CN114787273A - Dispersion liquid, liquid composition and method for producing same - Google Patents
Dispersion liquid, liquid composition and method for producing same Download PDFInfo
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- CN114787273A CN114787273A CN202080085659.5A CN202080085659A CN114787273A CN 114787273 A CN114787273 A CN 114787273A CN 202080085659 A CN202080085659 A CN 202080085659A CN 114787273 A CN114787273 A CN 114787273A
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- water
- dispersion
- particles
- glycol
- soluble compound
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
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- 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
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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- C08K5/00—Use of organic ingredients
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- C08K5/10—Esters; Ether-esters
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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
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- 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
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- C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
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Abstract
The invention provides a dispersion liquid containing particles of different tetrafluoroethylene polymers, which is excellent in liquid properties and can form a molded article having various excellent physical properties (particularly, adhesiveness to a substrate). The dispersion of the present invention comprises: particles of polytetrafluoroethylene, particles of a tetrafluoroethylene-based polymer containing a perfluoro (alkyl vinyl ether) -based unit, a water-soluble compound having a boiling point of 100 ℃ or higher, and water, wherein the water-soluble compound is at least one selected from the group consisting of a glycol, a monoether of a glycol, and a monoacetate of a glycol.
Description
Technical Field
The present invention relates to a dispersion liquid of a predetermined form containing polytetrafluoroethylene particles, a method for producing the same, a liquid composition that can be suitably used for producing the dispersion liquid, and a method for producing the same.
Background
As a coating agent for forming a layer having excellent chemical resistance, water/oil repellency, heat resistance, and electrical characteristics on a substrate surface, a dispersion liquid containing particles of a tetrafluoroethylene polymer is known.
Patent document 1 describes an aqueous dispersion containing polytetrafluoroethylene particles, tetrafluoroethylene polymer particles containing a perfluoro (alkyl vinyl ether) -based unit, a high-molecular-weight water-soluble polymer, and water, and a film formed by firing the film formed therefrom.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2008/018400
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have found that the aqueous dispersion is inhibited from cracking during film formation by the water-soluble polymer, but the liquid properties (dispersibility, viscosity, etc.) of the aqueous dispersion are easily degraded. The present inventors have also found that the shape and physical properties of the formed film are rather liable to deteriorate due to decomposition of the water-soluble polymer (generation of decomposition gas) or residues of the water-soluble polymer as the film is fired.
The purpose of the present invention is to provide a dispersion of particles comprising different kinds of tetrafluoroethylene polymers, which has excellent liquid properties and can form molded articles having various excellent properties (particularly, adhesion to a substrate). It is also an object of the present invention to provide a liquid composition which can be suitably used for producing the dispersion.
Further, the present invention aims to provide the dispersion and a method for producing the dispersion.
Technical means for solving the technical problems
The present invention has the following embodiments.
[1] A dispersion, comprising: particles of polytetrafluoroethylene, particles of a tetrafluoroethylene-based polymer containing a perfluoro (alkyl vinyl ether) -based unit, a water-soluble compound having a boiling point of 100 ℃ or higher, and water, wherein the water-soluble compound is at least one selected from the group consisting of a glycol, a glycol monoether, and a glycol monoacetate.
[2] The dispersion liquid according to [1] above, wherein the water-soluble compound is a glycol monoalkyl ether, a glycol monoaryl ether, a glycol monoalkyl ether acetate or a glycol monoaryl ether acetate.
[3] The dispersion liquid according to [1] or [2], wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having an oxygen-containing polar group and containing a perfluoro (alkyl vinyl ether) -based unit, or a tetrafluoroethylene polymer having no oxygen-containing polar group and containing 2.0 to 5.0 mol% of the perfluoro (alkyl vinyl ether) -based unit based on the whole units.
[4] The dispersion liquid according to any one of the above [1] to [3], wherein the polytetrafluoroethylene particles have an average particle diameter of 0.01 to 1 μm and the tetrafluoroethylene polymer particles have an average particle diameter of 0.01 to 10 μm.
[5] The dispersion liquid according to any one of the above [1] to [4], wherein a ratio of a content of the tetrafluoroethylene-based polymer to a content of the polytetrafluoroethylene by mass is 0.4 or less.
[6] The dispersion liquid according to any one of the above [1] to [5], wherein a ratio of a content of the water-soluble compound to a content of the water by mass is 2 or less.
[7] A process for producing a laminate, which comprises applying the dispersion liquid according to any one of the above [1] to [6] onto a surface of a substrate and heating the resulting coating to form a polymer layer comprising the polytetrafluoroethylene and the tetrafluoroethylene-based polymer, thereby obtaining a laminate having a substrate layer composed of the substrate and the polymer layer.
[8] A process for producing an impregnated woven fabric, which comprises impregnating a woven fabric with the dispersion liquid according to any one of the above [1] to [6] and heating the impregnated woven fabric to obtain an impregnated woven fabric comprising the polytetrafluoroethylene and the tetrafluoroethylene polymer.
[9] A method for producing a dispersion according to any one of the above [1] to [6], which comprises mixing an aqueous dispersion containing the polytetrafluoroethylene particles with a liquid composition containing the tetrafluoroethylene polymer particles and the water-soluble compound to obtain the dispersion.
[10] A liquid composition comprising: particles of a tetrafluoroethylene-based polymer containing a perfluoro (alkyl vinyl ether) -based unit, and a water-soluble compound having a boiling point of 100 ℃ or higher, wherein the water-soluble compound is at least one selected from the group consisting of a glycol, a monoether of a glycol, and a monoacetate of a glycol.
[11] The liquid composition according to the above [10], which further comprises water.
[12] The liquid composition according to any one of the above [10] or [11], which comprises 5 to 50 mass% of the tetrafluoroethylene polymer.
[13] The liquid composition according to any one of the above [10] to [12], wherein the HLB value of the water-soluble compound is 1 to 18.
[14] The liquid composition according to any one of the above [10] to [13], wherein the viscosity is 1000 mPas or less.
[15] A process for producing a liquid composition, characterized by subjecting a liquid composition comprising tetrafluoroethylene polymer particles containing a perfluoro (alkyl vinyl ether) -based unit and a water-soluble compound having a boiling point of 100 ℃ or higher, which is selected from at least one of a glycol, a monoether of a glycol and a monoacetate of a glycol, to a wet milling method to obtain a liquid composition comprising the tetrafluoroethylene polymer particles and the water-soluble compound.
Effects of the invention
According to the present invention, an aqueous dispersion containing particles of polytetrafluoroethylene and particles of a predetermined tetrafluoroethylene polymer and having excellent liquid properties (dispersibility, viscosity, etc.) can be obtained. Also, a liquid composition containing particles of a predetermined tetrafluoroethylene polymer and a predetermined water-soluble compound, which is suitable for easily producing the aqueous dispersion, can be obtained.
