CN117715993A - Aqueous dispersion and method for producing laminate - Google Patents
Aqueous dispersion and method for producing laminate Download PDFInfo
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- CN117715993A CN117715993A CN202280051808.5A CN202280051808A CN117715993A CN 117715993 A CN117715993 A CN 117715993A CN 202280051808 A CN202280051808 A CN 202280051808A CN 117715993 A CN117715993 A CN 117715993A
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- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910002028 silica xerogel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides an aqueous dispersion liquid excellent in dispersion stability, workability at the time of mixing or coating, and surface smoothness of a coating film obtained, and a method for producing a laminate obtained from the aqueous dispersion liquid. The aqueous dispersion contains particles containing a tetrafluoroethylene polymer, a polydimethylsiloxane compound, hydrophobic silica, and water.
Description
Technical Field
The present invention relates to an aqueous dispersion and a method for producing a laminate obtained from the aqueous dispersion. More specifically, the present invention relates to an aqueous dispersion containing a tetrafluoroethylene polymer and a method for producing a laminate obtained from the aqueous dispersion.
Background
The tetrafluoroethylene polymer is excellent in properties such as electrical insulation, water and oil repellency, chemical resistance and heat resistance. Therefore, a dispersion in which particles thereof are dispersed in water or an organic solvent can be used as a material for forming a resist, an adhesive, an electrically insulating layer, a lubricant, an ink, a paint, or the like. However, tetrafluoroethylene polymer has low surface energy, and the particles are easily aggregated. Therefore, low-viscosity dispersions having excellent dispersion stability are being developed.
For example, patent document 1 discloses a nonaqueous dispersion liquid containing fine particles of a tetrafluoroethylene polymer and a fluorine-based additive.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2015-199902
Disclosure of Invention
Technical problem to be solved by the invention
However, aqueous dispersions containing tetrafluoroethylene polymer particles in which water is used as the liquid dispersion medium tend to foam easily, and the ease of handling is poor when preparing the dispersion, when mixing the dispersion with other components such as resin varnish, or when coating the dispersion. In addition, the management of liquid properties such as pH and viscosity is complicated for stable storage of the dispersion over a long period of time.
The present inventors have found that an aqueous dispersion excellent in dispersion stability, handleability at the time of mixing or coating, and surface smoothness of the obtained coating film can be obtained by adding a polydimethylsiloxane-based compound and hydrophobic silica, and have completed the present invention.
The present invention provides an aqueous dispersion liquid excellent in dispersion stability, workability at the time of mixing or coating, and surface smoothness of a coating film obtained, and a method for producing a laminate obtained from the aqueous dispersion liquid.
Technical proposal adopted for solving the technical problems
The present invention has the following technical matters.
[1] An aqueous dispersion comprising particles containing a tetrafluoroethylene polymer, a polydimethylsiloxane compound, hydrophobic silica, and water.
[2] The aqueous dispersion according to [1], wherein at least a part of the polydimethylsiloxane-based compound is a hydrophilic polydimethylsiloxane having a polyoxyethylene group.
[3]Such as [1]]Or [2]]The aqueous dispersion comprises a hydrophilic polydimethylsiloxane having a polyoxyethylene group and a viscosity of 10 to 100000mm as the polydimethylsiloxane-based compound 2 Hydrophobic polydimethylsiloxane of/s.
[4] The aqueous dispersion according to any one of [1] to [3], wherein the hydrophobic silica has a methanol wetting value of 30 to 75.
[5] The aqueous dispersion according to any one of [1] to [4], wherein the hydrophobic silica has a primary particle diameter of 0.01 to 20. Mu.m.
[6]Such as [1]]～[5]The aqueous dispersion according to any one of the above, wherein the specific surface area of the hydrophobic silica is 100 to 700m 2 /g。
[7] The dispersion liquid according to any one of [1] to [6], wherein the content of the tetrafluoroethylene polymer-containing particles is 30% by mass or more.
[8] The aqueous dispersion according to any one of [1] to [7], wherein the aqueous dispersion comprises 11 parts by mass or less of the polydimethylsiloxane-based compound and 0.5 part by mass or less of the hydrophobic silica per 100 parts by mass of the tetrafluoroethylene-containing polymer particles.
[9] The aqueous dispersion according to any one of [1] to [8], further comprising a polyether compound.
[10] The aqueous dispersion according to [9], wherein the aqueous dispersion comprises 1 part by mass or less of the polyether compound per 100 parts by mass of the tetrafluoroethylene polymer-containing particles.
[11] The aqueous dispersion according to any one of [1] to [10], wherein the tetrafluoroethylene polymer is a polymer having an oxygen-containing polar group.
[12] The aqueous dispersion according to any one of [1] to [11], wherein the tetrafluoroethylene polymer-containing particles include particles containing a tetrafluoroethylene polymer having a heat-melting property and particles containing a tetrafluoroethylene polymer having a non-heat-melting property.
[13] A method for producing a laminate having a layer containing a tetrafluoroethylene polymer and a base material, comprising: a layer of the aqueous dispersion of any one of [1] to [12] is formed on the surface of a substrate, and then the layer of the aqueous dispersion is heated to remove water from the layer of the aqueous dispersion, thereby forming a layer containing a tetrafluoroethylene polymer on the surface of the substrate.
[14] The method according to [13], wherein the layer containing a tetrafluoroethylene polymer formed by heating to remove water is baked.
[15] The method of [13] or [14], wherein the tetrafluoroethylene polymer-containing layer has a thickness of 10 μm or more.
Effects of the invention
According to the present invention, an aqueous dispersion excellent in dispersion stability, workability in mixing with other materials or coating, and surface smoothness of the obtained coating film, and a method for producing a laminate obtained from the aqueous dispersion can be provided.
Detailed Description
The following terms have the following meanings.
The "tetrafluoroethylene polymer" is a polymer containing a unit based on tetrafluoroethylene (hereinafter also referred to as "TFE unit"), and is hereinafter also referred to as "F polymer".
The term "hot-melt tetrafluoroethylene polymer" means the tetrafluoroethylene polymer and is a melt-flowable polymer having a solution flow rate of 1 to 1000g/10 minutes under a load of 49N. Hereinafter, the "hot-melt F polymer" will also be abbreviated as "hot-melt F polymer".
The "glass transition temperature (Tg) of a polymer" is a value determined by analyzing a polymer by the dynamic viscoelasticity measurement (DMA) method.
"melting temperature (melting point) of a polymer" means a temperature corresponding to the maximum value of the melting peak of the polymer measured by a Differential Scanning Calorimeter (DSC) method.
The "D50" is the average particle diameter of the powder, which is the particle aggregate, and is the cumulative 50% diameter of the volume basis of the powder obtained by the laser diffraction scattering method. That is, the particle size distribution was measured by a laser diffraction scattering method, and a cumulative curve was obtained with the total volume of the powder being 100%, and the particle diameter at the point on the cumulative curve where the cumulative volume reached 50%.
"D90" is the cumulative volume particle diameter of the powder, and is the cumulative 90% diameter of the powder based on the volume of the powder obtained in the same manner as "D50".
"monomer-based unit" refers to an atomic group based on 1 molecule of a monomer formed by polymerization of the monomer. The unit may be a unit directly formed by polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treatment of a polymer. Hereinafter, the unit based on the monomer a is also simply referred to as "monomer a unit".
