CN114729171B - Dispersion, method for producing dispersion, and molded article - Google Patents
Dispersion, method for producing dispersion, and molded article Download PDFInfo
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- CN114729171B CN114729171B CN202080078871.9A CN202080078871A CN114729171B CN 114729171 B CN114729171 B CN 114729171B CN 202080078871 A CN202080078871 A CN 202080078871A CN 114729171 B CN114729171 B CN 114729171B
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- molded article
- polymer
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Classifications
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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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Abstract
The present invention provides a dispersion liquid containing a predetermined tetrafluoroethylene polymer and a predetermined anisotropic filler, a method for producing the same, and a molded article having both properties. The dispersion of the present invention comprises a powder of a tetrafluoroethylene polymer containing units based on perfluoro (alkyl vinyl ether) or units based on hexafluoropropylene, an anisotropic filler having a Mohs hardness of 4 or less, and a liquid dispersion medium, wherein the average particle diameter of the powder is smaller than the average particle diameter of the anisotropic filler. The molded article of the present invention comprises a predetermined tetrafluoroethylene polymer containing units based on perfluoro (alkyl vinyl ether) and the anisotropic filler, wherein the anisotropic filler is present in an amount of 10 mass% or more in the molded article.
Description
Technical Field
The present invention relates to a dispersion liquid containing a predetermined anisotropic filler, a method for producing the same, and a molded article.
Background
Tetrafluoroethylene Polymer (PFA) containing perfluoro (alkyl vinyl ether) unit and tetrafluoroethylene polymer (FEP) containing hexafluoropropylene unit are excellent in properties such as releasability, electrical insulation, water/oil repellency, chemical resistance, weather resistance and heat resistance, and are used for processing into various molded articles.
Patent document 1 describes an electric wire tube excellent in electric insulation obtained by melt-kneading a dry blend of PFA powder and a boron nitride filler and extrusion molding.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-224228
Disclosure of Invention
Technical problem to be solved by the invention
However, the fluoropolymer has high melt viscosity and requires a strong stress when the fluoropolymer and the filler are melt kneaded. At this time, the properties (in particular, physical properties such as shape and surface state) of the filler itself are impaired, and the physical properties of the filler in the molded article tend to be degraded. The inventors have found that this tendency becomes pronounced when brittle fillers of low hardness are used, and more pronounced when fillers of low hardness and anisotropy are used.
The present inventors have studied intensively on obtaining a material suitable for molding the molded article without melt-kneading. As a result, the dispersion liquid containing the powder of the predetermined fluoropolymer and the predetermined anisotropic filler is excellent in dispersion stability and good in handling properties such as coatability. Further, the anisotropic filler itself of the molded article formed from the anisotropic filler is not easily impaired in its properties, and has high physical properties.
The present invention aims to provide the dispersion liquid and the formed article.
Technical means adopted for solving the technical problems
The present invention has the following configurations.
[1] A dispersion liquid comprising a powder of a tetrafluoroethylene polymer containing a perfluoro (alkyl vinyl ether) -based unit or hexafluoropropylene-based unit, an anisotropic filler having a mohs hardness of 4 or less, and a liquid dispersion medium, wherein the average particle diameter of the powder is smaller than the average particle diameter of the anisotropic filler.
[2] The dispersion of [1], wherein the content of the tetrafluoroethylene polymer and the content of the anisotropic filler are each 5 mass% or more.
[3] The dispersion liquid according to [1] or [2], wherein the anisotropic filler has a scale-like or plate-like shape.
[4] The dispersion liquid according to any one of [1] to [3], wherein the aspect ratio of the anisotropic filler is 2 or more.
[5] The dispersion according to any one of [1] to [4], wherein the anisotropic filler is a boron nitride or talc-containing anisotropic filler
[6] The dispersion according to any one of [1] to [5], wherein polytetrafluoroethylene powder or an aromatic polymer is further contained.
[7] The dispersion liquid according to any one of [1] to [6], wherein the component dispersion layer ratio is 60% or more.
[8] A method for producing a dispersion according to any one of [1] to [7], wherein the powder, the anisotropic filler, an inorganic filler having an average particle diameter smaller than that of the anisotropic filler, and a liquid dispersion medium are mixed.
[9] The production method according to [8], wherein the mixing is performed by stirring.
[10] A molded article comprising a tetrafluoroethylene polymer containing units based on perfluoro (alkyl vinyl ether) and an anisotropic filler having a Mohs hardness of 4 or less,
the tetrafluoroethylene polymer is a polymer having a polar functional group or a polymer having no polar functional group and containing 2.0 to 5.0 mol% of the perfluoro (alkyl vinyl ether) -based unit relative to the total units, and the anisotropic filler is present in an amount of 10 mass% or more in the molded article.
[11] The molded article of [10], wherein the aspect ratio of the anisotropic filler is 2 or more.
[12] The molded article according to [11], wherein the anisotropic filler is a scaly anisotropic filler containing boron nitride or a platy anisotropic filler containing talc.
[13] The molded article according to any one of [10] to [12], wherein the average particle diameter of the anisotropic filler is 1 μm or more.
[14] The molded article according to any one of [10] to [13], wherein polytetrafluoroethylene or an aromatic polymer is further contained.
[15] The molded article according to any one of [10] to [14], wherein the molded article is a layered molded article having a thickness of 150 μm or less.
Effects of the invention
According to the present invention, a dispersion liquid excellent in dispersibility and handleability is obtained which contains a prescribed fluoropolymer powder and a prescribed anisotropic filler. Further, a molded article having both of the physical properties and the electrical properties and being excellent in a high degree is obtained.
Detailed Description
The "average particle diameter (D50)" is a cumulative 50% diameter based on the volume of the object (powder or filler) obtained by the laser diffraction/scattering method. That is, the particle size distribution of the object is measured by a laser diffraction/scattering method, and a cumulative curve is obtained with the total volume of the particle clusters of the object being 100%, and the particle diameter at the point on the cumulative curve where the cumulative volume reaches 50% is obtained.
"D90" is the cumulative 90% diameter of the volume basis of the object measured in the same manner.
The "particle size distribution" is a distribution obtained by plotting the particle size (%) of each particle size range obtained in the same manner as a curve and indicating the curve.
The "melting temperature" is a temperature corresponding to the maximum value of the melting peak of the polymer measured by the Differential Scanning Calorimeter (DSC) method.
The "glass transition temperature" is a value measured by analyzing a polymer by a dynamic viscoelasticity measurement (DMA) method.
The "unit" in the polymer may be an atomic group directly formed from a monomer by polymerization, or may be an atomic group in which a part of the structure is converted by treating the polymer obtained by polymerization by a predetermined method. The monomer a-based unit contained in the polymer is also simply referred to as "monomer a unit".