Detailed Description
The "melting temperature (melting point) of the polymer" is a temperature corresponding to the maximum value of a melting peak measured by a Differential Scanning Calorimetry (DSC) method.
The "viscosity of the dispersion" is the viscosity of the dispersion measured by a B-type viscometer at 25 ℃ and 30 rpm.
The "thixotropic ratio of the dispersion" is a value calculated by dividing the viscosity of the dispersion measured at a rotation speed of 30rpm by the viscosity of the dispersion measured at a rotation speed of 60 rpm.
The "static surface tension" was determined by the Wilhelmy method using an automatic surface tensiometer CBVP-Z type (manufactured by Kyowa interface science Co., Ltd.) using a 0.1 mass% aqueous solution of a water-soluble compound.
"dynamic surface tension" is a dynamic surface tension at a bubble generation period of 6Hz by a maximum bubble pressure method at 25 ℃ of a 0.1 mass% aqueous solution of a water-soluble compound; the dynamic surface tension of an aqueous solution containing a water-soluble compound at a ratio of 0.1% by mass is a value measured by the maximum bubble pressure method in which a sensor, a dynamic surface tension instrument SITA t60 manufactured by british herbal laboratories corporation (british herbal and reishi), is immersed in an aqueous solution in an environment at a temperature of 25 ℃. The measurement was performed with the bubble generation period of the aqueous solution set to 6 Hz.
The "average particle diameter (D50) of the particles" is a cumulative 50% diameter on a volume basis of the particles determined by a laser diffraction/scattering method. That is, the particle size distribution of the particles was measured by a laser diffraction scattering method, and a cumulative curve was obtained with the total volume of the particle group as 100%, and the particle size at the point where the cumulative volume reached 50% on the cumulative curve.
"90% cumulative volume particle diameter of powder (D90)" is a cumulative 90% diameter based on the volume of particles determined in the same manner.
The "unit" in the polymer may be a radical formed directly from a monomer by polymerization, or a radical obtained by treating a polymer obtained by polymerization in a predetermined method to convert a part of the structure. The unit based on the monomer a contained in the polymer is also referred to simply as "monomer a unit".
The dispersion liquid of the present invention (the present dispersion liquid) comprises: particles of Polytetrafluoroethylene (PTFE), particles of a tetrafluoroethylene-based polymer (hereinafter referred to as "PFA") containing units based on perfluoro (alkyl vinyl ether) (PAVE), a water-soluble compound having a boiling point of 100 ℃ or higher, and water, wherein the water-soluble compound is at least one selected from the group consisting of a glycol, a monoether of a glycol, and a monoacetate of a glycol.
PFA is a polymer containing units based on Tetrafluoroethylene (TFE) (TFE units), and is a polymer different from PTFE.
The dispersion has high dispersion stability and excellent liquid properties (viscosity or thixotropic ratio), and a molded article formed from the dispersion has excellent physical properties (particularly, adhesiveness to a substrate). The reason is not necessarily clear, but the following reason is considered.
The water-soluble compound contained in the dispersion liquid is a compound having a predetermined boiling point derived from the structure of a diol (formula: HO-Q-OH; wherein Q is a divalent aliphatic hydrocarbon group, and 2 hydroxyl groups are bonded to different carbon atoms). It is considered that the compound is highly soluble in the present dispersion containing polymer particles to exhibit various effects. Specific examples of the action include: the dispersant is effective for improving the dispersibility of the polymer particles by effectively covering the surfaces of the polymer particles, the dispersant is effective for serving as a dispersion medium which itself serves as a dispersoid of the polymer particles, and the viscosity modifier or thixotropy-imparting agent is effective for stabilizing the state of the dispersion (viscosity, thixotropic ratio, etc.).
PTFE has unique physical properties represented by fibrillar properties. Therefore, although PTFE particles have a certain water dispersibility, they are easily deteriorated by physical stress (shear, etc.), chemical change (temperature, pH, etc.), or change with time.
PFA is a crystalline polymer containing TFE units, the particles of which are still water-dispersible, and which is not easily affected by the above stress or the above change in an aqueous dispersion.
In the present dispersion, it is considered that the interaction between the PTFE particles and the PFA particles is promoted by the action of the water-soluble compound, and at least a part of the polymer particles of both form soft pseudo secondary particles, whereby the dispersion stability of the entire dispersion is improved.
Furthermore, since the boiling point of the water-soluble compound is within a predetermined range and the water-soluble compound is also volatilized and removed when water is removed from the dispersion by heating, molded articles having various excellent physical properties can be formed. Specifically, the dispersion can form a molded article having high physical properties of PTFE and also having adhesiveness derived from the physical properties of PFA.
The PTFE in the present invention may be a homopolymer of TFE, or a copolymer of TFE with a very small amount of a comonomer (PAVE, hexafluoropropylene, fluoroalkylethylene, etc.). The PTFE of the latter preferably contains 99.9 mol% or more of TFE units relative to the total units. The PTFE may also be a low molecular weight PTFE.
The melt viscosity of PTFE is 1X 10 at 380 deg.C2Pa · s or more, more preferably 1X 103Pa · s or more, and more preferably 1X 109Pa · s or more. The upper limit of the melt viscosity is usually 1X 1010Pa·s。
PTFE preferably has fibrillar properties.
The PTFE particles of the present invention are preferably made of PTFE. The PTFE content in the PTFE particles is preferably 80 mass% or more, and more preferably 100 mass%.
Examples of the other component that may be contained in the PTFE particles include aromatic polyesters, polyamide-imides, thermoplastic polyimides, polyphenylene ethers, and polyphenylene ethers.
The D50 of the PTFE particles is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.4 μm or less. The D50 of the PTFE particles is preferably 0.01 μm or more, more preferably 0.1 μm or more. The D90 of the PTFE particles is preferably 1 μm or less, more preferably 0.5 μm or less.
The PFA in the present invention is a polymer containing TFE units and PAVE units.
The melting temperature of PFA is preferably 260-325 ℃, more preferably 290-320 ℃.
The PFA preferably contains 2 to 10 moles or more of PAVE units based on the total units. In this case, the interaction between the PTFE particles and the PFA particles is further improved by the above action mechanism, and the dispersion stability of the present dispersion is more easily improved.
As PAVE, CF is mentioned2＝CFOCF3(PMVE)、CF2＝CFOCF2CF3、CF2＝CFOCF2CF2CF3(PPVE)、CF2＝CFOCF2CF2CF2CF3PMVE and PPVE are preferred.