The aqueous dispersion of the present invention (hereinafter also referred to as "present dispersion") contains particles containing an F polymer (hereinafter also referred to as "F particles"), a polydimethylsiloxane-based compound (hereinafter also referred to as "present silicone"), hydrophobic silica (hereinafter also referred to as "present silica"), and water.
The method for producing a laminate of the present invention (hereinafter also referred to as "the present method") is a method for producing a laminate (hereinafter also referred to as "the present laminate") comprising a layer containing an F polymer and a substrate, wherein a layer of the present dispersion is formed on the surface of the substrate, and then the layer containing the F polymer is formed on the surface of the substrate by heating the layer of the aqueous dispersion to remove water.
The F polymer is a polymer that is rigid and has extremely low affinity for other components. Therefore, an aqueous dispersion containing F particles, which uses water as a liquid dispersion medium, is easily foamed. Further, F particles have low wettability to water, and have poor handleability when they are prepared by themselves, when they are mixed with other components such as a resin varnish, or when they are coated.
The dispersion can inhibit foaming, and is excellent in dispersion stability, handleability and long-term storage property. The laminate formed from the dispersion has excellent physical properties based on the F polymer, such as electrical characteristics, and also has excellent surface smoothness.
The reason for this is not clear, but the following reasons are considered.
The present siloxane is considered to easily cover the surface of the F particles, and the interaction with the F particles is easily enhanced. That is, since the present siloxane is highly adhered to the F particles, the dispersion stability of the F particles in the present dispersion liquid is considered to be selectively improved, and the decrease in the physical properties of the liquid is suppressed.
Further, it is considered that the hydrophobic silica and the present siloxane act synergistically to improve the dispersion stability of the F particles and suppress foaming in the liquid, and therefore the workability at the time of mixing or coating of the present dispersion and the surface smoothness of a molded article such as a coating film obtained therefrom can be improved.
The F polymer used in the present invention may be hot-melt or non-hot-melt, and preferably at least a part thereof is hot-melt.
As described above, a polymer having a hot melt property means a polymer having a solution flow rate of 1 to 1000g/10 minutes under a load of 49N.
When the F polymer is hot-melt, the melting temperature is preferably 200℃or higher, more preferably 260℃or higher. When the F polymer is a heat-fusible F polymer, the melting temperature is preferably 325℃or less, more preferably 320℃or less. In this case, the F particles easily interact with the present siloxane, and the dispersion stability and handleability of the present dispersion are easily excellent.
The glass transition temperature of the F polymer is preferably 50℃or higher, more preferably 75℃or higher. The glass transition temperature of the F polymer is preferably 150℃or less, more preferably 125℃or less.
The 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 to 26mN/m. The surface tension of the F polymer can be measured by placing droplets of a wetting index reagent (manufactured by Wako pure chemical industries, ltd. (Wako pure chemical industries, ltd.) on a plate made of the F polymer.
While F polymers having a high fluorine content have excellent physical properties such as electric properties, on the other hand, they have low surface tension and are easily deteriorated in adhesion, the present invention can easily provide the dispersion liquid having excellent dispersion stability and handleability due to the above-mentioned mechanism of action.
The F polymer is preferably polytetrafluoroethylene (hereinafter also referred to as "PTFE"), a polymer containing TFE units and ethylene units, a polymer containing TFE units and propylene units, a polymer containing TFE units and units based on perfluoro (alkyl vinyl ether) (hereinafter also referred to as "PAVE") (hereinafter also referred to as "PFA"), a polymer containing TFE units and hexafluoropropylene units (hereinafter also referred to as "FEP"), more preferably PFA and FEP, and still more preferably PFA. These polymers may also contain units based on other comonomers.
PAVE is preferably CF 2 ＝CFOCF 3 、CF 2 ＝CFOCF 2 CF 3 And CF (compact F) 2 ＝CFOCF 2 CF 2 CF 3 (hereinafter also referred to as "PPVE"), more preferably PPVE.
From the viewpoint of improving the adhesion, the F polymer having hot-melt properties preferably has an oxygen-containing polar group, more preferably has a hydroxyl-containing group or a carbonyl-containing group, and still more preferably contains a carbonyl-containing group.
As the hydroxyl group-containing group, an alcoholic hydroxyl group-containing group is preferable, and-CF is more preferable 2 CH 2 OH and-C (CF) 3 ) 2 OH。
As the carbonyl group-containing group, preferred is a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH) 2 ) Anhydride residues (-C (O) OC (O) -), imide residues (-C (O) NHC (O) -, etc.), and carbonate groups (-OC (O) O-), more preferably anhydride residues.
In the case where the F polymer has an oxygen-containing polar group, the number of oxygen-containing polar groups in the F polymer is preferably per 1X 10 6 The number of carbon atoms in the main chain is 10 to 5000, more preferably 100 to 3000. The number of oxygen-containing polar groups in the F polymer can be determined according to the composition of the polymer or the method described in International publication No. 2020/145133.
The oxygen-containing polar groups may be contained in monomer-based units in the F polymer or may be contained in terminal groups of the F polymer backbone, with the former form being preferred. The latter form may be exemplified by an F polymer having an oxygen-containing polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, and an F polymer obtained by subjecting an F polymer to plasma treatment or ionizing radiation treatment.
As the monomer having a carbonyl 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 a carbonyl group and containing TFE units and PAVE units, more preferably a polymer containing TFE units, PAVE units and units based on a monomer having a carbonyl group, and containing 90 to 99 mol%, 0.99 to 9.97 mol%, 0.01 to 3 mol% of these units in this order with respect to the total units. Specific examples of such F polymers include those described in International publication No. 2018/16644.
The D50 of the F polymer particles in the present invention is preferably 0.1 μm or more, more preferably more than 0.3 μm, and still more preferably 1 μm or more. The D50 of the F particles is preferably 25 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less.
The specific surface area of the F particles is preferably 1 to 25m 2 /g。
The present dispersion may contain 2 or more types of F particles. The F particles containing 2 kinds of F particles are preferably particles of a heat-fusible F polymer and particles of a non-heat-fusible F polymer, and more preferably particles of a heat-fusible F polymer having a carbonyl group and containing TFE units and PAVE units and particles of a non-heat-fusible PTFE.
In this case, the dispersion stability and the handleability of the dispersion are easy to be excellent, and the electric characteristics of a molded article formed from the dispersion are easy to be excellent.
The proportion of the particles of the heat-fusible F polymer in the total amount of the particles of the heat-fusible F polymer and the particles of the non-heat-fusible F polymer is preferably 50 mass% or less, more preferably 25 mass% or less. The proportion is preferably 0.1% by mass or more, more preferably 1% by mass or more.
Further, it is preferable that the D50 of the particles of the heat-fusible F polymer is 1 to 4. Mu.m, and the D50 of the particles of the non-heat-fusible F polymer is 0.1 to 1. Mu.m.
The F particles are particles containing an F polymer, and preferably particles composed of an F polymer.
The F particles may further contain a resin or an inorganic compound other than the F polymer, may form a core-shell structure having the F polymer as a core and the resin or the inorganic compound other than the F polymer as a shell, or may form a core-shell structure having the F polymer as a shell and the resin or the inorganic compound other than the F polymer as a core.
Examples of the resin other than the F polymer include aromatic polyesters, polyamideimides, polyimides, and maleimides.
Examples of the inorganic compound include silica and boron nitride.
The content of F particles in the present dispersion is preferably 10 mass% or more, more preferably 20 mass% or more, and particularly preferably 30 mass% or more. The content of F particles is preferably 60 mass% or less, more preferably 40 mass% or less.
