mixer.
• a thin-film swirling high-speed mixer is a stirring device that spreads F particles and a liquid dispersion medium in the form of a thin film on the inner wall surface of a cylindrical stirring tank, swirls them, and mixes them while exerting centrifugal force.
• a layer of the present dispersion (hereinafter also referred to as “wet film layer”) is formed on the surface of the substrate, and then water is removed from the layer of the present dispersion by heating to form an F polymer on the surface of the substrate. (hereinafter also referred to as “dry film layer”) to produce the present laminate.
• dry film layer After the dry film layer is formed, the dry film layer is further heated to bake the F polymer to form a base layer and a layer containing the baked product of the F polymer on the surface of the base layer (hereinafter also referred to as "F layer”). ) is obtained.
• the formation of the F layer may be performed subsequently to the formation of the dry film layer, or may be performed in a separate step from the formation of the dry film layer.
• Substrates include metal substrates such as metal foils of copper, nickel, aluminum, titanium, and alloys thereof, polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester, and F polymer. , a prepreg substrate that is a precursor of a fiber-reinforced resin substrate, a ceramic substrate such as a ceramic substrate such as silicon carbide, aluminum nitride, silicon nitride, etc., and a glass substrate. Among these substrates, copper foils and polyimide films are preferable as substrates, and low-roughened copper foils are preferable. Examples of the shape of the base material include planar, curved, and uneven shapes. Moreover, the shape of the substrate may be any of foil, plate, film, and fiber.
• the ten-point average roughness of the substrate surface 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.
• Silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanate.
• Silane coupling agents with functional groups such as propyltriethoxysilane are preferred.
• Examples of methods for forming a wet film layer on the substrate surface using the present dispersion include a coating method.
• Coating methods include a coating method, a droplet discharge method, and an immersion method, with roll coating, knife coating, bar coating, die coating, and spraying being preferred.
• the heating for removing water from the wet film layer by heating to form the dry film layer is preferably carried out at 100 to 200° C. for 0.1 to 30 minutes. It is not necessary to completely remove the water in the heating at this time, and it may be removed to such an extent that the layer formed by the packing of the F particles can maintain a self-supporting film. In addition, during heating, air may be blown to promote the removal of water by air-drying. In addition, when a water-soluble liquid compound other than water is further included as the liquid dispersion medium of the present dispersion, it is preferable that the water-soluble liquid compound other than water is also removed together with the water by the above heating.
• the F layer is formed by heating the dry film layer to bake the F polymer.
• the F polymer may be baked by further raising the temperature in the heating step for forming the dry film layer. Heating for sintering the F polymer is more preferably carried out at 360 to 400° C. for 0.1 to 30 minutes.
• the heating for firing the F polymer is preferably carried out at a temperature higher than the melting temperature of the F polymer.
• Examples of the heating apparatus for heating for the formation of the dry film layer and the formation of the F layer include an oven and a ventilation drying furnace.
• the heat source in the apparatus may be a contact heat source such as hot air or a hot plate, or a non-contact heat source such as infrared rays. Each heating may be performed under normal pressure or under reduced pressure.
• the atmosphere in each heating may be an air atmosphere, an inert gas atmosphere such as helium gas, neon gas, argon gas, or nitrogen gas.
• the F layer is formed by bringing this dispersion liquid into contact with a base material and performing a heating process. These steps may be performed once each, or may be repeated twice or more.
• the surface of a base material is coated with the present dispersion, heated to form a dry film layer, followed by the formation of an F layer, and the surface of the F layer is further coated with the present dispersion and heated to form a second layer.
• the surface may be further coated with the present dispersion and heated to form the F layer.
• the dispersion may be brought into contact with only one surface of the substrate, or may be brought into contact with 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, the substrate layer and the F layer are provided on both surfaces of the substrate layer.
• a laminate is obtained.
• Preferred specific examples of the laminate include a metal foil and a metal-clad laminate having an F layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having an F layer on both surfaces of the polyimide film. is mentioned.
• the thickness of the F layer is preferably 10 ⁇ m or more, more preferably 10 to 200 ⁇ m, even more preferably 10 to 50 ⁇ m.