The PFA preferably has an oxygen-containing polar group (polar functional group). Since PFA having an oxygen-containing polar group has high affinity with a water-soluble compound, the interaction with the particles of PTFE is more easily improved by the above action mechanism, and the dispersion stability of the present dispersion is more easily improved.
The oxygen-containing polar groups may be included in units in the PFA or in the end groups of the polymer backbone.
The former embodiment may be a PFA containing a unit based on a monomer having an oxygen-containing polar group.
The latter embodiment may, for example, be PFA having an oxygen-containing polar group as an end group derived from a polymerization initiator, a chain transfer agent or the like, or PFA having an oxygen-containing polar group obtained by plasma treatment or ionization treatment.
The oxygen-containing polar group is preferably a hydroxyl-containing group or a carbonyl-containing group, and more preferably a carbonyl-containing group from the viewpoint of further improving the dispersibility of the present dispersion.
The hydroxyl-containing group is preferably an alcoholic hydroxyl-containing group, more preferably-CF2CH2OH or-C (CF)3)2OH。
The carbonyl-containing group is preferably a carbonyl (& gt, C (O)) containing group, a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH)2) An anhydride residue (-CO (O) OC (O) -), an imide residue (-C (O) NHC (O) -, etc.) or a carbonate group (-OC (O) O-).
When the PFA has a carbonyl group, the number of the carbonyl group in the PFA is 1X 10 carbon atoms per main chain6Preferably 10 to 5000, and more preferably 50 to 2000. The number of carbonyl groups contained in the PFA can be determined by the composition of the polymer or the method described in International publication No. 2010/145133.
The monomer having an oxygen-containing polar group is preferably itaconic anhydride, citraconic anhydride, and 5-norbornene-2, 3-dicarboxylic anhydride (alias: nadic anhydride; hereinafter also referred to as "NAH").
Preferred specific examples of the PFA include PFAs having a melting temperature of 260 to 320 ℃ and containing TFE units and PAVE units in an amount of 1.0 to 5.0 mol% based on the total units, PFAs (1) having an oxygen-containing polar group and containing TFE units, PAVE units and units based on a monomer having an oxygen-containing polar group, and PFAs (2) having no oxygen-containing polar group and containing TFE units and PAVE units in an amount of 2.0 to 5.0 mol% based on the total units.
These PFAs are excellent in particle dispersion stability, and can be more easily and densely and homogeneously distributed in a molded article (polymer layer or the like) formed from the present dispersion. Further, fine spherulites are easily formed in the molded article, and adhesion to other components is easily improved. As a result, a molded article having high physical properties of each of the three components can be more easily formed.
The PFA (1) preferably contains 90 to 99 mol% of TFE units, 1.5 to 5.0 mol% of PAVE units and 0.01 to 3 mol% of units based on the monomer having the oxygen-containing polar group, respectively, relative to the total units.
Specific examples of PFA (1) include the polymers described in International publication No. 2018/16644.
The PFA (2) preferably consists of only TFE units and PAVE units, and contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units relative to the total units.
The content of PAVE units in PFA (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on the total units.
The fact that the polymer (2) does not contain an oxygen-containing polar group means that the number of carbon atoms constituting the main chain of the polymer is 1X 106And the number of the oxygen-containing polar groups of the polymer is less than 500. The number of the oxygen-containing polar groups is preferably 100 or less, and more preferably less than 50. The lower limit of the number of the above-mentioned oxygen-containing polar groups is usually 0.
PFA (2) can be produced by using a polymerization initiator or a chain transfer agent that does not generate an oxygen-containing polar group that becomes a terminal group of a polymer chain, or by subjecting an F polymer having an oxygen-containing polar group (e.g., an F polymer having an oxygen-containing polar group derived from a polymerization initiator on a terminal group of a polymer main chain) to a fluorination treatment. As a method of the fluorination treatment, a method using a fluorine gas can be mentioned (see Japanese patent laid-open publication No. 2019-194314).
The particles of PFA in the present invention are preferably made of PFA. The content of PFA in the PFA particles is preferably 80% by mass or more, more preferably 100% by mass.
Examples of the other components that may be contained in the particles of the PFA include a resin different from the PFA and an inorganic substance. Examples of the different resin include aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene ether.
Examples of the inorganic substance include silicon dioxide (silica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, and the like), boron nitride, and magnesium metasilicate (talc).
The particles of PFA containing a resin or an inorganic substance different from PFA preferably have a core-shell structure in which PFA is a core and the resin or the inorganic substance is a shell, or a core-shell structure in which PFA is a shell and the resin or the inorganic substance is a core. The particles of the PFA can be obtained, for example, by bonding (collision, aggregation, or the like) the particles of the PFA to the particles of the resin or the inorganic substance.
The D50 of the PFA particles is preferably 5 μm or less, more preferably 0.4 μm or less. The D50 of the PFA particles is preferably 0.01 μm or more, more preferably 0.1 μm or more. The D90 of the PFA particles is preferably 10 μm or less, more preferably 5 μm or less.
The content of PTFE in the present dispersion is preferably 10 mass% or more, and more preferably 20 mass% or more. The content of PTFE is preferably 50 mass% or less, and more preferably 40 mass% or less.
The content of PFA in the present dispersion is preferably 1 mass% or more, and more preferably 2 mass% or more. The content of PFA is preferably 20% by mass or less, more preferably 10% by mass or less.
The ratio (mass ratio) of the content of PFA to the content of PTFE in the present dispersion by mass is preferably 0.4 or less, more preferably 0.2 or less, and further preferably 0.1 or less. The above ratio is preferably 0.01 or more, more preferably 0.05 or more.
Within this range, not only is the dispersion stability of the present dispersion improved more easily by the above-mentioned action mechanism, but also the physical properties of PTFE in the formed article are highly exhibited and the adhesion to the substrate is also improved easily.
The water-soluble compound in the dispersion is a compound having a boiling point of 100 ℃ or higher, which is at least one compound selected from the group consisting of a glycol, a monoether of a glycol, and a monoacetate of a glycol. The water-soluble compound may be one kind or two or more kinds. In the case of two or more species, different water-soluble compounds are preferably compatible with each other.
The water-soluble compound is preferably a non-ionic compound in a non-polymeric form.
The molecular weight of the water-soluble compound is preferably 60 to 2000, more preferably 100 to 1000.
The boiling point of the water-soluble compound is 100 ℃ or higher, preferably 100 to 400 ℃, more preferably 100 to 300 ℃, further preferably 105 to 275 ℃, and particularly preferably 200 to 250 ℃. In this case, when a molded article is formed by removing water from the dispersion by heating, the water-soluble compound is less likely to remain in the molded article, and various physical properties (electrical insulation and the like) of the molded article are likely to be improved. In addition, since the water-soluble compound is removed slower than water, the surface smoothness of the molded article is more likely to be improved.