The present siloxane is an organopolysiloxane having dimethylsiloxane as a structural unit, and may have dimethylpolysiloxane units (- (CH) in the main chain 3 ) 2 SiO 2/2 (-) may have a dimethylpolysiloxane unit in the side chain, or may have dimethylpolysiloxane units in both the main chain and the side chain. As the present siloxane, a linear polymer having a dimethylpolysiloxane unit in the main chain is preferable.
From the viewpoint of dispersion stability of the present dispersion, the present siloxane is preferably a polyoxyalkylene-modified polydimethylsiloxane. Examples of the polyoxyalkylene-modified polydimethylsiloxane include polyoxyalkylene-modified polydimethylsiloxane having a dimethylsiloxane unit in the main chain and an oxyalkylene group in the side chain, and polyoxyalkylene-modified polydimethylsiloxane having a dimethylsiloxane unit in the main chain and an oxyalkylene group in the terminal of the main chain.
As the former polyoxyalkylene-modified polydimethylsiloxane, it is preferable to contain the formula- (R) in the non-terminal portion of the main chain 1 )(R 2 )SiO 2/2 -the indicated diorganosiloxy groupsAn alkane unit. As the latter polyoxyalkylene-modified polydimethylsiloxane, it is preferable to contain the formula (R) 1 ) 2 (R 2 )SiO 2/2 -the diorganosiloxane units represented.
R in the formula 1 Represents alkyl, preferably methyl.
R in the formula 2 Represents a radical having polyoxyalkylene groups, preferably of the formula-X 2 -O-(Y 2 ) n -Z 2 The radicals represented (in the formula, X 2 Represents methylene, Y 2 Represents polyoxyalkylene radical, Z 2 Represents a hydrogen atom, an alkyl group or an acyl group, and n represents an integer of 2 to 100).
As X 2 Examples of the "vinyl" may include an ethenyl group, an propenyl group and a butenyl group.
As Y 2 Examples of the "oxyethylene" and "oxypropylene" may be mentioned.
As Z 2 Examples of the "alkyl" or "acyl" related to the above are methyl and acetyl.
The polyoxyalkylene group contained in the polyoxyalkylene-modified dimethylsiloxane may be composed of 2 or more kinds of oxyalkylene groups. In the latter case, the different alkylene oxide groups may be randomly linked or may be linked in a block form.
The polymerization degree of the oxyalkylene group in the polyoxyalkylene-modified polydimethylsiloxane, that is, the number of repeating units of the oxyalkylene group is preferably 2 or more. The polymerization degree is preferably 100 or less, more preferably 50 or less, and still more preferably 20 or less.
The present silicone preferably uses both hydrophilic polydimethylsiloxane (hereinafter also referred to as "hydrophilic silicone") and hydrophobic polydimethylsiloxane (hereinafter also referred to as "hydrophobic silicone").
Hydrophilic silicones are silicones that are substantially hydrophilic. Here, substantially hydrophilic means that even if a part of the functional groups contains hydrophobic groups, the silicone compound exhibits hydrophilicity.
Preferably, the hydrophilic siloxane has polyoxyethylene groups. In this case, the dispersion stability and the handleability of the dispersion are easily excellent.
Examples of the hydrophilic siloxane include hydrophilic siloxanes among the above-mentioned polyoxyalkylene-modified polydimethylsiloxane, and examples thereof include polyoxyalkylene-modified polydimethylsiloxane having a structure represented by the following formula (I) or (II).
R 1 2 R 3 SiO-((CH 3 ) 2 SiO) x -(R 1 R 2 SiO) y )-SiR 1 2 R 3 (I)
Wherein in formula (I), R 1 、R 3 Alkyl groups having 1 to 18 carbon atoms, R 2 Is of the formula-R 4 -O(CH 2 CH 2 O) a -[CH 2 (CH 3 )CHO] b -R 5 The group represented is that x is an integer of 5 to 150 and y is an integer of 1 to 15. R is R 4 Is alkylene with 2-6 carbon atoms, R 5 Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acetyl group or an isocyano 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 value obtained by dividing a by b when b is not 0 is in the range of 0.25 to 4.
R 1 、R 3 Preferably all methyl groups, R 3 Alkyl groups other than methyl groups may be used as the case may be.
R 6 2 R 7 SiO-((CH 3 ) 2 SiO) n -SiR 6 2 R 7 (II)
Wherein in formula (II), R 6 Is C1-18 alkyl, R 7 Is of the formula-R 8 -O(CH 2 CH 2 O) c -R 9 The group represented by c is an integer of 20 to 100. R is R 8 Is alkylene with 2-6 carbon atoms, R 9 Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acetyl group or an isocyano group.
R 6 Preferably methyl.
The hydrophobic siloxane is a substantially hydrophobic siloxane. Here, substantially hydrophobic means that even if a part of the functional groups contains hydrophilic groups, the functional groups are hydrophobic as a silicone compound.
From the viewpoint of defoaming property and operabilityIn consideration of the viscosity of the hydrophobic siloxane at 25℃as measured by an Ostwald viscometer, it is preferable that the viscosity be 10 to 100000mm 2 Preferably 50 to 10000mm 2 /s。
The silica may be wet silica or dry silica. Examples of the silica include precipitated silica, silica xerogel, and fumed silica, and specific examples thereof include commercially available products such as Nipsil (from Tonka Cao Guihua corporation), SYLYSIA (from Fuji chemical Co., ltd.), aerosil (from Japanese AEROSIL Co., ltd.).
The methanol wettability of the silica is preferably 30 to 75, more preferably 40 to 75. The methanol wettability is a lower limit value of the methanol concentration (vol%) of the aqueous methanol solution for dispersing the entire amount of hydrophobic silica to form a dispersion after adding 5mL of the aqueous methanol solution and 0.2g of hydrophobic silica to a test tube having an inner volume of 10mL and standing for 2 minutes after turning upside down 20 times. In addition, the methanol wettability is sometimes referred to as the M value. The silica having such methanol wettability is balanced between a dispersed state and a settled or floating state in a liquid, and in addition to the synergistic effect with the silicone, the foam breaking effect is easily enhanced, and the liquid properties such as defoaming property of the dispersion are easily improved.
The primary particle diameter of the silica is preferably 0.001 to 2.0. Mu.m, more preferably 0.01 to 1.0. Mu.m.
As the specific surface area of the silica, the specific surface area measured by BET method is preferably 100 to 700m 2 Preferably 100 to 500m 2 /g。
The present silica having at least one of the primary particle diameter and the specific surface area in the above-mentioned range is balanced between a dispersed state and a settled or floating state in a liquid, and in addition to the synergistic effect with the present siloxane, the foam breaking effect is easily enhanced, and the liquid properties such as defoaming property of the present dispersion are easily improved.
The silica may be surface treated. The surface treatment may be performed by using a mixing and dispersing apparatus such as a henschel mixer, a Lodige mixer, a high-speed mixer, or the like, or by adding a raw powder of the present silica to the apparatus, spraying the organopolysiloxane before stirring, or spraying the organopolysiloxane while stirring. If necessary, heating and adding an alkaline catalyst such as ammonia may be performed. In this case, the treatment is preferably carried out at a temperature of room temperature to 100 ℃, more preferably at a temperature of 50 to 80 ℃ for 10 to 120 minutes, still more preferably for 15 to 60 minutes.