• the peel strength between the F layer and the substrate layer is preferably 10 to 100 N/cm. Further, the substrate layer may be removed from the laminate to obtain a film containing the F polymer.
• the laminate Since the laminate has excellent electrical properties, it is suitable as a material for printed circuit boards. Specifically, it can be used for manufacturing printed circuit boards as flexible metal-clad laminates and rigid metal-clad laminates. In particular, it can be suitably used for manufacturing a flexible printed circuit board as a flexible metal-clad laminate.
• an interlayer insulating film may be formed on the transmission circuit, a solder resist may be laminated on the transmission circuit, or a coverlay film may be laminated on the transmission circuit. These interlayer insulating films, solder resists and coverlay films may be formed from this dispersion.
• the laminate is useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sporting goods, food industry goods, heat dissipation parts, paints, cosmetics and the like.
• the printed circuit board it can be used as a new printed circuit board material to replace the conventional glass epoxy board in order to prevent the temperature rise of the printed circuit board on which electronic parts are mounted at high density.
• wire coating materials for aircraft wires enameled wire coating materials used for motors such as electric vehicles, electrical insulating tapes, insulating tapes for oil drilling, printed circuit board materials, microfiltration membranes, Separation membranes such as outer filtration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, electrode binders for lithium secondary batteries and fuel cells, copy rolls, furniture, automobile dashboards, home appliances, etc.
• sealing materials for processing machines, vacuum ovens, plasma processing equipment, etc. that heat-process under low-oxygen conditions such as PC and display housings, electronic device materials, interior and exterior of automobiles, etc., sputtering and various dry etching. It is useful as a heat dissipation component in a processing unit such as an apparatus.
• the present dispersion is impregnated with the insulating layer of a printed wiring board, a thermal interface material, a substrate for a power module, a coil used in a power unit such as a motor, and dried to form a thermally conductive heat-resistant coating layer.
• a thermally conductive heat-resistant coating layer It can also be used for bonding ceramic parts and metal parts in automotive engines, for providing corrosion resistance to heat exchangers and their constituent fins or tubes, and for coating the inside and outside of glass containers. . It is particularly suitable for coating for imparting impact resistance.
• glass containers include vials, syringes, needle-equipped syringes, cartridge-type syringes, and ampoules.
• the present dispersion can be used for secondary batteries such as lithium ion batteries, primary batteries such as lithium batteries, radical batteries, solar batteries, especially dye-sensitized solar batteries, fuel cells, lithium ion capacitors, hybrid capacitors, electric double layers.
• secondary batteries such as lithium ion batteries, primary batteries such as lithium batteries, radical batteries, solar batteries, especially dye-sensitized solar batteries, fuel cells, lithium ion capacitors, hybrid capacitors, electric double layers.
• Capacitors such as capacitors, aluminum electrolytic capacitors, various capacitors such as tantalum electrolytic capacitors, electrochromic elements, electrochemical switching elements, electrochemical devices with electrodes such as various electrochemical sensors, electrode binder materials, separator materials It can be used as a coating material and as a coating material for positive or negative electrodes.
• the present dispersion contains a conductive filler, it can be suitably used in applications requiring conductivity, such as the field of printed electronics. Specifically, energizing elements in printed circuit boards, sensor electrodes, displays, backplanes, RFID (radio frequency identification), photovoltaics, lighting, disposable electronics, automotive heaters, electromagnetic wave (EMI) shields, membrane switches, etc. Can be used in manufacturing.
• the baked product obtained from this dispersion can be used as an adhesive for bonding electronic components such as IC chips, resistors, and capacitors mounted on substrates in semiconductor devices, high-density substrates, module parts, etc., and for circuit substrates. It can be used for bonding heat sinks and LED chips to substrates.
• the baked product can also be used as a conductive bonding material (as an alternative to solder bonding) between circuit wiring and electronic components in the process of mounting electronic components. It can also be used as an adhesive between ceramic parts and metal parts in vehicle engines. Moreover, the baked product can also be used for applications described in paragraph [0149] of International Publication No. 2016/017801.
• the present invention is not limited to the configurations of the above-described embodiments.