The dispersion of the present invention (hereinafter referred to as "the present dispersion") contains a powder (hereinafter referred to as "F powder") of a tetrafluoroethylene polymer (hereinafter referred to as "F polymer") containing units based on perfluoro (alkyl vinyl ether) (PAVE units) or units based on Hexafluoropropylene (HFP) (HFP units), an anisotropic filler having a mohs hardness of 4 or less, and a liquid dispersion medium.
The average particle size of the F powder is smaller than that of the anisotropic filler. The dispersion has F powder and anisotropic filler dispersed therein.
The dispersion is excellent in dispersion stability and handleability, and can be easily formed into a molded article having high physical properties of an F polymer and an anisotropic filler. The reason for this is not clear, but the following is considered.
The anisotropic filler of the present invention is amorphous and has various properties (nodules and the like), and is said to be a fragile filler. In the present dispersion, the state of the anisotropic filler is unstable, and aggregation or sedimentation is likely to occur. In addition, the anisotropic filler is in a state in which its shape or properties are easily broken by physical stress (shear stress or the like).
On the other hand, the F polymer is a polymer having plasticity represented by hot melt processability, and the powder (fpowder) thereof is not easily affected by physical stress, and is excellent in dispersibility.
The present dispersion is in a state in which the average particle diameter of the F powder is smaller than the average particle diameter of the anisotropic filler, in other words, in a state in which the dispersion is densely contained and affinity between the anisotropic filler and the F powder tends to be relatively high. That is, since the F powder is densely contained in the dispersion liquid in a more particulate form, it is considered that pseudo secondary particles are easily formed between the F powder and the anisotropic filler. As a result, the dispersion state of the anisotropic filler is stabilized, and therefore, the dispersion stability and the handleability of the present dispersion are considered to be excellent.
If the F powder is melt-baked while removing the liquid dispersion medium from the present dispersion liquid, it is easy to mold the molded article while suppressing deformation of the anisotropic filler. In addition, in the course of removal of the liquid dispersion medium, highly filled shaped articles are easily obtained while the anisotropic filler is oriented. As a result, it is considered that a molded article having high physical properties of the F polymer and physical properties of the anisotropic filler is obtained from the present dispersion.
For example, if a molded article is formed from the present dispersion liquid containing a scaly or plate-like anisotropic filler, the anisotropic filler is oriented parallel to the surface (plane direction) of the molded article, and the physical properties of the anisotropic filler in the molded article are likely to be highly exhibited. Therefore, even a lamellar molded article tends to highly exhibit the physical properties of the F polymer and the physical properties of the anisotropic filler if the dispersion is used.
In addition, if the anisotropic filler is in a scale-like or plate-like form, the anisotropic filler forms a card house structure, and not only the liquid properties (viscosity, dispersion stability, etc.) of the present dispersion are improved, but also the anisotropic filler is more easily highly dispersed in a molded article formed from the anisotropic filler. As a result, the electrical characteristics of the molded article can be easily improved. In addition, when the molded article is subjected to stress, the anisotropic filler tends to disperse the stress and the mechanical strength (bending property, etc.) tends to be improved. In addition, since the channels of the anisotropic filler are formed in the molded article, the thermal conductivity of the molded article is easily improved.
The F powder in the present dispersion is preferably formed from an F polymer. The content of the F polymer in the powder is preferably 80 mass% or more, more preferably 100 mass%.
Examples of the other component that may be contained in the F powder include a resin or an inorganic substance different from the F polymer. Examples of the "different resins" may include aromatic polyesters, polyamideimides, thermoplastic polyimides, polyphenylene oxides and polyphenylene ethers.
Examples of the inorganic substance include silica (silica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (talc).
The F powder containing a resin or an inorganic substance different from the F polymer preferably has a core-shell structure having the F polymer as a core and the resin or the inorganic substance as a shell, or a core-shell structure having the resin or the inorganic substance as a core and the F polymer as a shell. The F powder can be obtained by, for example, combining (collision, aggregation, etc.) a powder of the F polymer with a powder of the aforementioned resin or inorganic substance.
The D50 of the F powder is preferably 10 μm or less, more preferably 6 μm or less, and still more preferably 4 μm or less. The D50 of the F powder is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 1 μm or more. Further, D90 of the F powder is preferably 20 μm or less, more preferably 10 μm or less. When the D50 and D90 of the F powder are within this range, the affinity with the anisotropic filler is further improved, and the dispersion stability of the dispersion liquid and the physical properties of the molded article thereof are more easily improved.
The content of the F powder in the present dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 25% by mass or more. The content of the F powder is preferably 50 mass% or less, more preferably 40 mass% or less, and still more preferably 30 mass% or less. When the content of the F powder is within this range, the densely contained F powder can improve the affinity between the F powder and the anisotropic filler, and the dispersion stability of the dispersion liquid can be easily further improved. In addition, the physical properties of the F polymer tend to be remarkably exhibited in the molded article.
The F polymer in the present dispersion is a polymer containing Tetrafluoroethylene (TFE) based units (TFE units). The F polymer may comprise both PAVE units and HFP units, or may comprise only either of them.
As PAVE, CF can be exemplified 2 ＝CFOCF 3 、CF 2 ＝CFOCF 2 CF 3 Or CF (CF) 2 ＝CFOCF 2 CF 2 CF 3 (PPVE), preferably PPVE.
The melting temperature of the F polymer is preferably 280 to 325℃and more preferably 285 to 320 ℃.
The glass transition temperature of the F polymer is preferably 75 to 125℃and more preferably 80 to 100 ℃.
The F polymer may have polar functional groups (polar functional groups). The polar functional groups may be contained in units in the F polymer or in terminal groups of the polymer backbone. The latter form may be exemplified by an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, and an F polymer having a polar functional group obtained by subjecting an F polymer to plasma treatment or ionizing radiation treatment.
The polar functional group is preferably a hydroxyl group-containing group or a carbonyl group-containing group, and from the viewpoint of further improving the dispersion stability of the present dispersion, a carbonyl group-containing group is more preferred.
The hydroxyl-containing group is preferably an alcoholic hydroxyl-containing group, more preferably-CF 2 CH 2 OH or-C (CF) 3 ) 2 OH。
The carbonyl-containing group is preferably a carbonyl (> C (O)) containing group, a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH) 2 ) Anhydride residues (-CO (O) OC (O) -), imide residues (-C (O) NHC (O) -, etc.) or carbonate groups (-OC (O) O-).