The water-soluble compound in the present dispersion can also be said to be a compound having a structure derived from an oxyalkylene group.
The molecular weight dispersion of the water-soluble compound is preferably less than 2.0, more preferably 1.8 or less. The lower limit of the molecular weight dispersity is preferably more than 1.0.
The HLB value of the water-soluble compound is preferably 1 to 18, more preferably 10 to 16, and still more preferably 10 to 14. The HLB value is calculated by Griffin's formula, and is obtained by multiplying a value obtained by dividing the molecular weight of the polyoxyalkylene moiety in the water-soluble compound by the molecular weight of the water-soluble compound by 20 times.
The static surface tension of the water-soluble compound is preferably 28N/cm or less. The static surface tension is preferably 20N/cm or more, more preferably 22N/cm or more.
The dynamic surface tension of the water-soluble compound is preferably 40m N/m or less, more preferably 35mN/m or less, and the dynamic surface tension is preferably 20mN/m or more.
When the physical properties of the water-soluble compound satisfy these ranges, the above-mentioned action mechanism is enhanced, and a dispersion or a liquid composition having low viscosity, in particular, the physical properties of the present dispersion, can be easily obtained.
Specific examples of the diol include: 2, 4-diethyl-1, 5-pentanediol [264 ℃ C ], 1, 2-propanediol [187 ℃ C ], 2-methyl-2, 4-pentanediol [197 ℃ C ], 2-butyl-2-ethyl-1, 3-propanediol [178 ℃ C ], ethylene glycol [198 ℃ C ], 2-ethyl-1, 3-hexanediol [ 241-249 ℃ C ], diethylene glycol [245 ℃ C ], triethylene glycol [288 ℃ C ].
Specific examples of the monoether of a glycol include: diethylene glycol monomethyl ether [194 ℃ C ], diethylene glycol monoethyl ether [202 ℃ C ], diethylene glycol monobutyl ether [230 ℃ C ], ethylene glycol mono-2-ethylhexyl ether [229 ℃ C ], dipropylene glycol monobutyl ether [ 222-232 ℃ C ], triethylene glycol monomethyl ether [248 ℃ C ], tripropylene glycol monobutyl ether [242 ℃ C ], and other glycol monoaryl ethers such as propylene glycol monophenyl ether [243 ℃ C ].
Specific examples of the monoacetate of a diol include: diethylene glycol monoethyl ether acetate [217 ℃ C ], diethylene glycol monobutyl ether acetate [247 ℃ C ].
The temperatures in parentheses in the above examples are the boiling points of the respective compounds.
The water-soluble compound is preferably a glycol monoalkyl ether, a glycol monoaryl ether, a glycol monoalkyl ether acetate, and a glycol monoaryl ether acetate, and more preferably a glycol monoalkyl ether.
The glycol monoalkyl ether is preferably a polyoxyethylene glycol monoalkyl ether. Oxyethylene unit (-COCH) contained in polyoxyethylene glycol2CH2-) preferably 1 to 10, and monoalkyl ether groups preferably being highly branched.
Preferable specific examples of the water-soluble compound include: polyoxyethylene decyl ether, polyoxyethylene undecyl ether, polyoxyethylene dodecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene tetradecyl ether, triethylene glycol monomethyl ether, polyethylene glycol trimethylnonyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate.
The water-soluble compounds are commercially available (from Tao chemical company, ダウケミカル, "Tergitol" and the like), and specifically "Tergitol TMN-100X" (produced by Tao chemical Co., Ltd), "Lutensol TO 8", "Lutensol XL 70", "Lutensol XL 80", "Lutensol XL 90", "Lutensol XP 80", "Lutensol M5" (produced by BASF Co., Ltd.), "Newcol 1305", "Newcol FA 1308", "Newcol 1310" (produced by Nippon emulsifier Co., Ltd.), "Leocol TDol N-90-80", "Leocol SC-90" (produced by Leo king specialty Chemicals Co., Ltd. (ライオン, スペシャリティ, ケミカルズ)).
The content of water in the present dispersion is preferably 10% by mass or more, more preferably 20% by mass or more. The water content is preferably 70% by mass or less, more preferably 60% by mass or less.
The content of the water-soluble compound in the present dispersion is preferably 1% by mass or more, more preferably 5% by mass or more. The content of the water-soluble compound is preferably 50% by mass or less, more preferably 40% by mass or less.
The ratio by mass (mass ratio) of the content of the water-soluble compound to the content of water in the present dispersion is preferably 2 or less, more preferably 1.5 or less. The above ratio is preferably 0.1 or more, more preferably 0.5 or more.
Within this range, the dispersion stability of the present dispersion is more easily improved by the interaction between the PTFE particles and the PFA particles through the above action mechanism.
The dispersion may contain other components such as a surfactant, a thixotropy-imparting agent, a viscosity-adjusting agent, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weather-resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a mold release agent, a surface treatment agent, a flame retardant, and various fillers, in addition to the PTFE particles, the PFA particles, water, and the water-soluble compound.
The present dispersion liquid preferably further contains a surfactant from the viewpoint of further improving dispersion stability, improving particle settling properties, and handling properties. The surfactant is preferably nonionic.
The hydrophilic site of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
The oxyalkylene group may be composed of one kind of oxyalkylene group, or may be composed of two or more kinds of oxyalkylene groups. In the latter case, the different types of oxyalkylene groups may be arranged randomly or in blocks.
The oxyalkylene group is preferably an oxyethylene group.
The hydrophobic portion of the surfactant preferably has an ethynyl group, a polysiloxane group, a perfluoroalkyl group, or a perfluoroalkenyl group. In other words, the surfactant is preferably an acetylene type surfactant, a silicone type surfactant, or a fluorine type surfactant.
Among these, the surfactant is more preferably a fluorine-based surfactant, and still more preferably a fluorine-based surfactant having a hydroxyl group (particularly, an alcoholic hydroxyl group) or an oxyalkylene group and a perfluoroalkyl group or a perfluoroalkenyl group.
Specific examples of the surfactant include: "Ftergent" series (available from Nippon corporation, ネオス), "Surflon" series (available from AGC Kaishi (AGC セイミケミカル)), "MEGA FACE" series (available from DIC Kaishi (DIC Co., Ltd.), "Unidyne" series (available from Dajin Industrial Co., Ltd. (ダイキン, )).
When the dispersion contains a surfactant, the content thereof is preferably 1 to 15% by mass. In this case, the dispersion stability of the present dispersion liquid is more easily improved.