The amount of the surface treatment agent such as organopolysiloxane relative to the silica varies depending on the specific surface area of the silica, but the specific surface area of the silica is 100 to 700m in terms of BET specific surface area 2 In the case of per g, the amount is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the silica.
The present dispersion preferably contains 11 parts by mass or less of the present siloxane and 0.5 parts by mass or less of the present silica per 100 parts by mass of the F particles. The present dispersion contains 0 or more parts by mass of the present siloxane and 0 or more parts by mass of the present silica relative to 100 parts by mass of the F particles, but from the viewpoint of the effect, it is preferable to contain 0.1 part by mass or more of the present siloxane and 0.01 part by mass or more of the present silica.
When the hydrophilic silicone and the hydrophobic silicone are used in combination in the present dispersion, the present dispersion preferably contains 10 parts by mass or less of the hydrophilic silicone, 1 part by mass or less of the hydrophobic silicone, and 0.5 part by mass or less of the present silica per 100 parts by mass of the F particles. When the hydrophilic silicone and the hydrophobic silicone are used in combination in the present dispersion, the present dispersion preferably contains 0.1 part by mass or more of the hydrophilic silicone, 0.1 part by mass or more of the hydrophobic silicone, and 0.01 part by mass or more of the present silica per 100 parts by mass of the F particles.
The present dispersion may contain a polyether compound in addition to the present siloxane and the present silica. In this case, since the polyether compound interacts with the F particles and also has an antifoaming effect, the dispersion stability and the operability of the present dispersion are easily improved. The polyether compound means a polyoxyalkylene compound represented by the following formula (III).
R 10 O-(R 11 O) z -R 10 (III)
Wherein in the above formula (III), R 10 Is a hydrogen atom or a monovalent organic group. 2R 10 May be the same or different. z is an integer of 2 to 150.
Examples of the monovalent organic group include: alkyl groups such as methyl, ethyl, propyl and butyl, alkenyl groups such as vinyl and allyl, monovalent organic groups having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, such as acetyl and stearyl. R is R 11 Is ethylene or propylene. Multiple R' s 11 May be 2 or more groups different from each other.
The weight average molecular weight of the polyether compound measured by GPC is preferably 500 to 5000, more preferably 1000 to 4000, from the viewpoints of dispersion stability and operability at the time of coating.
When the present dispersion contains the polyether compound, the present dispersion preferably contains 10 parts by mass or less of the present siloxane, 0.5 parts by mass or less of the present silica, and 1 part by mass or less of the polyether compound per 100 parts by mass of the F particles, from the viewpoint of dispersion stability. When the present dispersion contains the polyether compound, the present dispersion preferably contains 0.1 part by mass or more of the present siloxane, 0.01 part by mass or more of the present silica, and 0.1 part by mass or more of the polyether compound per 100 parts by mass of the F particles.
In the case of blending the polyether compound, the present siloxane is preferably the hydrophilic siloxane.
The present dispersion comprises the above-mentioned F particles, the present siloxane, the present silica, and water. The water content in the present dispersion is preferably 40% by mass or more, more preferably 60% by mass or more. The water content is preferably 90 mass% or less, more preferably 80 mass% or less.
The dispersion may further contain a water-soluble liquid compound as a dispersion medium. The water-soluble liquid compound may be, for example, a water-soluble alcohol or a water-soluble amide.
The viscosity of the dispersion is preferably 10 mPas or more, more preferably 100 mPas or more. The viscosity of the present composition is preferably 10000 mPas or less, more preferably 3000 mPas or less.
The viscosity of the dispersion was measured using a B-type viscometer at 25℃and a rotation speed of 30 rpm. The measurement was repeated 3 times, and the average of the 3 measured values was taken.
The thixotropic ratio of the present dispersion is preferably 1.0 to 3.0.
The thixotropic ratio of the dispersion is the viscosity eta to be measured at a rotational speed of 30rpm 1 Divided by the viscosity eta measured at a speed of 60rpm 2 And the calculated value. The measurement of each viscosity was repeated 3 times, and calculated as an average of 3 measured values.
The pH of the dispersion is preferably greater than 7, more preferably from 8 to 10. In this case, the silicone is not easily decomposed, and the dispersion is easily excellent in long-term storage.
To adjust the pH value, the present dispersion may further comprise a pH adjuster or a pH buffer. Examples of the pH adjuster include amine, ammonia, and citric acid. Examples of the pH buffer include tris (hydroxymethyl) aminomethane, ethylenediamine tetraacetic acid, ammonium bicarbonate, ammonium carbonate, and ammonium acetate.
The dispersion may contain a nonionic surfactant.
The nonionic surfactant is preferably a glycol surfactant, an acetylene surfactant, a silicone surfactant, or a fluorine surfactant, and more preferably a silicone surfactant. More than 2 nonionic surfactants can be used. The nonionic surfactant in the case of using 2 nonionic surfactants is preferably a combination of a silicone surfactant and a glycol surfactant.
As a specific example of the nonionic surfactant, examples thereof include "FTERGENT" series (made by majoram corporation), "SURFLON" series (made by AGC spa corporation), "mergface" series (made by DIC corporation), "UNIDYNE" series (made by dago corporation), "BYK-347", "BYK-349", "BYK-378", "BYK-3451", "BYK-3455", "BYK-3456" (made by bik chemical japan corporation), and "KF-6011", "KF-6043" (made by singer chemical industry corporation), and "tergo chemical corporation" (made by tmr corporation), "tergo chemical corporation) series (made by tmr corporation)," BYK-347"," BYK-349"," BYK-378"," BYK-3455"," BYK-3456 "(made by BYK chemical corporation).
When the dispersion liquid contains a nonionic surfactant, the content of the nonionic surfactant in the dispersion liquid is preferably 1 to 15% by mass.
The present dispersion may also contain a resin different from the F polymer.
Resins other than the F polymer may be thermosetting or thermoplastic. The resin other than the F polymer may be dissolved in the present dispersion liquid or may be dispersed in the present dispersion liquid. Resins other than the F polymer may be contained in the present dispersion as precursors thereof. Examples of the resin other than the F polymer include polyester resins (liquid crystalline aromatic polyesters and the like), imide resins, epoxy resins, maleimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, and fluoropolymers other than the F polymer.
The resin other than the F polymer is preferably an aromatic polymer or a fluoropolymer other than the F polymer.
The aromatic polymer may be exemplified by aromatic polyimide, aromatic polyimide precursor which is polyamic acid or a salt thereof, aromatic polyamideimide precursor, aromatic polyether imide and aromatic polyether imide precursor. The aromatic polymer is preferably water-soluble, more preferably a water-soluble aromatic polyimide precursor, and a water-soluble polyamideimide or precursor thereof.
The water-soluble aromatic polyimide precursor may be a polyamic acid obtained by polymerizing a tetracarboxylic dianhydride and a diamine, and a salt thereof.
The water-soluble aromatic polyamideimide or a precursor thereof may be, for example, a polyamideimide or a precursor thereof obtained by reacting at least one of diisocyanate and diamine with a ternary acid anhydride.
Examples of the tetracarboxylic dianhydride include pyromellitic anhydride and biphenyl tetracarboxylic anhydride. Examples of the diamine include phenylenediamine, 3 '-dimethylbiphenyl-4, 4' -diamine, 4 '-diaminodiphenylmethane and 4,4' -diaminodiphenyl ether.