F the number of carbonyl-containing groups in the polymer is 1X 10 relative to the number of main chain carbons 6 Preferably 10 to 5000, more preferably 100 to 3000, and even more preferably 800 to 1500. The number of carbonyl groups in the F polymer can be quantified by the composition of the polymer or by the method described in International publication No. 2020/145133.
The F polymer is preferably a tetrafluoroethylene polymer containing PAVE units and containing 1.5 to 5.0 mol% of PAVE units relative to the total units, more preferably a polymer (1) having polar functional groups containing PAVE units and units based on a monomer having polar functional groups, or a polymer (2) having no polar functional groups containing PAVE units and containing 2.0 to 5.0 mol% of PAVE units relative to the total units.
These F polymers are not only excellent in dispersion stability of the powder, but also more easily densely and homogeneously distributed in a molded article (polymer layer or the like) formed from the present dispersion. Further, the formed product is liable to form fine spherulites, and adhesion with other components is liable to be improved. As a result, a molded article having three components with high physical properties can be formed more easily.
The polymer (1) preferably contains 90 to 99 mol% of TFE unit, 1.5 to 9.97 mol% of PAVE unit and 0.01 to 3 mol% of unit based on the monomer having polar functional group, respectively, with respect to the total units.
The monomer having a polar functional group is preferably itaconic anhydride, citraconic anhydride or 5-norbornene-2, 3-dicarboxylic anhydride (alias: nadic anhydride; hereinafter also referred to as "NAH").
As a specific example of the polymer (1), there can be mentioned a polymer described in International publication No. 2018/16644.
The polymer (2) preferably comprises only TFE units and PAVE units, and contains 95.0 to 98.0 mol% TFE units and 2.0 to 5.0 mol% PAVE units relative to the total units.
The PAVE unit content in the polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on the total units.
In addition, the fact that the polymer (2) has no polar functional group means that the number of carbon atoms relative to the main chain of the polymer is 1X 10 6 The polymer has less than 500 polar functional groups. The number of the polar functional groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of polar functional groups is usually 0.
The polymer (2) can be produced using a polymerization initiator, a chain transfer agent, or the like that does not generate a polar functional group that becomes an end group of a polymer chain, or can be produced by subjecting an F polymer having a polar functional group (an F polymer having a polar functional group derived from a polymerization initiator on an end group of a polymer main chain, or the like) to a fluorination treatment. Examples of the method of the fluorination treatment include a method using fluorine gas (see, for example, japanese patent application laid-open No. 2019-194314).
The anisotropic filler of the present invention has a mohs hardness of 4 or less, preferably 3 or less. The mohs hardness of the anisotropic filler is preferably 1 or more, more preferably 2 or more. Even in the case of a brittle anisotropic filler having a Mohs hardness in this range, the affinity of the anisotropic filler for F powder can provide the dispersion liquid with excellent dispersion stability, and the physical properties of the filler in the molded article can be easily improved.
The anisotropic filler may be used in 1 kind or 2 or more kinds different in average particle diameter or kind.
The shape of the anisotropic filler of the present invention may be any of a granular shape, a needle shape (fibrous shape), and a plate shape. Specific examples of the anisotropic filler include spherical, scaly, lamellar, leaf-like, almond-like, columnar, cockscomb-like, equiaxed, leaf-like, mica-like, block-like, flat-plate-like, wedge-like, rosette-like, grid-like, and square columnar.
The shape of the anisotropic filler is preferably a scale-like or plate-like shape. When a scaly or plate-like anisotropic filler is used, it forms a card house structure, and not only the liquid properties (viscosity, dispersion stability, etc.) of the dispersion are easily improved, but also the orientation of the filler in the molded article is easily improved, and the functions (mechanical strength, thermal conductivity, electrical characteristics, etc.) thereof are easily improved.
Examples of the anisotropic filler include carbon fillers, nitride fillers, mica fillers, clay fillers, and talc fillers, preferably boron nitride-containing or talc-containing fillers, and more preferably boron nitride-containing fillers. The crystal form of boron nitride may be any of hexagonal, rhombohedral, cubic, wurtzite. The dispersion liquid containing the anisotropic filler is excellent in dispersion stability and handleability. Further, the electric interference imparted to the F polymer by the filler in the molded article tends to increase, and as a result, the electric characteristics (particularly dielectric loss tangent) of the molded article tend to be good. In addition, the thermal conductivity of the molded article is easily improved.
The content of boron nitride in the boron nitride-containing filler is preferably 95 mass% or more, more preferably 99 mass% or more, and still more preferably 99.5 mass% or more. The upper limit of the content is 100 mass%. In this case, the low linear expansibility and electrical characteristics of the molded article tend to be improved.
When the anisotropic filler is added to water, the pH of the water may be any of acidic, neutral and alkaline, and is preferably alkaline.
The specific surface area of the anisotropic filler is preferably 1 to 20m 2 Preferably 3 to 8m 2 And/g. In this case, the anisotropic filler in the dispersion is easily wetted, and affinity with the F polymer is easily improved. In addition, the anisotropic filler and the F polymer in the molded article are more easily uniformly dispersed (distributed), and the physical properties of both are more easily exhibited with good balance.
The surface of the anisotropic filler may be surface treated.
Examples of the surface treatment agent include polyhydric alcohols (trimethylolethane, pentaerythritol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkanolamines, amines (trimethylamine, triethylamine, etc.), paraffins, silane coupling agents, silicones, polysiloxanes, and inorganic substances (oxides, hydroxides, hydrous oxides, or phosphates of aluminum, silicon, zirconium, tin, titanium, antimony, etc.).
As the surface treatment agent, a silane coupling agent is preferable. In this case, the anisotropic filler is more compatible with the powder of the F polymer, and the dispersion stability of the present dispersion is easily improved. The silane coupling agent preferably has an amino group, a mercapto group, a vinyl group, an acryloxy group or a methacryloxy group.
The anisotropic filler may be an anisotropic filler having a hydrophobic portion and a hydrophilic portion. Examples of the anisotropic filler include an anisotropic filler having a hydrophobic layer on the surface and a hydrophilic layer in the interior. Specific examples thereof include plate-like multilayer fillers having a water repellent layer, a hydrophilic layer (aqueous layer), and a water repellent layer in this order. The water content of the hydrophilic layer is preferably 0.3 mass% or more. In this case, not only is the dispersion state of the anisotropic filler in the dispersion easily stabilized, but also the orientation of the anisotropic filler in forming a molded article from the dispersion is further improved, and a molded article having the physical properties of the F polymer and the physical properties of the anisotropic filler can be easily obtained.