The present dispersion may contain a resin (polymer) other than PTFE and PFA. The other resin may be a thermosetting resin or a thermoplastic resin.
Examples of the other resin include: epoxy resin, maleimide resin, polyurethane resin, elastomer, polyimide, polyamic acid, polyamide imide, polyphenylene ether, liquid crystal polyester.
A preferable embodiment of the other resin is an aromatic polymer. The aromatic polymer is preferably an aromatic polyimide and an aromatic polyamic acid, and more preferably a thermoplastic aromatic polyimide. In this case, when a molded article is formed from the dispersion, chipping of the PTFE particles and the PFA particles is also suppressed, and the adhesiveness is more easily improved.
When the dispersion contains an aromatic polymer, the content thereof is preferably 5 to 25% by mass. Further, the ratio by mass (mass ratio) of the aromatic polymer to the total content of PTFE and PFA is preferably 1.0 or less, and more preferably 0.1 to 0.7.
The present dispersion liquid in the case of containing another resin may be produced by mixing the present dispersion liquid with particles of another resin, or may be produced by mixing the present dispersion liquid with a varnish containing another resin.
The viscosity of the present dispersion is preferably 50 mPas or more, more preferably 100 mPas or more. The viscosity of the present dispersion is preferably 1000 mPas or less, more preferably 800 mPas or less, still more preferably 500 mPas or less, particularly preferably 360 mPas or less.
The thixotropic ratio of the present dispersion is preferably 1.0 or more. The thixotropic ratio of the present dispersion is preferably 3.0 or less, more preferably 2.0 or less.
The dispersion liquid can be easily adjusted to the viscosity or thixotropy in the above range by the above mechanism of action, and is excellent in dispersion stability and workability.
The pH value of the dispersion liquid is preferably 1-8. In this case, the dispersion is likely to have excellent hue and storage stability.
Examples of the method for producing the dispersion include: a method of mixing an aqueous dispersion of particles containing PTFE with a liquid composition containing particles of PFA and a water-soluble compound, or a method of mixing an aqueous dispersion of particles containing PTFE and an aqueous dispersion of particles containing PFA with a water-soluble compound. In the latter method, the water-soluble compound may be mixed after the two aqueous dispersions are mixed, or may be mixed in advance in either aqueous dispersion.
It is preferable that the aqueous dispersion and the liquid composition are mixed in each well-dispersed state. For example, in the case where the solid content in the liquid composition is observed to be settled, it is preferable to perform a dispersion treatment of the liquid composition with a homomixer and then a dispersion treatment with a homogenizer immediately before mixing. Particularly, when a liquid composition stored at 0 to 40 ℃ is used, it is preferable to perform these dispersion treatments.
The aqueous dispersion containing PTFE particles may be prepared by dispersing PTFE particles in water, or a commercially available aqueous dispersion may be used as it is.
A liquid composition containing particles of PFA and a water-soluble compound (hereinafter also referred to as "the present liquid composition") is preferably prepared by dispersing the particles of PFA in a water-soluble compound. The liquid composition is preferably a dispersion liquid in which particles of PFA are dispersed in a water-soluble compound.
The dispersion medium in the present liquid composition preferably contains a water-soluble compound as a main component, and preferably consists of a water-soluble compound. The term "comprising a water-soluble compound as a main component" means that the content of the water-soluble compound in the dispersion medium is 90% by mass or more. The dispersion medium other than the water-soluble compound may, for example, be water, an amide or an ester, and is preferably water.
The content of PFA in the liquid composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
The content of the water-soluble compound in the liquid composition is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass. When the liquid composition further contains a dispersion medium other than the water-soluble compound, the content is preferably 1 to 10% by mass.
In the present liquid composition, the form of PFA, particles of PFA, or water-soluble compound includes the same preferred forms as those in the present dispersion.
The present liquid composition may also contain other components in addition to the particles of PFA and the water-soluble compound. The forms of the other ingredients, including their preferred forms, are the same as those in the present dispersion.
Specifically, it is preferable that the present liquid composition further comprises a surfactant. The forms of the surfactants are the same as those in the present dispersion.
When the liquid composition contains a surfactant, the content of the surfactant is preferably 1 to 30% by mass.
The liquid composition may also be used in a wet milling process. When the liquid composition is subjected to wet grinding, the dispersion state and particle size of the PFA particles in the liquid composition can be easily adjusted.
The D50 of the particles of the regulated PFA is preferably 1 μm or less, more preferably 0.8 μm or less. The D50 of the PFA particles is preferably 0.1 μm or more, more preferably 0.2 μm or more. When the present liquid composition containing such PFA fine particles is used, the present dispersion having a higher density (density) can be produced.
The wet polishing method may, for example, be a wet jet polishing method.
In the wet jet milling method, the liquid composition is preferably supplied to the jet mill 20 to 60 times, more preferably 30 to 50 times. In this case, a sufficient effect of micronization can be obtained without impairing the state of the PFA particles.
The dispersion liquid is excellent in dispersion stability and storage stability, and can form a molded article which is excellent in crack resistance and exhibits strong adhesion to a substrate without impairing the physical properties of PTFE.
When the dispersion is applied to the surface of a substrate and heated to form a polymer layer (hereinafter also referred to as "F layer") containing PTFE and PFA, a laminate (this laminate) having a substrate layer composed of the substrate and the F layer can be produced.
In the production of the laminate of the present invention, the F layer may be formed on at least one surface of the substrate, and the F layer may be formed only on one surface of the substrate or may be formed on both surfaces of the substrate. The surface of the substrate may be subjected to surface treatment such as silane coupling agent.
In the case of the dispersion liquid coating, a coating method such as a spray method, a roll coating method, a spin coating method, a gravure coating method, a microgravure coating method, a gravure offset coating method, a blade coating method, a kiss coating method, a bar coating method, a die coating method, a jet meyer bar coating method, or a comma coating method can be used.
The F layer is preferably formed by heating to remove the dispersion medium and then firing the polymer, and particularly preferably formed by heating the substrate to a temperature at which the dispersion medium volatilizes (100 to 300 ℃) and then heating the substrate to a temperature range at which the polymer is fired (300 to 400 ℃). That is, the F layer preferably contains a fired product of PTFE and PFA.
The thickness of the F layer is preferably 0.1 μm or more, more preferably 1 μm or more. The upper limit of the thickness is 100. mu.m. Within this range, an F layer having excellent crack resistance can be easily formed.
The peel strength between the F layer and the substrate layer is preferably 10N/cm or more, more preferably 15N/cm or more. The peel strength is preferably 100N/cm or less. By using the dispersion, the laminate can be easily formed without impairing the physical properties of PTFE in the F layer.
Examples of the material of the substrate include: copper, aluminum, iron, glass, resin, silicon, ceramics.