Examples of the diisocyanate include 4,4 '-diphenylmethane diisocyanate, xylylene isocyanate, 3' -dimethylbiphenyl-4, 4 '-diisocyanate and 3,3' -diphenylmethane diisocyanate.
The number average molecular weight (Mn) of the aromatic polymer is preferably 5000 to 50000.
The acid value of the aromatic polymer is preferably 20 to 100mg/KOH.
The acid value of the aromatic polymer can be determined by titrating a mixed solution of 0.5g of the aromatic polymer, 0.15g of 1, 4-diazabicyclo [2.2.2] octane, 60g of N-methyl-2-pyrrolidone and 1mL of ion-exchanged water with a potentiometric titration apparatus using a potassium hydroxide ethanol solution of 0.05 mol/L. In addition, when the aromatic polymer has an acid anhydride group, the acid value at the time of opening the acid anhydride group is the acid value of the aromatic polymer.
In the case where the present dispersion contains 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.
Examples of the "fluoropolymer" other than the "F" polymer include polytrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride.
When the dispersion liquid contains a fluoropolymer other than the F polymer, the content of the fluoropolymer other than the F polymer is preferably 0.1 mass% or more, more preferably 0.3 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. The inorganic filler may be used in an amount of 2 or more.
The shape of the inorganic filler is preferably spherical, needle-like, fibrous or plate-like, more preferably spherical, scaly or lamellar, and still more preferably spherical or scaly.
The spherical inorganic filler is preferably substantially spherical. The substantially spherical shape means that the ratio of the short diameter to the long diameter of the inorganic filler is not less than 0.7 and not less than 95% when the inorganic filler is observed by a Scanning Electron Microscope (SEM).
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.
The inorganic filler is preferably a carbon filler, an inorganic nitride filler, or an inorganic oxide filler, more preferably a carbon fiber filler, a boron nitride filler, an aluminum nitride filler, a beryllium oxide filler, a silica filler other than hydrophobic silica, a wollastonite filler, a talc filler, a cerium oxide filler, an alumina filler, a magnesium oxide filler, a zinc oxide filler, or a titanium oxide filler, and still more preferably a boron nitride filler, or a silica filler other than hydrophobic silica.
The silica filler other than the hydrophobic silica is preferably a hydrophilic silica filler, and is preferably not subjected to surface treatment or is subjected to surface treatment with a hydrophilic surface treatment agent.
The D50 of the inorganic filler is preferably 20 μm or less, more preferably 10 μm or less. The D50 is preferably 0.01 μm or more, more preferably 0.1 μm or more. The specific surface area of the inorganic filler is preferably 1 to 20m 2 /g。
The surface of the inorganic filler may be surface-treated with a silane coupling agent.
The silane coupling agent is preferably a silane coupling agent having a functional group such as 3-aminopropyl triethoxysilane, vinyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, or 3-isocyanatopropyl triethoxysilane.
Specific examples of the silica filler other than the hydrophobic silica include "admafin" series (manufactured by jac Mar technology Co., ltd.), "SFP" series (manufactured by electric Co., ltd.), and "E-SPHERES" series (manufactured by Pacific cement Co., ltd.).
As a specific example of the zinc oxide filler, FINEX series (made by Sakai chemical Co., ltd.) can be mentioned.
Specific examples of the titanium oxide filler include "TIPAQUE" series (manufactured by Shiyuan Co., ltd.) and "JMT" series (manufactured by Teapot Co., ltd.).
Specific examples of talc fillers include "SG" series (manufactured by japan talc).
Specific examples of the steatite filler include the "BST" series (manufactured by Japanese talc Co., ltd.).
Specific examples of the boron nitride filler include "UHP" series (manufactured by Showa Denko Co., ltd.), and "GP" and "HGP" series (manufactured by Denka boron nitride Co., ltd.).
When the dispersion contains an inorganic filler other than hydrophobic silica, the content of the inorganic filler in the dispersion is preferably 10 to 40 mass%.
The present dispersion may further contain a polyol other than the polyether compound. Such a polyol is a compound having two or more alcoholic hydroxyl groups other than the polyoxyalkylene compound represented by the above formula (III), and is hereinafter simply referred to as a polyol.
As the polyol, preferred is an aliphatic polyol having 2 or 3 alcoholic hydroxyl groups, containing no nitrogen atom and having a boiling point of 100℃or higher.
The boiling point of the polyol is preferably 150℃or higher, more preferably 200℃or higher. The boiling point is preferably below 340 ℃.
Further, the polyol is preferably a polyol mixed with water.
Examples of the "polyol" may include ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 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, and 1,2, 6-hexanetriol.
As the polyhydric alcohol, glycerin is preferable. In this case, the dispersibility of the F particles in the dispersion is further improved, and the dispersion stability and the operability of the dispersion are easily improved.
The polyhydric alcohol may be used alone or in combination of 1 or more than 2.
When the present dispersion contains a polyol, the mass ratio of the polyol to water content is preferably 0.2 or more, more preferably 0.5 or more. The content mass ratio is preferably 10 or less, more preferably 5 or less. When the content ratio is within this range, the aggregation inhibition effect and the rheology adjustment effect of the polyol are exerted in a well-balanced manner, and the present dispersion is easy to have excellent dispersion stability.
In addition to the above components, the dispersion may contain additives such as thixotropic agents, viscosity modifiers, antifoaming agents, dehydrating agents, plasticizers, weather-proofing agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, and various fillers, as required.
The present dispersion is preferably prepared by the following method: a method in which F particles, the silicone and the silica, and other components such as the polyether compound, the inorganic filler, a resin different from the F polymer, and an additive, which are added as needed, are added to water at once and mixed; a method of sequentially adding the F particles and other components to water and mixing; a method of pre-mixing the F particles with water and other components with water, respectively, and then mixing the mixture; and mixing the F particles with other components and then mixing with water. These mixing may be carried out in a batch manner or in a continuous manner.
Examples of the mixing device include: examples of the dispersing device include a stirring device having blades such as a henschel mixer, a pressure kneader, a banbury mixer, and a planetary mixer, a grinding device having a medium such as a ball mill, a pulverizer, a basket mill, a sand mill, a DYNO mill, a DISPERMAT disperser, an SC mill, a Spike mill, or a stirring mill, a microfluidizer, a nanocrystallizer, an Ultimaizer disperser, an ultrasonic homogenizer, a dissolver, a disperser, a high-speed impeller disperser, a rotation revolution stirrer, or a thin film rotation type high-speed mixer, and dispersing devices having other mechanisms.
The preferred method for producing the present dispersion is a method in which the F particles are kneaded with a part of water in advance to obtain a kneaded product, and the kneaded product is added to the remaining water to obtain a dispersion. In the case where the present dispersion further contains other components such as a polyether compound, an inorganic filler, and other resins, the other components may be mixed at the time of kneading or may be mixed at the time of adding.
The kneaded material obtained by kneading may be pasty or wet powdery. The paste is a paste having a viscosity of 1000 to 100000 mPas, and the like. The wet powder means wet powder having a viscosity of 10000 to 100000 Pa.s as measured by a capillary rheometer.
The viscosity measured by the capillary rheometer means that a capillary having a capillary length of 10mm and a capillary radius of 1mm was used, and the viscosity was measured at a furnace diameter of 9.55mm, a load cell capacity of 2t, a temperature of 25℃and a shear rate of 1s -1 Is determined under the conditions of (a) and (b).
Mixing during kneading is preferably performed using a planetary mixer. The planetary mixer is a stirring device having two-axis stirring blades that rotate and revolve with each other.