• the present dispersion liquid may be added to any other configuration in the configurations of the above-described embodiments, or may be replaced with any configuration that exhibits similar functions.
• the manufacturing method of this laminated body may additionally have another arbitrary process, and may replace it with the arbitrary processes which produce a similar effect
• Siloxane compound Hydrophilic polyoxyalkylene-modified polydimethylsiloxane ("BYK-3450" manufactured by BYK-Chemie Japan Co., Ltd.) having a dimethylsiloxane unit in the main chain and an oxyethylene group in the side chain.
• Siloxane 2 Hydrophobic polydimethylsiloxane (viscosity at 25° C. measured by Ostwald viscometer: 8000 mm 2 /s)
• Silica 1 Hydrophobic silica surface-treated with hydroxydimethylpolysiloxane at both ends (specific surface area: 300 m 2 /g, “AEROSIL 300” manufactured by Nippon Aerosil Co., Ltd.)
• Silica 2 Surface-treated hydrophobic silica having a trimethylsilyl group (primary particle size: 0.01 ⁇ m, specific surface area: 130 m 2 /g, methanol wettability: 70, “RX200” manufactured by Nippon Aerosil Co., Ltd.)
• Silica 3 Surface-treated hydrophobic silica having an alkylsilyl group (primary particle size: 0.01 ⁇ m, specific surface area: 150 m 2 /g, methanol wettability: 50, “R805” manufactured by Nippon Aerosil Co., Ltd.)
• Silica 3 surface-treated hydrophobic silica having a dimethylsilyl group (primary particle size: 0.01 ⁇ m,
• Polyether 1 Ring-opening addition polymer of ethylene oxide and propylene oxide having 25 oxyethylene units and 35 oxypropylene units
• Varnish 1 water varnish [polyurethane] containing aromatic polyamideimide precursor (PAI1)
• PAI1 aromatic polyamideimide precursor
• Polyurethane 1 Polyurethane thickener ("ADEKA NOL UH450VF” manufactured by ADEKA)
• Dispersion liquid 1 containing 1 part by mass of polyurethane 1 and having F particles 1 dispersed therein was obtained.
• Dispersions 2 to 6 were obtained in the same manner as Dispersion 1, except that the composition of the dispersion was changed as shown in Table 1.
• Laminate Dispersion 1 was applied to the surface of a long copper foil having a thickness of 18 ⁇ m by a small-diameter gravure reverse method to form a wet film layer.
• the copper foil on which the wet film layer was formed was passed through a drying furnace at 110° C. for 5 minutes and dried by heating to obtain a dry film layer.
• the dry film layer was heated at 380° C. for 3 minutes in an oven with a nitrogen gas atmosphere.
• Laminates 2 to 6 were produced in the same manner as in Laminate 1, except that Dispersion 1 was changed to Dispersions 2 to 6.
• Dispersed layer ratio is 60% or more, re-dispersion is easy
• Dispersion 21 containing silica 2, dispersion 31 containing silica 3, and dispersion containing silica 4 were prepared in the same manner except that silica 1 in the production of dispersion 2 was changed to silica 2, silica 3, or silica 4. Liquid 41 was obtained respectively.
• the dispersion stability of each dispersion liquid was equivalent to that of dispersion liquid 2, and the dispersion stability of dispersion liquid 31 was particularly excellent.
• the dispersion 21 and the dispersion 31 generate less foam than the dispersion 41, and the dispersion 21 In particular, the antifoaming property was also excellent.
• Siloxane 2 and Silica 1 When both Siloxane 2 and Silica 1 were used, they were mixed in advance and used as a silicone oil compound. Commercial products such as BYK-017, BYK-1786, and BYK-1789 (all manufactured by BYK-Chemie Japan) can be substituted for this. When polyether 1 and silica 1 were used together, they were mixed in advance and used as a silicone oil compound. This can be replaced with a commercially available product such as BYK-012 (manufactured by BYK-Chemie Japan).
• the present dispersion is excellent in dispersion stability, handleability during coating, and surface smoothness of the resulting coating film.
• the laminate obtained from this dispersion is sufficiently equipped with the electrical properties of the F polymer and has excellent peel strength to the substrate.

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