The D50 of the anisotropic filler is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. The D50 of the anisotropic filler is preferably 25 μm or less, more preferably 20 μm or less. The D90 of the anisotropic filler is preferably 10 μm or more, more preferably 15 μm or more. The D90 of the anisotropic filler is preferably 30 μm or less, more preferably 20 μm or less. When the D50 and D90 of the anisotropic filler are in the above ranges, the affinity with the F powder is improved, and the dispersion stability of the dispersion liquid and the physical properties of the molded product thereof are more easily improved. Specific examples of the anisotropic filler include a scaly boron nitride filler and a platy talc filler.
The aspect ratio of the anisotropic filler is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and particularly preferably 10 or more. The aspect ratio of the anisotropic filler is preferably 10000 or less. In this case, the orientation of the filler in the molded article can be more easily improved, and the function can be more easily improved. Specifically, not only is the dispersion state of the anisotropic filler in the dispersion easily stabilized, but also the orientation of the anisotropic filler is further improved when a molded article is formed from the dispersion, and it is easy to obtain a molded article having high properties of the F polymer and the anisotropic filler.
The aspect ratio of the anisotropic filler is a value obtained by dividing the average particle diameter (D50) of the anisotropic filler by the average minor diameter (average of the length in the short side direction) of the anisotropic filler.
Specific examples of the anisotropic filler include a filler having an average minor diameter of 1 μm or less and an average major diameter (average longitudinal length) of 1 μm or more. Specific examples of the anisotropic filler include a platy talc filler.
The anisotropic filler may have a single-layer structure or a multilayer structure. Examples of the anisotropic filler include talc fillers having a three-layer structure.
Preferred specific examples of the anisotropic filler include a boron nitride filler (UHP series produced by sho-o electric corporation, HGP series produced by dupont, GP series, etc.), and a talc filler (SG series produced by japan talc corporation, etc.).
In the present dispersion, the D50 of the F powder is less than the D50 of the anisotropic filler. That is, in the present dispersion, since fine granular F powder is densely contained, the affinity between the F powder and the anisotropic filler is improved, and the dispersion stability of the present dispersion is improved. In addition, the anisotropic filler is more uniformly dispersed in the molded article, and the physical properties thereof are more easily apparent.
Specifically, the F powder preferably has a D50 of 0.1 μm or more and less than 5 μm, and the anisotropic filler preferably has a D50 of 1 μm or more and 25 μm or less.
The preferable form of the filler contained in the present dispersion may be, for example, a form containing an anisotropic filler (hereinafter referred to as "anisotropic filler 1") and containing an inorganic filler (hereinafter referred to as "different filler") having an average particle diameter smaller than that of the anisotropic filler 1. In this case, the interaction between the fillers improves the dispersion stability of the dispersion, balances the ability to form a dense molded article with a different filler, and facilitates further improvement of various physical properties (water resistance, low linear expansion, electrical characteristics, etc.) of the resulting molded article. The different filler may be any inorganic filler having an average particle diameter smaller than that of the anisotropic filler 1, and may be the same as or different from the anisotropic filler 1.
In a preferred form, the average particle size of the anisotropic filler 1 is preferably more than 6 μm and 15 μm or less, and the average particle size of the different filler is preferably 1 μm or more and 6 μm or less. In this case, it is preferable that the anisotropic filler 1 is a filler containing boron nitride and the different filler is a filler containing boron nitride or a magnesium metasilicate filler (talc filler). Furthermore, it is preferable that the aspect ratio of the anisotropic filler 1 is 10 or more, and that the aspect ratio of the different filler is 40 or less, more preferably less than 10.
In this case, the random orientation of the anisotropic filler is promoted by the different fillers in the obtained molded article, and the physical properties of the filler and the physical properties (adhesiveness, rigidity, etc.) of the molded article are easily balanced.
In a preferred form, the average particle size of the anisotropic filler 1 is preferably more than 1 μm and 15 μm or less, and the average particle size of the different filler is preferably 0.01 μm or more and less than 1 μm. In this case, it is preferable that the anisotropic filler 1 is a filler containing boron nitride and the different filler is a filler containing silicon oxide.
The silica-containing filler is preferably a silica filler or a magnesium metasilicate filler (talc filler). Further, it is preferable that the surface of the filler containing silicon oxide is surface-treated with a silane coupling agent.
The silica-containing filler is preferably substantially spherical. In this case, a dense molded article is easily formed. The substantially spherical shape means that the ratio of the shorter diameter to the longer diameter of spherical particles having a ratio of 0.7 or more is 95% or more when observed by a Scanning Electron Microscope (SEM).
Specific examples of the silica-containing filler include a spherical silica filler (admafin series, etc. manufactured by ya Dou Ma k corporation), a spherical fused silica (SFP series, etc. manufactured by electrochemical corporation), a hollow silica filler (E-SPHERES series, etc. manufactured by pacific cement corporation), a SiliNax series, manufactured by japanese iron industry corporation (japanese k corporation), an elsholty series, etc. manufactured by elsholty corporation, and a talc series, etc. manufactured by japanese talc corporation.
In this preferred embodiment, the random orientation of the anisotropic filler 1 in the molded article is promoted by the different fillers, so that the filler physical properties in the molded article and the molded article physical properties (adhesiveness, surface smoothness, rigidity, etc.) are easily balanced. That is, the molded article is highly likely to have electrical characteristics and low linear expansibility due to disorder of the alignment portion of the anisotropic filler 1 and the height of the filler alignment, and rigidity, adhesiveness and surface smoothness due to disorder of the filler alignment.
Furthermore, the filler of this preferred morphology may be contained in a state having a multimodal particle size distribution. In this case, from the viewpoint of easy formation of a dense molded article, it is preferable that the peak generated by the present filler 1 among the peaks in the particle size distribution is the highest. Specifically, the filler is preferably contained in a state having a bimodal particle size distribution having peaks in a region of 6 μm or less and in a region exceeding 6 μm.
At least a part of the filler in the preferred form may be contained by adhering to the surface of the F powder, or may be contained by adhering at least a part of the F powder to the surface thereof. In this case, it can be said that the dispersion liquid contains a composite of the F powder and the anisotropic filler 1, and the dispersion stability thereof is further improved, whereby various physical properties (water resistance, low linear expansion property, electric characteristics, and the like) of the formed product are easily further improved.
In the preferred embodiment, the mass ratio of the content of the different filler to the content of the anisotropic filler 1 is preferably 0.1 or more, more preferably 0.2 or more. The mass ratio is preferably 2 or less, more preferably 1 or less. In this case, the dispersion stability of the dispersion liquid and the physical properties of the molded article are easily balanced.
The content of the anisotropic filler in the present dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 25% by mass or more. The content of the F powder is preferably 50 mass% or less, more preferably 40 mass% or less, and still more preferably 30 mass% or less.