The mixing at the time of addition is preferably performed using a film-spinning type high-speed mixer. The film-spinning type high-speed mixer is a stirring device for mixing the F particles and the liquid dispersion medium while applying centrifugal force by spreading the F particles and the liquid dispersion medium in a film-like rotation on the inner wall surface of a cylindrical stirring tank.
The present method is a method of forming a layer of the present dispersion (hereinafter also referred to as a "wet film layer") on a substrate surface, and then heating the layer of the present dispersion to remove water, thereby forming a layer containing an F polymer (hereinafter also referred to as a "dry film layer") on the substrate surface, to thereby produce the present laminate. After forming the dry film layer, if the dry film layer is further heated and the F polymer is fired, a laminate having a base layer and a layer containing a fired product of the F polymer (hereinafter also referred to as "F layer") on the surface of the base layer can be obtained. The formation of the F layer may follow the formation of the dry film layer, or may be performed in a process separate from the formation of the dry film layer.
Examples of the substrate include: metal substrates such as metal foils of copper, nickel, aluminum, titanium, alloys of these metals, and the like, heat-resistant resin films such as polyimide, polyamide, polyether amide, polyphenylene sulfide, polyaryletherketone, polyamide imide, liquid-crystalline polyester, F polymer, and the like, prepreg substrates as fiber-reinforced resin substrate precursors, ceramic substrates such as silicon carbide, aluminum nitride, silicon nitride, and the like, and glass substrates.
Among these substrates, copper foil and polyimide film are preferable, and low-roughened copper foil is more preferable.
The shape of the substrate may be a planar shape, a curved shape, or an uneven shape. 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 μm.
The surface of the substrate may be subjected to a surface treatment with a silane coupling agent or may be subjected to a plasma treatment.
The silane coupling agent is preferably a silane coupling agent having a functional group such as 3-aminopropyl triethoxysilane, vinyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, or 3-isocyanatopropyl triethoxysilane.
Examples of a method for forming a wet film layer on the surface of a substrate using the dispersion include a coating method. Examples of the coating method include a coating method, a droplet discharge method, and a dipping method, and roll coating, blade coating, bar coating, die coating, and spray coating are preferable.
The heating for removing moisture from the wet film layer by heating to form a dry film layer is preferably performed at 100 to 200 ℃ for 0.1 to 30 minutes. In this case, the water is not required to be completely removed during heating, but may be removed to such an extent that the layer formed by the accumulation of the F particles can maintain the self-supporting film. In addition, air may be blown during heating, and air drying may be performed to promote removal of water.
In the case where the present dispersion further contains a water-soluble liquid compound other than water as a liquid dispersion medium, it is preferable that the water-soluble liquid compound other than water is removed together with water by the above-mentioned heating.
The F layer may be formed by firing the F polymer by heating the dry film layer. The F polymer may be fired by further increasing the temperature during the heating stage described above to form the dry film layer. The heating during firing of the F polymer is more preferably carried out at 360 to 400℃for 0.1 to 30 minutes. When the F polymer is a heat-fusible F polymer, heating at the time of firing the F polymer is preferably performed at a temperature equal to or higher than the melting temperature of the F polymer.
Examples of the heating device for heating each of the dry film layer and the F layer include an oven and a ventilating drying oven. The heat source in the device may be a contact type heat source such as hot air or a heating plate, or may be a non-contact type heat source such as infrared rays.
The heating may be performed under normal pressure or under reduced pressure.
The atmosphere at the time of each heating may be any of an air atmosphere, helium gas, neon gas, argon gas, nitrogen gas, and the like.
The F layer is formed by bringing the dispersion into contact with a substrate and performing a heating step. These steps may be performed 1 time each, or may be repeated 2 or more times. For example, the present dispersion may be applied to the surface of a substrate and heated to form a dry film layer and then an F layer, and further the present dispersion may be applied to the surface of the F layer and heated to form an F layer of a second layer. In the step of forming the dry film layer by applying the present dispersion on the surface of the substrate and heating, the F layer may be formed by applying the present dispersion on the surface and heating.
The present dispersion may be in contact with only one surface of the substrate or may be in contact with both surfaces of the substrate. The former case can obtain a laminate having a base material layer and an F layer on a single surface of the base material layer, and the latter case can obtain a laminate having a base material layer and an F layer on both surfaces of the base material layer.
Preferable 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 F layers on both surfaces of the polyimide film.
The thickness of the F layer is preferably 10 μm or more, more preferably 10 to 200 μm, and still more preferably 10 to 50 μm.
The peel strength of the F layer and the base material layer is preferably 10 to 100N/cm.
The substrate layer may be further removed from the laminate to obtain a film comprising the F polymer.
The laminate is excellent in electrical characteristics, and therefore is suitable as a material for a printed board, and is particularly useful for manufacturing a printed board as a flexible metal-clad laminate or a rigid metal-clad laminate. Particularly, the flexible metal-clad laminate is preferably used for manufacturing a flexible printed board.
In the production of such a printed board, an interlayer insulating film may be formed on a transmission circuit, a solder resist may be laminated on the transmission circuit, or a coating film may be laminated on the transmission circuit. These interlayer insulating films, solder resist and coating films can be formed using the present dispersion.
The laminate can be used as antenna parts, printed boards, aircraft parts, automobile parts, sports equipment, food industry products, heat dissipation parts, paints, cosmetics, and the like. The material can be used as a novel material for a printed board instead of a conventional glass epoxy board to prevent the temperature of a printed board on which electronic components are mounted at high density from rising.
Specifically, the present invention can be used as wire coating materials for electric wires for aircraft, wire coating materials for motors for electric vehicles, etc., electrically insulating tapes for petroleum drilling, materials for printed circuit boards, precision filtration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, separation membranes for gas separation membranes, electrode adhesives for lithium secondary batteries, fuel cells, etc., copying rolls, furniture, automobile dashboards, covers for household electric appliances, etc., sliding parts for load bearings, sliding shafts, valves, bearings, bushings, seals, thrust washers, wear rings, pistons, sliding switches, gears, cams, conveyor belts, food transport belts, etc., wear parts for wear pads, wear strips, tubing lamps, test sleeves, wafer rails, centrifugal pumps, pumps for supplying hydrocarbons/chemicals and water, tools such as shovels, files, cones, saws, boilers, hoppers, pipes, ovens, baking molds, spouts, toilets, container coating materials, power devices, transistors, crystal thyristors, rectifiers, power MOS, FETs, CPUs, wind-driven plates, metals, windmill or blade-powered electricity generating devices for aircraft, etc.
More specifically, the heat sink can be used as a housing of a computer or a display, an electronic device material, an interior and exterior material of an automobile, a sealing material for a processing machine or a vacuum furnace for performing heat treatment under low oxygen, a plasma processing apparatus, or the like, or a heat sink in a processing unit of a sputtering or various dry etching apparatuses, or the like.
The dispersion can be used for impregnating and drying a coil used for a power device such as a printed wiring board insulating layer, a thermal interface material, a power module substrate, or an electric motor to form a heat-conductive heat-resistant coating layer, for bonding ceramic members or metal members to each other in a vehicle-mounted engine, for imparting corrosion resistance to a heat exchanger or fins or tubes constituting the heat exchanger, and for coating the inside and outside of a glass container. Is particularly suitable for coating for imparting impact resistance. Examples of the glass container include a vial, a syringe (syringe), a syringe with needle, a barrel-type syringe, and an ampoule.