The shape of the substrate may be, for example, a planar shape, a curved shape, an uneven shape, or any of a foil shape, a plate shape, a film shape, and a fiber shape.
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, a multilayer film having a polyimide film and F layers on both surfaces of the polyimide film. These laminates are excellent in various physical properties such as electrical properties and are suitable as printed wiring board materials and the like. Specifically, the laminate can be used for manufacturing a flexible printed circuit board or a rigid printed circuit board.
When the woven fabric is impregnated with the dispersion and dried by heating, an impregnated woven fabric (woven fabric) in which the woven fabric is impregnated with PTFE and PFA can be obtained. The woven fabric may be a coated woven fabric in which the woven fabric is coated with the F layer.
The woven fabric is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric, and is preferably a glass fiber woven fabric or a carbon fiber woven fabric. The woven fabric may be treated with a silane coupling agent from the viewpoint of improving the adhesion to the F layer.
The total content of PTFE and PFA in the woven fabric is preferably 30 to 80 mass%.
Examples of the method for impregnating a woven fabric with the dispersion include: a method of immersing a woven fabric in the dispersion, and a method of applying the dispersion to a woven fabric.
The polymer may be calcined when the woven fabric is dried. The method of firing the polymer may, for example, be a method of passing the woven fabric through a through-air drying oven at 300 to 400 ℃. Further, the drying of the woven fabric and the firing of the polymer may be performed in one step.
The fabric has excellent properties such as high adhesion (adhesiveness) between the F layer and the fabric, high surface smoothness, and less deformation. When the woven fabric is thermally pressure-bonded to a metal foil, a metal-clad laminate having high peel strength and being less likely to warp can be obtained, and the metal-clad laminate is suitable for use as a printed board material.
In the production of the woven fabric, the woven fabric impregnated with the dispersion may be applied to the surface of a substrate, heated and dried to form an impregnated woven fabric layer containing PTFE, PFA and woven fabric, and a laminate in which the substrate and the impregnated woven fabric layer are sequentially laminated may be produced. The form of the dispersion is not particularly limited, and an impregnated woven fabric layer can be formed on a part or all of the inner wall surface of a member such as a tank, a pipe, or a container by applying the woven fabric impregnated with the dispersion to a part or all of the inner wall surface and heating the member while rotating the member. The production method is also used as a lining method for inner wall surfaces of members such as tanks, pipes, and vessels.
The dispersion liquid has excellent dispersion stability as described above, and can highly impregnate a porous or fibrous material.
Examples of such porous or fibrous materials include materials other than the woven fabric, specifically, plate-like, columnar, or fibrous materials. These materials may be pretreated with a curable resin, a silane coupling agent, or the like in advance, or may be filled with an inorganic filler or the like. In addition, these materials may also be twisted into filaments, cables, threads. In the case of twisting, an interlayer made of another polymer such as polyethylene may be disposed.
As an example of a method for producing a molded article by impregnating the material with the present dispersion liquid, a method of impregnating a fibrous material carrying a curable resin or a cured product thereof with the present dispersion liquid may be mentioned.
The fibrous material may be a high-strength and low-elongation fiber such as a carbon fiber, an aramid fiber, or a silicon carbide fiber.
The curable resin is preferably a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, or a polyurethane resin.
A specific example of the above embodiment is a composite cable obtained by impregnating a cable obtained by twisting carbon fibers carrying a thermosetting resin with the dispersion, and then heating the resulting cable to sinter the F polymer. The composite cable can be used as a cable for large-scale structures, ground anchoring, oil excavation, cranes, cableways, elevators, agriculture, forestry, aquatic products and suspension cables.
Examples
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
The following materials were used.
＜PFA＞
PFA 1: a carbon number of 1X 10 relative to the main chain, containing TFE units, NAH units and PPVE units in an amount of 97.9 mol%, 0.1 mol% and 2.0 mol% in this order6A copolymer having 1000 carbonyl groups (melting point: 300 ℃ C.)
PFA 2: a carbon number of 1X 10 relative to the main chain, containing 97.5 mol% and 2.5 mol% of TFE unit and PPVE unit in this order6Copolymer having 40 carbonyl groups (melting point: 305 ℃ C.)
< surfactant >
Surfactant 1: f (CF)2)6CH2(OCH2CH2)7OCH2CH(CH3)OH
< Water-soluble Compound >
Water-soluble compound 1: triethylene glycol monomethyl ether
Water-soluble compound 2: a glycol monoalkyl ether (polyoxyethylene tridecyl ether) having an HLB value of 14, a static surface tension of 28mN/m, and a boiling point of 100 ℃ or higher
Water-soluble compound 3: a glycol monoalkyl ether (polyoxyethylene tridecyl ether) having an HLB value of 11, a static surface tension of 27mN/m, and a boiling point of 100 ℃ or higher
Example 1 preparation of liquid composition
After 15 parts by mass of PFA1 particles (D50: 2.0 μm), 5 parts by mass of surfactant 1 and 80 parts by mass of water-soluble compound 1 were put into a pot, zirconia balls were put into the pot, and the pot was rolled at 150 rpm. times.1 hours to obtain liquid composition 1.
Then, the liquid composition 11 was subjected to wet grinding using a wet jet mill ("JN 100" manufactured by Kokuku K.K.; flow channel diameter: 100 μm). The wet grinding method was carried out at an internal temperature of 15 ℃ and a pressure of 150MPa for 30 passage times to obtain a liquid composition 12 containing PFA1 particles (D50: 0.3 μm).
Example 2 preparation of Dispersion
To 70 parts by mass of an aqueous dispersion (AGC corporation, "AD-911E") containing 60% by mass of particles (D50: 0.3 μm) made of PTFE, 30 parts by mass of a liquid composition 11 was added to obtain a dispersion 1 containing PTFE particles, PFA1 particles, a water-soluble compound 1, and water (PFA 1/PTFE: 1/9 (mass ratio)).
Dispersion 2 was obtained in the same manner as dispersion 1 except that liquid composition 12 was used instead of liquid composition 11.
Dispersion 3 was obtained in the same manner as in dispersion 1 except that dimethyl glycol was used instead of water-soluble compound 1.
A polyoxyalkylene polymer having a molecular weight of 1 ten thousand or more was mixed with an aqueous dispersion containing PTFE particles and PFA1 particles to obtain dispersion 4.
Liquid composition 13 was obtained in the same manner as liquid composition 12 except that particles of PFA1 (D50: 2.0 μm) were replaced with particles of PFA2 (D50: 1.8 μm). Dispersion 5 was obtained in the same manner as dispersion 1 except that liquid composition 13 was used instead of liquid composition 11.