The content of the F polymer in the dispersion is preferably 5% by mass or more. The sum of the contents of both is preferably 60 mass% or less. The F polymer and the anisotropic filler may be contained in the above-mentioned high proportions (contents), respectively, and the dispersion is excellent in dispersion stability and can easily form a molded article having high physical properties of both of them, as described in the above-mentioned mechanism of action.
From the viewpoint of improving dispersion stability and handleability, the present dispersion preferably further contains a surfactant.
The surfactant is preferably a nonionic surfactant.
The hydrophilic part of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
The oxyalkylene group may be constituted of one kind of oxyalkylene group or may be constituted of 2 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, and more preferably a silicone type surfactant.
The fluorine-based surfactant is more preferably a fluorine-based surfactant having a hydroxyl group (especially an alcoholic hydroxyl group) or an oxyalkylene group and a perfluoroalkyl group or a perfluoroalkenyl group.
Specific examples of the surfactant include "Ftergent" series (produced by Nieuse corporation), "Surflon" series (produced by AGC Konj corporation), "MEGA FACE" series (produced by DIC corporation), the "Unidyne" series (produced by DIC corporation), and "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", and "BYK-3456" (produced by Picker Japanese corporation), and "KF-6011", and "KF-6043" (produced by Xin chemical industry Co., ltd.).
The content of the surfactant in the present dispersion is preferably 1 to 15 mass%. In this case, the affinity between the components is improved, and the dispersion stability of the dispersion liquid is more easily improved.
The liquid dispersion medium of the present invention is a liquid compound inert at 25 ℃ and functioning as a dispersion medium for the F powder and the anisotropic filler. The liquid dispersion medium may be water or a nonaqueous dispersion medium. The liquid dispersion medium may be 1 or 2 or more. In this case, it is preferable that the different liquid compounds are compatible.
The boiling point of the liquid dispersion medium is preferably 125 to 250 ℃. In this case, the anisotropic filler tends to be oriented when forming a molded article from the dispersion, and the physical properties of the molded article tend to be improved.
The liquid dispersion medium is preferably one or more liquid compounds selected from the group consisting of amides, ketones and esters, more preferably N-methyl-2-pyrrolidone, γ -butyrolactone, cyclohexanone and cyclopentanone, from the viewpoint of dispersion stability of the present dispersion liquid.
The content of the liquid dispersion medium in the present dispersion is preferably 50% by mass or more, more preferably 60% by mass or more. The content of the liquid dispersion medium is preferably 90 mass% or less, more preferably 80 mass% or less.
The viscosity of the dispersion is preferably 50 mPas or more, more preferably 100 mPas or more. The viscosity of the dispersion is preferably 10000 mPas or less, more preferably 1000 mPas or less, and even more preferably 800 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 component dispersion layer ratio of the present dispersion is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more. Here, the component dispersion layer ratio was a value calculated by the following formula from the total height of the present dispersion liquid and the height of the component dispersion layer in the spiral tube before and after standing at 25℃for 14 days when the present dispersion liquid (18 mL) was charged into the spiral tube (internal volume: 30 mL).
Component dispersion layer ratio (%) = (height of component dispersion layer)/(total height of present dispersion liquid) ×100
When no change in the state or the component dispersion layer was observed after standing, the entire height of the dispersion was unchanged, and the component dispersion layer rate was 100%.
The viscosity, thixotropy, or component dispersion layer ratio of the dispersion can be easily adjusted to the above range by the above action mechanism, and the operability is excellent.
The present dispersion may also contain other resins (polymers) than the F polymer. The other resin may be a thermosetting resin or a thermoplastic resin.
Examples of the other resin include epoxy resin, maleic amide resin, polyurethane resin, elastomer, polyimide, polyamic acid, polyamideimide, polyphenylene ether, liquid crystal polyester, and fluoropolymer other than F polymer.
The preferable form of the other resin is a varnish of an aromatic polymer. The aromatic polymer is preferably an aromatic polyimide and an aromatic polyamic acid, more preferably a thermoplastic aromatic polyimide. In this case, the molded article tends to significantly exhibit physical properties of the F polymer and the anisotropic filler. In addition, when a molded article is formed from the dispersion, powder falling of the F powder is suppressed, and the adhesiveness is also more easily improved.
The content of the aromatic polymer in the present dispersion is preferably 1 to 30% by mass, more preferably 5 to 25% by mass. The mass ratio of the content of the aromatic polymer to the content of the F polymer is preferably 1.0 or less, more preferably 0.1 to 0.7.
As a preferred form of the other resin, polytetrafluoroethylene (PTFE) powder may be mentioned. In this case, the molded article tends to exhibit physical properties (electrical characteristics such as low dielectric loss tangent) derived from PTFE. In addition, PTFE is a nucleating agent, and the F polymer in the molded article is liable to form fine crystals, so that the adhesion to the surface of the molded article is improved, and the adhesiveness is more liable to be improved. In addition, the orientation of the filler in the molded article can be easily improved, and the function can be easily improved.
PTFE is preferably PTFE (low molecular weight PTFE) having a number average molecular weight (Mn) of 20 ten thousand or less, which is calculated from the following formula (1).
Mn＝2.1×10 10 ×ΔHc -5.16 ···(1)
In the formula (1), Δhc represents the crystallization heat (card/g) of PTFE measured by differential scanning calorimetry.
The Mn of the low molecular weight PTFE is preferably 10 ten thousand or less, more preferably 5 ten thousand or less. Mn of the low molecular weight PTFE is preferably 1 ten thousand or more.
The PTFE content in the present dispersion is preferably 1 to 30 mass%, more preferably 5 to 20 mass%. The mass ratio of the PTFE content to the F polymer content is preferably 1.0 or less, more preferably 0.1 to 0.4.
The present dispersion liquid in the case of containing another resin may be produced by mixing the present dispersion liquid with a powder of another resin, or may be produced by mixing the present dispersion liquid with a varnish containing another resin.
The dispersion may contain, in addition to the above-mentioned components, additives such as a thixotropic agent, a defoaming 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 viscosity regulator, a flame retardant, and an isotropic filler.
The dispersion may be prepared by mixing the F powder, the anisotropic filler and the liquid dispersion medium, and preferably by preparing a liquid composition containing the F powder and a liquid composition containing the anisotropic filler, respectively, and then mixing the two.
The specific method for producing the present dispersion may be a method for producing a liquid dispersion medium by mixing the powder F, the anisotropic filler 1, a different filler, and the liquid dispersion medium. In the mixing, the powder F and the liquid dispersion medium may be mixed in advance to form a liquid composition, or the anisotropic filler 1 and the above-mentioned different filler may be mixed in advance.