The dispersion can be used as an electrode binder, a separator coating material, and a positive electrode or negative electrode coating material for electrochemical devices including electrodes, such as secondary batteries such as lithium ion batteries, primary batteries such as lithium batteries, radical batteries, and solar batteries, particularly dye-sensitized solar batteries, fuel cells, lithium ion capacitors, hybrid capacitors, and capacitors such as electric double layer capacitors, various capacitors such as aluminum electrolytic capacitors and tantalum electrolytic capacitors, electrochromic devices, electrochemical conversion devices, and various electrochemical sensors.
In addition, when the dispersion contains a conductive filler, the dispersion can be suitably used for applications requiring conductivity, for example, in the field of printed electronics. Specifically, the method can be used for manufacturing energizing elements such as printed circuit boards, sensor electrodes, displays, backplanes, RFID (radio frequency identification), solar power generation, illumination, disposable electronic devices, automobile heaters, electromagnetic wave (EMI) shields, membrane switches, and the like.
The fired product obtained from the dispersion can be used as an adhesive for bonding an IC chip mounted on a substrate, an electronic component such as a resistor or a capacitor, bonding a circuit board to a heat sink, bonding an LED chip to a substrate, or the like in a semiconductor element, a high-density substrate, a module component, or the like. The fired product can also be used as a conductive bonding material between a circuit wiring and an electronic component (as an alternative to solder bonding) in a mounting process of the electronic component. In addition, the adhesive can be used for an adhesive between ceramic parts or metal parts in an in-vehicle engine. The above-mentioned calcined product can also be used for the purposes described in paragraph [0149] of International publication No. 2016/017801.
The present dispersion and the method for producing the laminate are described above, but the present invention is not limited to the configuration of the above embodiment.
For example, the present dispersion may be added to the above-described embodiment, or may be replaced with any composition that exhibits the same function. In the above-described structure of the embodiment, the method for producing the laminate, any other process may be added, or any process that performs the same function may be substituted.
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
1. Preparation of the ingredients
[ F particles ]
F particle 1: every 1X 10 unit comprising 97.9 mol%, 0.1 mol%, 2.0 mol% of TFE unit, NAH unit and PPVE unit in this order 6 Particles of powder of a polymer having 1000 carbonyl groups in the main chain carbon number (melting temperature: 300 ℃ C.) (D50: 1.7 μm)
F particle 2: particles (D50: 1.8 μm) constituting a powder of a polymer having no oxygen-containing polar group (melting temperature: 305 ℃) comprising 98.7 mol%, 1.3 mol% of TFE unit and PPVE unit in this order
[ Silicone Compound ]
Siloxane 1: hydrophilic polyoxyalkylene-modified polydimethylsiloxane having dimethylsiloxane units in the main chain and oxyethylene groups in the side chains (BYK-3450, manufactured by Pick chemical Co., ltd.)
Siloxane 2: hydrophobic polydimethylsiloxane (viscosity at 25℃measured by means of an Ostwald viscometer: 8000mm 2 /s)
[ hydrophobic silica ]
Silica 1: hydrophobic silica surface-treated with hydroxydimethylpolysiloxane at both terminals (specific surface area: 300 m) 2 Per g, "AEROSIL 300", manufactured by AEROSIL Co., ltd., japan)
Silica 2: surface-treated hydrophobic silica having trimethylsilyl groups (primary particle diameter: 0.01 μm, specific surface area: 130 m) 2 Per g, methanol wet out: 70, "RX200" manufactured by AEROSIL Co., ltd., japan)
Silica 3: surface-treated alkylsilyl-containing hydrophobic silica (primary particle diameter: 0.01 μm, specific surface area: 150 m) 2 Per g, methanol wet out: 50, "R805" manufactured by AEROSIL Co., ltd., japan)
Silica 3: surface-treated hydrophobic silica having dimethylsilyl groups (primary particle diameter: 0.01 μm, specific surface area: 170 m) 2 Per g, methanol wet out: 35, "R974" manufactured by AEROSIL Co., ltd., japan)
[ polyether ]
Polyether 1: ring-opening addition polymer of ethylene oxide and propylene oxide having an oxyethylene unit number of 25 and an oxypropylene unit number of 35
[ aromatic Polyamide imide varnishes ]
Varnish 1: aqueous varnish comprising an aromatic polyamideimide precursor (PAI 1)
[ polyurethane ]
Polyurethane 1: polyurethane thickener (ADEKANOL UH450VF from ADEKA Co., ltd.)
2. Preparation of the Dispersion
Into a tank containing zirconia balls, water and F particles 1 were placed, and then silicone 1, silicone 2, silica 1, varnish 1 and polyurethane 1 were added, and the tank was rolled, and 56.5 parts by mass of water, 40 parts by mass of F particles, 2 parts by mass of silicone 1, 0.3 part by mass of silicone 2, 0.1 part by mass of silica 1, 0.1 part by mass of PAI1 and 0.8 part by mass of polyurethane 1 were added to obtain a dispersion liquid 1 in which F particles 1 were dispersed.
Dispersions 2 to 6 were obtained in the same manner as in dispersion 1, except that the compositions of the dispersions were changed according to table 1.
TABLE 1
The numbers are all parts by mass.
3. Manufacture of laminate
The dispersion 1 was applied by a small-diameter gravure reverse method to the surface of a long copper foil having a thickness of 18 μm to form a wet film layer. Next, the copper foil with the wet film layer formed thereon was passed through a drying oven at 110 ℃ for 5 minutes, and dried by heating, to obtain a dry film layer. The dry film layer was then heated in an oven under nitrogen atmosphere at 380 ℃ for 3 minutes. Thereby, a laminate 1 having a copper foil and a polymer layer of 25 μm in thickness containing the F polymer 1 as a molded article on the surface thereof was produced.
Laminates 2 to 6 were produced in the same manner as laminate 1, except that dispersion 1 was changed to dispersions 2 to 6.
4. Evaluation
4-1 evaluation of Dispersion stability
Each dispersion (18 mL) was placed in a coil (inner volume: 30 mL) and allowed to stand at 25℃for 14 days. The dispersion layer ratio was calculated from the height of the whole dispersion liquid and the height of the sedimented layer (dispersion layer) in the coil after standing, and the redispersibility after shaking the coil by hand was further confirmed, and the dispersion stability was evaluated according to the following criteria.
[ evaluation criterion ]
And (2) the following steps: the dispersion layer ratio is 60% or more, and redispersion is also easy.
Delta: the dispersion layer ratio was less than 60%, but redispersion was easy.
X: the dispersion layer ratio is less than 60% and redispersion is difficult.
4-2 evaluation of coatability
The surface of the polymer layer of the laminate obtained when the laminate was produced from each dispersion was visually observed for the presence or absence of cracks, and the film forming property was evaluated according to the following criteria.
[ evaluation criterion ]
And (3) the following materials: no cracks were observed
O: small cracks were observed at the edges of the polymer layer
Delta: small cracks were observed throughout the polymer layer
X: large cracks were observed throughout the polymer layer
4-3 evaluation of electric characteristics of laminate
Rectangular test pieces having a length of 100mm and a width of 50mm were cut from each laminate, and copper foil was removed by etching with an aqueous solution of ferric chloride to obtain a polymer layer monomer. The dielectric loss tangent (measurement frequency: 10 GHz) of the polymer layer was measured by the SPDR (separation column dielectric resonator) method, and evaluated according to the following criteria.