Example 3 evaluation of Dispersion
The dispersibility of each dispersion immediately after preparation was visually confirmed, and the evaluation was performed according to the following criteria.
Good: no sediment was confirmed.
And (delta): the precipitate was confirmed, but dispersed by shaking with a hand.
X: it became a mousse-like shape and was not dispersed by merely shaking with hands.
The results are shown in Table 1.
| Number of Dispersion | Dispersibility |
| 1 | △ |
| 2 | 〇 |
| 3 | × |
| 4 | × |
| 5 | △ |
Example 4 evaluation of Dispersion
The dispersion 1 was applied to the surface of a copper foil (thickness: 18 μm), dried at 100 ℃ for 10 minutes, fired at 380 ℃ for 10 minutes in a nitrogen atmosphere, and then gradually cooled to obtain a laminate 1 of a copper foil and a polymer layer (thickness: 5 μm) comprising PTFE and PFA1 formed on the surface of the copper foil.
A laminate 2 was obtained in the same manner as the laminate 1, except that the dispersion 2 was used instead of the dispersion 1.
Rectangular (length: 100mm, width: 10mm) samples were cut out from the laminates 1 and 2. The sample was fixed at a distance of 50mm from one end in the longitudinal direction, and the metal foil and the polymer layer were peeled off at an angle of 90 ° from one end in the longitudinal direction at a stretching speed of 50 mm/min. The maximum load applied at this time was measured as the peel strength (N/cm), and as a result, the peel strength of the laminate was 10N/cm or more, respectively.
The surfaces of the polymer layers of laminates 1 and 2 were observed by SEM (magnification: 30000 times), and as a result, a dense fibrous layer derived from PTFE was formed on both surfaces without defects.
Example 5 production of liquid composition and Dispersion
After 5 parts by mass of the water-soluble compound 2 and 55 parts by mass of water were put into a pot, 40 parts by mass of PFA1 particles (D50: 2.0 μm) and zirconia balls were put into the pot, and the pot was rolled at 150 rpm.times.1 hours to obtain a liquid composition 1A (viscosity: 37 mPas).
After 5 parts by mass of the water-soluble compound 3 and 55 parts by mass of water were put into a pot, 40 parts by mass of PFA1 particles (D50: 2.0 μm) and zirconia balls were put into the pot, and the pot was rolled at 150 rpm.times.1 hours to obtain a liquid composition 1B (viscosity: 376 mPas).
After 5 parts by mass of the water-soluble compound 2 and 55 parts by mass of water were put into a pot, 40 parts by mass of PFA2 particles (D50: 1.8 μm) and zirconia balls were put into the pot, and the pot was rolled at 150 rpm.times.1 hour to obtain a liquid composition 1C (viscosity: 300 mPas).
The dispersibility of the liquid compositions 1A, 1B and 1C was evaluated in the same manner as in the dispersion, and the results were good, good and Δ in this order. In particular, the liquid composition 1A is a low-viscosity aqueous dispersion, and is excellent in miscibility with an aqueous dispersion of PTFE (manufactured by AGC, Ltd. "AD-1911E").
Industrial applicability of the invention
The dispersion liquid of the present invention has excellent dispersion stability, and can be used for producing molded articles (films, impregnated articles such as prepregs, laminated sheets, etc.) having the physical properties of PTFE and substrate adhesiveness. The dispersion of the present invention can be used as a material for antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, paints, cosmetics, and the like. Printed circuit boards can also be used as a novel printed circuit board material in place of conventional glass epoxy boards in order to prevent temperature rise in printed circuit boards on which electronic components are mounted at high density.
Specifically, the resin composition can be used as a coating material for electric wires (e.g., electric wires for aircraft), an electrically insulating tape, an insulating tape for oil drilling, a material for printed boards, a separation membrane (e.g., a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane, an ion exchange membrane, a dialysis membrane, or a gas separation membrane), an electrode adhesive (e.g., for lithium secondary batteries or fuel cells), a copying roll, furniture, an instrument panel of automobiles, a cover for home electric appliances, a sliding member (e.g., a load bearing, a sliding shaft, a valve, a bearing, a sleeve, a seal, a thrust washer, a wear ring, a piston, a slide switch, a gear, a cam, a conveyor belt, or a food conveyor belt), a wear pad, a wear strip, a tube lamp, a test sleeve, a wafer guide, a wear part for centrifugal pumps, hydrocarbons, chemicals, and water supply pumps, tools (e.g., a shovel, a file, a awl, or a saw), a boiler, a hopper, a pipeline, an oven, or a water supply pump, Barbecue molds, chutes, molds, toilets, container coating materials, coating materials inside and outside of glass containers. Examples of the glass container include vials, syringes (syringes), needle syringes, syringe barrels, and ampoules.
The dispersion of the present invention further containing a conductive filler is also suitable for applications requiring conductivity, such as the field of printed electronics. The method can be used for manufacturing conductive elements such as printed circuit boards, sensor electrodes, displays, base plates, RFID (radio frequency identification), solar power generation, illumination, disposable electronic equipment, automobile heaters, electromagnetic wave (EMI) shields and membrane switches.
The molded article obtained from the dispersion of the present invention 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, or for bonding a circuit board and a heat sink, or for bonding an LED chip and a substrate, in a semiconductor element, a high-density substrate, a module component, or the like. The molded article can also be used as a conductive bonding material between a circuit wiring and an electronic component in a mounting process of the electronic component (as an application in place of soldering). In addition, the adhesive can be used for an adhesive between a ceramic member and a metal member in an in-vehicle engine. The molded article can also be used in the application described in International publication No. 2016/017801 paragraph 0149.
Claims (15)
1. A dispersion, comprising: particles of polytetrafluoroethylene, particles of a tetrafluoroethylene-based polymer containing a perfluoro (alkyl vinyl ether) -based unit, a water-soluble compound having a boiling point of 100 ℃ or higher, and water, wherein the water-soluble compound is at least one selected from the group consisting of a glycol, a glycol monoether, and a glycol monoacetate.
2. The dispersion of claim 1 wherein the water soluble compound is a glycol monoalkyl ether, a glycol monoaryl ether, a glycol monoalkyl ether acetate or a glycol monoaryl ether acetate.
3. The dispersion liquid according to claim 1 or 2, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having an oxygen-containing polar group containing a perfluoro (alkyl vinyl ether) -based unit, or a tetrafluoroethylene-based polymer having no oxygen-containing polar group containing 2.0 to 5.0 mol% of the perfluoro (alkyl vinyl ether) -based unit relative to the total units.
4. The dispersion liquid according to any one of claims 1 to 3, wherein the average particle diameter of the polytetrafluoroethylene particles is 0.01 to 1 μm, and the average particle diameter of the tetrafluoroethylene polymer particles is 0.01 to 10 μm.