Examples of the mixer used for mixing include a mixer using stirring blades, a henschel mixer, a ribbon blender, a shaking mixer, a vibration mixer, and a rotary mixer, and specifically include a homogenizing and dispersing machine, a homogenizer, and a ball mill.
The mixing method may be batch-type or continuous-type. The mixer used for batch mixing is preferably a Henschel mixer, a pressure kneader, a Banbury mixer or a planetary mixer.
The mixing is preferably performed by stirring, more preferably by rotating stirring with stirring blades.
The stirring speed is preferably 800rpm or more, more preferably 2000rpm or more. The stirring speed is preferably 10000rpm or less, more preferably 8000rpm or less. In this case, shearing is applied to the F powder and the anisotropic filler, so that aggregates are easily broken, and a dispersion of the present invention excellent in dispersibility is easily obtained.
In addition, if the anisotropic filler is in a scale-like or plate-like form, lamellar aggregates (secondary particles) of the anisotropic filler which are usually formed are likely to be broken efficiently and form a card house structure, so that the present dispersion liquid having good dispersibility is likely to be formed.
The molded article of the present invention (hereinafter referred to as "the present molded article") comprises a tetrafluoroethylene polymer containing PAVE units (hereinafter referred to as "PFA polymer") and an anisotropic filler having a mohs hardness of 4 or less. The PFA polymer is a polymer having a polar functional group or a polymer having no polar functional group and containing 2.0 to 5.0 mol% of PAVE units relative to the total units, and the anisotropic filler is present in the present molded article in a proportion (content) of 10 mass% or more.
Examples of the shape of the present molded article include a layer, a plate, and a block, and a layer is preferable. The thickness of the layered product is preferably 150 μm or less. The layered product can be used for producing impregnated articles such as films and prepregs, laminated plates, and the like.
The definition and scope of the anisotropic filler in the present molding include those in which the preferred morphology is the same as that of the anisotropic filler in the present dispersion.
The types and ranges of the polar functional groups contained in the PFA-based polymer in the present molded article include those in which the preferable morphology is the same as those in the F-based polymer. The PFA-based polymer is preferably the polymer (1) or the polymer (2).
The content of the anisotropic filler in the present molded article is preferably 15 mass% or more, more preferably 25 mass% or more. The content of the anisotropic filler is preferably 50 mass% or less, more preferably 40 mass% or less.
The content of the PFA-based polymer in the molded article is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. The content of the PFA-based polymer is preferably 95% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. If the content of the PFA-based polymer is within this range, the physical properties of the PFA-based polymer tend to be remarkably exhibited in the molded article. In addition, the anisotropic filler is inhibited from falling out of powder from the present molded article.
The present shaped article preferably also comprises an aromatic polymer (in particular aromatic polyimide) or PTFE. The definition and extent of each of the aromatic polymer and PTFE in the present molding and the mass ratio of the content of each to the content of F polymer are the same as those in the present dispersion.
The present molded article is preferably formed from the present dispersion. Specifically, when the present dispersion is applied to the surface of a substrate and the liquid dispersion medium is removed, a layer containing a PFA-based polymer and an anisotropic filler (hereinafter referred to as "the present layer") as the present molded article can be easily formed on the surface of the substrate. More specifically, the present dispersion is applied to the surface of a substrate, the substrate is heated to remove the liquid dispersion medium, and the PFA-based polymer is melted and burned by heating, whereby a laminate comprising the substrate and the present layer formed on the surface of the substrate can be obtained. The former is preferably 120 to 200 ℃. The latter is preferably 250 to 400℃and more preferably 300 to 380 ℃.
Examples of the substrate include a metal substrate (metal foil such as copper, nickel, aluminum, titanium, or an alloy thereof), a resin film (film of polyimide, polyacrylate, polysulfone, polyarylsulfone, polyamide, polyether amide, polyphenylene sulfide, polyaryletherketone, polyamide imide, liquid crystal polyester, and liquid crystal polyester amide), and a prepreg (precursor of a fiber-reinforced resin substrate).
The administration of the present dispersion is preferably performed by coating. Examples of the coating method include a spray method, a roll coating method, a spin coating method, a gravure coating method, a micro gravure coating method, a gravure offset coating method, a doctor blade coating method, a touch coating method, a bar coating method, a die coating method, a jet meyer bar coating method, and a comma coating method.
Examples of the respective heating methods include a method using a heating furnace, a method using a ventilating drying furnace, and a method of radiating heat rays such as infrared rays.
The thickness of the layer is preferably 0.1 to 150. Mu.m. Specifically, if the substrate is a metal foil, the thickness of the present layer is preferably 1 to 30 μm. If the substrate is a resin film, the thickness of the present layer is preferably 1 to 150. Mu.m, more preferably 10 to 50. Mu.m.
The dispersion may be applied to only one side of the substrate, or may be applied to both sides of the substrate. In the former case, a laminate having a substrate and the present layer on one surface of the substrate can be obtained, and in the latter case, a laminate of the substrate and the present layer on both surfaces of the substrate can be obtained. The latter laminate is less likely to warp, and therefore is excellent in handling property during processing.
Specific examples of the laminate include a metal-clad laminate having a metal foil and a layer on at least one surface of the metal foil, and a multilayer film having a polyimide film and a layer on both surfaces of the polyimide film.
These laminates are excellent in various physical properties such as electrical characteristics and are suitable for use as printed circuit board materials and the like. Specifically, the laminate can be used for manufacturing a flexible printed board or a rigid printed board.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
1. Preparation of the ingredients
[ powder ]
Powder 1: from a main chain having a carbon number of 1X 10, which comprises 97.9 mol%, 0.1 mol%, 2.0 mol% of TFE unit, NAH unit and PPVE unit in this order 6 Powder (D50: 2.1 μm) of PFA-based Polymer 1 having 1000 carbonyl groups (melting temperature: 300 ℃ C.)
Powder 2: from a main chain having a carbon number of 1X 10, based on the main chain, of 97.5 mol%, 2.5 mol% of TFE units and PPVE units in this order 6 Powder (D50: 1.8 μm) of PFA-based Polymer 2 having 40 carbonyl groups (melting temperature: 305 ℃ C.)
Powder 3: powder of PFA-based Polymer 2 (D50: 5.3 μm)
Powder 4: powder (D50: 3.2 μm) formed from PTFE having a number average molecular weight of 2 ten thousand
[ Anisotropic filler ]
Filler 1: scale-like filler formed of boron nitride (D50:7.0 μm)
Filler 2: scale-like filler formed of boron nitride (D50:3.7 μm)
And (3) filling material: scale-like filler formed of boron nitride (D50:7.3 μm)
Filler 4: a plate-like talc filler having a three-layer structure comprising a water-repellent layer, a hydrophilic layer and a water-repellent layer in this order (D50: 4.5 μm, average major diameter: 5.1 μm, average minor diameter: 0.2 μm, aspect ratio: 25, and "SG-95" manufactured by Japanese talc Co., ltd.).