[ evaluation criterion ]
And (2) the following steps: dielectric loss tangent of less than 0.0020
Delta: dielectric loss tangent of 0.0020 to 0.0025
X: dielectric loss tangent of greater than 0.0025
4-4 evaluation of peel Strength of laminate
Rectangular (100 mm long and 10mm wide) test pieces were cut from each laminate, the position 50mm away from one end of the test piece in the longitudinal direction was fixed, and the metal foil was peeled from the polymer layer at a stretching speed of 50 mm/min from the other end of the test piece in the longitudinal direction at 90 °. The maximum load at this time was the peel strength, and the peel strength was evaluated according to the following criteria.
[ evaluation criterion ]
O: peel strength of more than 12N/cm
Delta: peel strength of 8N/cm or more and 12N/cm or less
X: peel strength of less than 8N/cm
The evaluation results are summarized in table 2.
TABLE 2
| Dispersion liquid | 1 | 2 | 3 | 4 | 5 | 6 |
| Dispersion stability | ○ | ○ | ○ | △ | × | × |
| Laminate body | 1 | 2 | 3 | 4 | 5 | 6 |
| Coating/film Forming Properties | ◎ | ◎ | ○ | △ | × | × |
| Electrical characteristics of the laminate | ○ | ○ | ○ | △ | - | - |
| Peel strength of laminate | ○ | ○ | △ | △ | - | - |
The dispersion 21 containing silica 2, the dispersion 31 containing silica 3, and the dispersion 41 containing silica 4 were obtained in the same manner, respectively, except that the silica 1 in the production of the dispersion 2 described above was changed to silica 2, silica 3, or silica 4. The dispersion stability of each dispersion was the same as that of dispersion 2, and the dispersion stability of dispersion 31 was particularly excellent. Further, after 25 parts by mass of the boron nitride particles were mixed with 100 parts by mass of each of the dispersions by shearing stirring, the dispersion 21 and the dispersion 31 were less foamed than the dispersion 41, and the defoaming property of the dispersion 21 was also particularly excellent.
In addition, in the case of using the silicone 2 and the silica 1 together, they are used as silicone oil compounds after being subjected to a mixing treatment in advance. This may be replaced with commercially available products such as BYK-017, BYK-1786 and BYK-1789 (all manufactured by Pick chemical Co., ltd.).
In the case where polyether 1 and silica 1 are used together, they are also used as silicone oil compounds after being subjected to a mixing treatment in advance. This may be replaced with a commercially available product such as BYK-012 (manufactured by Pick chemical Co., ltd.).
From the above results, it was found that the dispersion stability of the present dispersion, the workability at the time of coating, and the surface smoothness of the obtained coating film were excellent. The laminate obtained from the dispersion liquid is a laminate which has sufficient electrical characteristics of the F polymer and also has excellent peel strength from the substrate.
Further, the entire contents of the specification, claims and abstract of Japanese patent application No. 2021-131924 filed on 8/13 of 2021 are incorporated herein by reference as if fully set forth in the specification of the present invention.
Claims (15)
1. An aqueous dispersion comprising particles containing a tetrafluoroethylene polymer, a polydimethylsiloxane compound, hydrophobic silica, and water.
2. The aqueous dispersion according to claim 1, wherein at least a part of the polydimethylsiloxane-based compound is a hydrophilic polydimethylsiloxane having a polyoxyethylene group.
3. The aqueous dispersion according to claim 1 or 2, wherein the polydimethylsiloxane-based compound comprises a hydrophilic polydimethylsiloxane having a polyoxyethylene group and a viscosity of 10 to 100000mm 2 Hydrophobic polydimethylsiloxane of/s.
4. The aqueous dispersion according to any one of claims 1 to 3, wherein the hydrophobic silica has a methanol wetting value of 30 to 75.
5. The aqueous dispersion according to claim 1 to 4, wherein the hydrophobic silica has a primary particle diameter of 0.01 to 20. Mu.m.
6. The aqueous dispersion according to claim 1 to 5, wherein the hydrophobic silica has a specific surface area of 100 to 700m 2 /g。
7. The dispersion according to any one of claims 1 to 6, wherein the content of the tetrafluoroethylene polymer-containing particles is 30% by mass or more.
8. The aqueous dispersion according to any one of claims 1 to 7, wherein the aqueous dispersion comprises 11 parts by mass or less of the polydimethylsiloxane-based compound and 0.5 parts by mass or less of the hydrophobic silica per 100 parts by mass of the tetrafluoroethylene-containing polymer particles.
9. The aqueous dispersion according to any one of claims 1 to 8, further comprising a polyether compound.
10. The aqueous dispersion according to claim 9, wherein the polyether compound is contained in an amount of 1 part by mass or less per 100 parts by mass of the tetrafluoroethylene polymer-containing particles.
11. The aqueous dispersion according to any one of claims 1 to 10, wherein the tetrafluoroethylene polymer is a polymer having an oxygen-containing polar group.
12. The aqueous dispersion according to any one of claims 1 to 11, wherein the tetrafluoroethylene polymer-containing particles include tetrafluoroethylene polymer-containing particles having a hot-melt property and tetrafluoroethylene polymer-containing particles having a non-hot-melt property.
13. A method for producing a laminate having a layer containing a tetrafluoroethylene polymer and a base material, comprising: forming the layer of the aqueous dispersion according to any one of claims 1 to 12 on the surface of the substrate, and then heating the layer of the aqueous dispersion to remove water therefrom to form the layer containing the tetrafluoroethylene polymer on the surface of the substrate.
14. The method according to claim 13, wherein the layer containing a tetrafluoroethylene polymer formed by heating to remove the water is baked.
15. The method according to claim 13 or 14, wherein the tetrafluoroethylene polymer-containing layer has a thickness of 10 μm or more.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021131924 | 2021-08-13 | ||
| JP2021-131924 | 2021-08-13 | ||
| PCT/JP2022/030317 WO2023017811A1 (en) | 2021-08-13 | 2022-08-08 | Aqueous dispersion and method for producing laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117715993A true CN117715993A (en) | 2024-03-15 |
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| CN202280051808.5A Pending CN117715993A (en) | 2021-08-13 | 2022-08-08 | Aqueous dispersion and method for producing laminate |
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| JP (1) | JPWO2023017811A1 (en) |
| CN (1) | CN117715993A (en) |
| TW (1) | TW202313725A (en) |
| WO (1) | WO2023017811A1 (en) |
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| JP4116763B2 (en) * | 2000-10-19 | 2008-07-09 | 株式会社ソフト９９コーポレーション | Coating composition for painted surface |
| JP2007283551A (en) * | 2006-04-13 | 2007-11-01 | Oji Paper Co Ltd | Thermal recording medium |
| CN102558721B (en) * | 2010-12-31 | 2014-08-20 | 杜邦公司 | Novel polytetrafluoroethylene aqueous dispersion |
| EP3546517B1 (en) * | 2016-11-28 | 2023-03-08 | Agc Inc. | Aqueous polytetrafluoroethylene dispersion |
| CN113557262B (en) * | 2019-03-12 | 2024-02-02 | Ａｇｃ株式会社 | Liquid composition, ferroelectric insulating sheet and method for producing same |
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- 2022-08-08 WO PCT/JP2022/030317 patent/WO2023017811A1/en active Application Filing
- 2022-08-08 JP JP2023541445A patent/JPWO2023017811A1/ja active Pending
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