5. The dispersion liquid according to any one of claims 1 to 4, wherein a ratio of the content of the tetrafluoroethylene-based polymer to the content of the polytetrafluoroethylene by mass is 0.4 or less.
6. The dispersion liquid according to any one of claims 1 to 5, wherein a ratio of the content of the water-soluble compound to the content of the water by mass is 2 or less.
7. A process for producing a laminate, which comprises applying the dispersion liquid according to any one of claims 1 to 6 onto a surface of a substrate and heating the applied solution to form a polymer layer comprising the polytetrafluoroethylene and the tetrafluoroethylene-based polymer, thereby obtaining a laminate comprising a substrate layer comprising the substrate and the polymer layer.
8. A process for producing an impregnated woven fabric, which comprises impregnating a woven fabric with the dispersion liquid according to any one of claims 1 to 6 and heating the impregnated woven fabric to obtain an impregnated woven fabric comprising the polytetrafluoroethylene and the tetrafluoroethylene-based polymer.
9. A method for producing a dispersion according to any one of claims 1 to 6, wherein the dispersion is obtained by mixing an aqueous dispersion containing the polytetrafluoroethylene particles with a liquid composition containing the tetrafluoroethylene polymer particles and the water-soluble compound.
10. A liquid composition comprising: particles of a tetrafluoroethylene-based polymer containing a perfluoro (alkyl vinyl ether) -based unit, and a water-soluble compound having a boiling point of 100 ℃ or higher, wherein the water-soluble compound is at least one selected from the group consisting of a glycol, a glycol monoether, and a glycol monoacetate.
11. The liquid composition of claim 10, further comprising water.
12. The liquid composition according to claim 10 or 11, comprising 5 to 50 mass% of the tetrafluoroethylene polymer.
13. A liquid composition according to any one of claims 10 to 12, wherein the water-soluble compound has an HLB value of from 1 to 18.
14. The liquid composition according to any one of claims 10 to 13, wherein the viscosity is 1000 mPa-s or less.
15. A method for producing a liquid composition, characterized in that a liquid composition comprising particles of a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit and a water-soluble compound having a boiling point of 100 ℃ or higher, wherein the water-soluble compound is at least one selected from the group consisting of a glycol, a monoether of a glycol and a monoacetate of a glycol, is subjected to a wet milling method to obtain a liquid composition comprising the particles of the tetrafluoroethylene polymer and the water-soluble compound.
Applications Claiming Priority (7)
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| JP2019-230682 | 2019-12-20 | ||
| JP2019230682 | 2019-12-20 | ||
| JP2020-017845 | 2020-02-05 | ||
| JP2020017845 | 2020-02-05 | ||
| JP2020169406 | 2020-10-06 | ||
| JP2020-169406 | 2020-10-06 | ||
| PCT/JP2020/046899 WO2021125210A1 (en) | 2019-12-20 | 2020-12-16 | Dispersion liquid, liquid composition, and manufacturing methods therefor |
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| CN114787273A true CN114787273A (en) | 2022-07-22 |
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| JP (1) | JPWO2021125210A1 (en) |
| CN (1) | CN114787273A (en) |
| TW (1) | TW202140696A (en) |
| WO (1) | WO2021125210A1 (en) |
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| CN1180364A (en) * | 1995-03-31 | 1998-04-29 | 大金工业株式会社 | Aqueous polytetrafluoroethylene dispersion composition and use thereof |
| JP2001164064A (en) * | 1999-12-10 | 2001-06-19 | Daikin Ind Ltd | Dispersion composition of fluorine containing meltable resin and coated product |
| CN102993854A (en) * | 2011-09-09 | 2013-03-27 | 杜邦公司 | Coating composition used for non-stick coating and coating base material comprising patterns made from coating composition |
| WO2019131805A1 (en) * | 2017-12-27 | 2019-07-04 | Ａｇｃ株式会社 | Dispersion, metal laminate plate, and production method for printed board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0776302B2 (en) * | 1989-10-06 | 1995-08-16 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | Processing aids for polymers |
| JP3636531B2 (en) * | 1995-03-03 | 2005-04-06 | 株式会社クリエィティブ・プロダクツ・タシロ | Coating products |
| JP4306072B2 (en) * | 2000-01-28 | 2009-07-29 | ダイキン工業株式会社 | Fluoropolymer aqueous dispersion that can be melt processed |
| JP3873727B2 (en) * | 2001-12-04 | 2007-01-24 | ダイキン工業株式会社 | Fluorine-containing material-dispersed aqueous composition, coated article manufacturing method, and coated article |
| JP2003183565A (en) * | 2001-12-18 | 2003-07-03 | Daikin Ind Ltd | Fluorine-containing primer composition |
| JP2018002833A (en) * | 2016-06-30 | 2018-01-11 | セイコーエプソン株式会社 | Inkjet ink composition, and recording method |
| JP6811649B2 (en) * | 2017-03-07 | 2021-01-13 | ダイキン工業株式会社 | Compositions and coatings |
| JP7335685B2 (en) * | 2018-06-07 | 2023-08-30 | 三井・ケマーズ フロロプロダクツ株式会社 | Hot-melt fluororesin composition and injection-molded article made from the same |
| CN112334534B (en) * | 2018-06-27 | 2023-05-02 | Ａｇｃ株式会社 | Powder dispersion, laminate, film, and impregnated woven fabric |
-
2020
- 2020-12-16 WO PCT/JP2020/046899 patent/WO2021125210A1/en active Application Filing
- 2020-12-16 JP JP2021565613A patent/JPWO2021125210A1/ja active Pending
- 2020-12-16 CN CN202080085659.5A patent/CN114787273A/en active Pending
- 2020-12-18 TW TW109145023A patent/TW202140696A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180364A (en) * | 1995-03-31 | 1998-04-29 | 大金工业株式会社 | Aqueous polytetrafluoroethylene dispersion composition and use thereof |
| JP2001164064A (en) * | 1999-12-10 | 2001-06-19 | Daikin Ind Ltd | Dispersion composition of fluorine containing meltable resin and coated product |
| CN102993854A (en) * | 2011-09-09 | 2013-03-27 | 杜邦公司 | Coating composition used for non-stick coating and coating base material comprising patterns made from coating composition |
| WO2019131805A1 (en) * | 2017-12-27 | 2019-07-04 | Ａｇｃ株式会社 | Dispersion, metal laminate plate, and production method for printed board |
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| TW202140696A (en) | 2021-11-01 |
| WO2021125210A1 (en) | 2021-06-24 |
| JPWO2021125210A1 (en) | 2021-06-24 |
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