The mohs hardness of the fillers 1 to 3 is 2, and the mohs hardness of the filler 4 is 1. Fillers 1, 2 and 4 were surface treated with a silane coupling agent.
[ liquid Dispersion Medium ]
NMP: n-methyl-2-pyrrolidone
[ surfactant ]
Surfactant 1: CH (CH) 2 ＝C(CH 3 )C(O)OCH 2 CH 2 (CF 2 ) 6 F and CH 2 ＝C(CH 3 )C(O)(OCH 2 CH 2 ) 23 OH copolymer, nonionic polymer with a fluorine content of 35 mass%.
[ varnishes of aromatic polymers ]
Varnish 1: varnish (solid content concentration: 18% by mass) obtained by dissolving thermoplastic aromatic polyimide (PI 1) in NMP
2. Preparation example of dispersion
Example 1
First, powder 1, varnish 1, surfactant 1 and NMP were put into a pot, and zirconia balls were put into. The can was then rolled at 150rpm for 1 hour to make the composition. Then, filler 1, surfactant 1 and NMP were put into another pot, and zirconia balls were put into the pot, and the pot was rolled at a rotation speed of 150rpm for 1 hour to prepare a composition.
Subsequently, the two compositions were put into another pot, and zirconia balls were put into the pot. Thereafter, the pot was rolled at a rotation speed of 150rpm for 1 hour to obtain a dispersion liquid 1 (viscosity: 400 mPa.s) containing powder 1 (11 parts by mass), filler 1 (11 parts by mass), PI1 (7 parts by mass), surfactant 1 (4 parts by mass) and NMP (67 parts by mass).
Examples 2 to 9
Dispersions 2 to 9 were obtained in the same manner as in example 1, except that the types and amounts of the powder, filler, varnish, surfactant and liquid dispersion medium were changed as shown in table 1 below.
Example 10
A dispersion 10 was obtained in the same manner as in example 1, except that 3 parts by mass of filler 1 and 8 parts by mass of filler 2 were used in place of 11 parts by mass of filler 1.
TABLE 1
* The values in parentheses in the columns for the powder, filler and varnish types show their content in the dispersion (unit: mass%).
3. Production example of molded article
The dispersion 1 was applied by a bar coating method to the surface of a long copper foil (thickness: 18 μm) to form a wet film. Then, the metal foil having the wet film formed thereon was passed through a drying oven at 120 ℃ for 5 minutes, and dried by heating to obtain a dry film. Thereafter, the dry film was heated at 380℃for 3 minutes in a nitrogen oven. Thereby, a laminate 1 having a metal foil and a polymer layer (thickness: 5 μm) as a molded product containing a melt-burned product of the powder 1 and the filler 1 on the surface thereof was produced.
Laminates 2 to 10 were obtained in the same manner as laminate 1, except that dispersions 2 to 10 were used instead of dispersion 1, respectively.
4. Evaluation
4-1 dispersion stability of the Dispersion
After storing the dispersions 1 to 10 in a container at 25 ℃, the dispersibility was visually confirmed, and the dispersion stability was evaluated according to the following criteria.
[ evaluation criterion ]
And (3) the following materials: no agglutinates were found.
And (2) the following steps: the vessel sidewall was seen to have fine agglomerates adhering. The mixture was gently stirred and then uniformly redispersed.
Delta: the condensate precipitation was also visible at the bottom of the vessel. Shear is applied to stir and then uniformly redisperse.
X: the condensate precipitation was also visible at the bottom of the vessel. Even if shear is applied to stir, redispersion is difficult.
4-2 physical Properties of laminate
4-2-1 surface smoothness
The polymer layers of the laminates 1 to 9 were visually checked for surface smoothness, and the surface smoothness was evaluated according to the following criteria.
[ evaluation criterion ]
And (2) the following steps: the entire surface of the polymer layer was smooth.
Delta: the irregularities due to the absence of polymer or filler are visible at the surface edges of the polymer layer.
X: the polymer layer has irregularities on the entire surface thereof due to the absence of the polymer or inorganic filler
4-2-2 coefficient of linear expansion
For the laminates 1 to 4, 9 and 10, square test pieces of 180mm square were cut, and the linear expansion coefficients of the test pieces in the range of 25 to 260℃were measured according to the measurement method prescribed in JIS C6471:1995.
[ evaluation criterion ]
And (2) the following steps: 30 ppm/DEG C or less.
X: exceeding 30 ppm/. Degree.C.
4-2-3 dielectric loss tangent
For each of the laminates 1 to 4, 9 and 10, copper foil of the laminate was etched with an iron chloride solution and removed to prepare a separate polymer layer, and the dielectric loss tangent (measurement frequency: 10 GHz) of the polymer layer was measured by the SPDR (separation medium resonance) method.
[ evaluation criterion ]
And (2) the following steps: the dielectric loss tangent of which is less than 0.0010.
Delta: the dielectric loss tangent is not less than 0.0010 and not more than 0.0025.
X: the dielectric loss tangent thereof exceeds 0.0025.
The evaluation results are summarized in Table 2 below.
TABLE 2
5. Production example of dispersion (II)
Example 11
First, powder 1 and surfactant 1 and NMP were added to a pot and mixed, and stirred at 2000rpm for 1 hour with a homogenizing-dispersing machine to obtain a composition. In another pot, filler 1, surfactant 1 and NMP were charged and stirred with a homogenizing disperser at 2000rpm for 1 hour to obtain a composition. Subsequently, the two compositions were put into an additional pot and stirred with a homogenizer at 2000rpm for 1 hour to obtain a dispersion 11 (viscosity: 300 mPas, component dispersion layer ratio: 80%) containing powder 1 (11 parts by mass), filler 1 (11 parts by mass), surfactant 1 (4 parts by mass) and NMP (74 parts by mass).
Example 12
A dispersion 12 (viscosity: 300 mPas, component dispersion layer ratio: 50%) was obtained in the same manner as in example 11 except that an ultrasonic homogenizer not accompanied by stirring by a stirring blade was used instead of the homogenizing disperser.
6. Production example of laminate (II)
The dispersion 11 was applied to the surface of an aluminum foil having a thickness of 18 μm by a gravure roll-to-roll method to form a liquid coating. Then, the aluminum foil on which the liquid coating was formed was passed through a drying furnace at 120 ℃ for 5 minutes, and dried by heating. Thereafter, the dry film was heated at 340℃for 3 minutes in a far infrared oven under a nitrogen atmosphere. Thus, a laminate 11 in which a polymer layer (thickness: 10 μm) was formed on the surface of an aluminum foil was produced. A laminate 12 was produced in the same manner as the laminate 11, except that the dispersion 12 was used instead of the dispersion 11.
As a result of observation of the cross section of each laminate by SEM, the distribution state of the filler 1 in the polymer layer of the laminate 11 was denser than that of the polymer layer of the laminate 12. In addition, the dielectric loss tangent of the polymer layer of the laminate 11 is lower than that of the polymer layer of the laminate 12. The thermal conductivity and bendability of the laminate 11 are superior to those of the laminate 12.
Industrial applicability
The dispersion of the present invention is excellent in dispersion stability, and can be used for producing a molded article (a film, an impregnated product such as a prepreg, a laminated plate, a coating material, etc.) having physical properties based on an F polymer (PFA polymer) and characteristics based on an anisotropic filler. The molded article of the present invention can be used as an antenna member, a printed circuit board, an aircraft member, an automobile member, an exercise machine, a food industry product, a paint, a cosmetic product, etc., and specifically, can be used as a heat radiating member, an electric wire coating material (an aircraft electric wire, etc.), an electric insulating tape, an insulating tape for oil excavation, a material for a printed circuit board, a separation membrane (a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane, an ion exchange membrane, a dialysis membrane, a gas separation membrane, etc.), an electrode adhesive (a lithium secondary battery, a fuel cell, etc.), a copying roller, a furniture, a motor vehicle instrument panel, a cover for a household electrical appliance, etc., a sliding member (a load bearing, a sliding shaft, a valve, a bearing, a gear, a cam, a conveyor belt, a food conveyor belt, etc.), a tool (a shovel, a file, an awl, a saw, etc.), a boiler, a hopper, a pipe, an oven, a baking mold, a chute, a toilet, a container coating material, a heat exchanger (a fan, a heat transfer pipe, etc.), etc.
Claims (14)
1. A dispersion comprising a powder of a tetrafluoroethylene polymer containing units based on perfluoro (alkyl vinyl ether) or units based on hexafluoropropylene, an anisotropic filler having a Mohs hardness of 4 or less, and a liquid dispersion medium, wherein the average particle diameter of the powder is smaller than that of the anisotropic filler, the anisotropic filler is an anisotropic filler containing boron nitride or talc, and
the content of the anisotropic filler is 10 mass% or more, and the sum of the content of the tetrafluoroethylene polymer and the content of the anisotropic filler is 60 mass% or less.
2. The dispersion according to claim 1, wherein the content of the tetrafluoroethylene polymer and the content of the anisotropic filler are each 5% by mass or more.
3. The dispersion as claimed in claim 1 or 2, wherein the anisotropic filler has a scale-like or plate-like shape.
4. The dispersion according to claim 1 or 2, wherein the anisotropic filler has an aspect ratio of 2 or more.
5. The dispersion according to claim 1 or 2, further comprising polytetrafluoroethylene powder or an aromatic polymer.
6. The dispersion according to claim 1 or 2, wherein the component dispersion layer ratio is 60% or more.
7. A method for producing the dispersion according to any one of claims 1 to 6, wherein the powder, the anisotropic filler, an inorganic filler having an average particle diameter smaller than that of the anisotropic filler, and a liquid dispersion medium are mixed.
8. The production method according to claim 7, wherein the mixing is performed by stirring.
9. A molded article comprising a tetrafluoroethylene polymer containing units based on perfluoro (alkyl vinyl ether) and an anisotropic filler having a Mohs hardness of 4 or less,
the tetrafluoroethylene polymer is a polymer having a polar functional group or a polymer having no polar functional group and containing 2.0 to 5.0 mol% of the perfluoro (alkyl vinyl ether) -based unit relative to the total units, and the anisotropic filler is an anisotropic filler containing boron nitride or talc, and the proportion of the anisotropic filler in the molded article is 10 mass% or more.
10. The molded article according to claim 9, wherein the aspect ratio of the anisotropic filler is 2 or more.
11. The molded article according to claim 10, wherein the anisotropic filler is a scale-like anisotropic filler containing boron nitride or a plate-like anisotropic filler containing talc.
12. The molded article according to any one of claims 9 to 11, wherein the anisotropic filler has an average particle diameter of 1 μm or more.
13. The shaped article according to any one of claims 9 to 11, further comprising polytetrafluoroethylene or an aromatic polymer.
14. The molded article according to any one of claims 9 to 11, wherein the molded article is a layered molded article having a thickness of 150 μm or less.
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| JP2019-221564 | 2019-12-06 | ||
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| JP2020-016436 | 2020-02-03 | ||
| JP2020-077294 | 2020-04-24 | ||
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| JP2020-154348 | 2020-09-15 | ||
| JP2020154348 | 2020-09-15 | ||
| PCT/JP2020/044992 WO2021112164A1 (en) | 2019-12-06 | 2020-12-03 | Dispersion liquid, method for producing dispersion liquid, and molded article |
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| WO2023163025A1 (en) * | 2022-02-28 | 2023-08-31 | Ａｇｃ株式会社 | Composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5000875A (en) * | 1987-10-16 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Conductive filled fluoropolymers |
| CN1345349A (en) * | 1999-03-31 | 2002-04-17 | 纳幕尔杜邦公司 | Sprayable powder of non-fibrillatable fluoropolymer |
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| JP5757347B2 (en) | 2013-01-24 | 2015-07-29 | ダイキン工業株式会社 | Composition, and method for producing foamed molded article and electric wire |
| CN109476897B (en) * | 2016-07-22 | 2021-12-14 | Ａｇｃ株式会社 | Liquid composition, and method for producing film and laminate using same |
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- 2020-12-03 WO PCT/JP2020/044992 patent/WO2021112164A1/en active Application Filing
- 2020-12-04 TW TW109142815A patent/TW202130732A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5000875A (en) * | 1987-10-16 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Conductive filled fluoropolymers |
| CN1345349A (en) * | 1999-03-31 | 2002-04-17 | 纳幕尔杜邦公司 | Sprayable powder of non-fibrillatable fluoropolymer |
Also Published As
| Publication number | Publication date |
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| TW202130732A (en) | 2021-08-16 |
| KR20220113354A (en) | 2022-08-12 |
| CN114729171A (en) | 2022-07-08 |
| JPWO2021112164A1 (en) | 2021-06-10 |
| WO2021112164A1 (en) | 2021-06-10 |
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