KR20220113354A - Dispersions, methods for preparing dispersions and moldings - Google Patents

Abstract

(Project) Provision of a dispersion containing a predetermined tetrafluoroethylene-based polymer and a predetermined anisotropic filler, a method for producing the same, and a molded article highly equipped with both physical properties.
(Solution) The dispersion liquid of the present invention comprises a powder of a tetrafluoroethylene polymer containing units based on perfluoro (alkylvinyl ether) or units based on hexafluoropropylene, and anisotropy having a Mohs hardness of 4 or less. A filler and a liquid dispersion medium are included. The average particle diameter of the said powder is smaller than the average particle diameter of the said anisotropic filler. The molded article of the present invention contains a predetermined tetrafluoroethylene polymer containing units based on perfluoro (alkyl vinyl ether), and the anisotropic filler. The proportion of the anisotropic filler in the molded product is 10 mass% or more.

Description

Dispersions, methods for preparing dispersions and moldings

The present invention relates to a dispersion containing a predetermined anisotropic filler, a method for producing the same, and a molded article.

Heat meltability of tetrafluoroethylene polymer (PFA) containing units based on perfluoro (alkyl vinyl ether), tetrafluoroethylene polymer (FEP) containing units based on hexafluoropropylene, etc. Fluoropolymers are excellent in physical properties such as releasability, electrical insulation, water and oil repellency, chemical resistance, weather resistance, heat resistance, and the like, and are processed and used in various molded products.

Patent Document 1 describes a wire tube having excellent electrical insulation properties obtained by melt-kneading a dry blend of PFA powder and boron nitride filler and extrusion molding.

Japanese Patent Laid-Open No. 2014-224228

However, the melt viscosity of such a fluoropolymer is generally high, and a strong stress is required when melt-kneading the fluoropolymer and the filler. In that case, the properties (particularly, physical properties such as shape and surface state) inherent in the filler are impaired, and the physical properties of the filler in a molded product are likely to decrease. The present inventors have discovered that this tendency becomes remarkable in the case of a brittle filler of low hardness, especially in the case of a low hardness and anisotropic filler.

The present inventors earnestly studied in order to obtain a material suitable for the shaping|molding of such a molded object not by melt-kneading. As a result, it was found that a dispersion containing a predetermined fluoropolymer powder and a predetermined anisotropic filler was excellent in dispersion stability and also excellent in handling properties such as coatability. Moreover, it was also discovered that the molded article formed therefrom is not easily impaired in the properties originally possessed by the anisotropic filler, and is highly equipped with both physical properties.

It is an object of the present invention to provide such dispersions and moldings.

The present invention has the following aspects.

[1] A powder of a tetrafluoroethylene polymer containing a unit based on perfluoro (alkyl vinyl ether) or a unit based on hexafluoropropylene, an anisotropic filler having a Mohs hardness of 4 or less, and a liquid dispersion medium And, the average particle diameter of the powder is smaller than the average particle diameter of the anisotropic filler, dispersion.

[2] The dispersion liquid of [1], wherein the content of the tetrafluoroethylene-based polymer and the content of the anisotropic filler are 5 mass% or more, respectively.

[3] The dispersion liquid according to [1] or [2], wherein the shape of the anisotropic filler is flaky or plate-like.

[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 liquid according to any one of [1] to [4], wherein the anisotropic filler is an anisotropic filler containing boron nitride or talc.

[6] The dispersion liquid according to any one of [1] to [5], further comprising a polytetrafluoroethylene powder or an aromatic polymer.

[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 the 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. Way.

[9] The manufacturing method of [8], wherein mixing is performed by stirring.

[10] A molded article comprising a tetrafluoroethylene-based polymer containing a unit based on perfluoro (alkyl vinyl ether) and an anisotropic filler having Mohs hardness of 4 or less,

The tetrafluoroethylene-based polymer is a polymer having a polar functional group, or a polymer containing 2.0 to 5.0 mol% of a unit based on the perfluoro (alkylvinyl ether) with respect to all units, and having no polar functional group, , The molded article, wherein the proportion of the anisotropic filler in the molded article is 10 mass% or more.

[11] The molded product according to [10], wherein the aspect ratio of the anisotropic filler is 2 or more.

[12] The molded product according to [11], wherein the anisotropic filler is a flaky anisotropic filler containing boron nitride or a plate-shaped anisotropic filler containing talc.

[13] The molded product according to any one of [10] to [12], wherein the anisotropic filler has an average particle diameter of 1 µm or more.

[14] The molded article according to any one of [10] to [13], further comprising polytetrafluoroethylene or an aromatic polymer.

[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.

According to the present invention, a dispersion comprising a predetermined fluoropolymer powder and a predetermined anisotropic filler and excellent in dispersibility and handling properties is obtained. Moreover, a molded article which is highly equipped with both physical properties and is especially excellent in an electrical property is obtained.

The following terms have the following meanings.

"Average particle diameter (D50)" is the volume-based cumulative 50% diameter of the target object (powder or filler) calculated|required by the laser diffraction/scattering method. That is, the particle size distribution of the object is measured by the laser diffraction and scattering method, the cumulative curve is obtained with the total volume of the population of particles of the object being 100%, and the particle diameter at the point where the cumulative volume becomes 50% on the cumulative curve. .

"D90" is a volume-based cumulative 90% diameter of an object measured in the same way.

"Particle size distribution" is a distribution shown by the curve which plotted the particle|grain amount (%) in each particle diameter range calculated|required similarly.

The "melting temperature" is a temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method.

A "glass transition point" 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 formed directly from a monomer by a polymerization reaction, or an atomic group in which a part of the structure is converted by treating the polymer obtained by the polymerization reaction by a predetermined method. A unit based on the monomer A contained in the polymer is also simply described as a “monomer A unit”.

The dispersion of the present invention (hereinafter also referred to as “the present dispersion”) is a unit based on perfluoro(alkylvinyl ether) (PAVE) (PAVE unit) or a unit based on hexafluoropropylene (HFP) ( HFP unit) containing powder (hereinafter also referred to as “F polymer”) of a tetrafluoroethylene-based polymer (hereinafter also referred to as “F powder”), an anisotropic filler having a Mohs hardness of 4 or less, and a liquid dispersion medium includes

Moreover, the average particle diameter of F powder is smaller than the average particle diameter of an anisotropic filler. In the present dispersion, the F powder and the anisotropic filler are dispersed.

This dispersion liquid is excellent in dispersion stability and handling property, and it is easy to form a molded article equipped with the physical property of F polymer and an anisotropic filler highly. Although the reason is not necessarily clear, it can think as follows.

The anisotropic filler in the present invention can be said to be a weak filler having an irregular shape and various properties (such as a regular wall). In the present dispersion, the anisotropic filler is unstable in its state and tends to aggregate or settle. Moreover, the anisotropic filler is in a state in which the shape or property is easily destroyed by physical stress (shear stress, etc.).

On the other hand, F polymer is a polymer having plasticity typified by heat melt workability, and the powder (F powder) is not easily affected by physical stress and has excellent dispersibility.

This dispersion contains such F powder in a state smaller than the average particle diameter of the anisotropic filler, in other words, densely, and the affinity between the anisotropic filler and F powder is relatively easy to increase. In other words, in the present dispersion, since the F powder is more densely contained in a fine particle form, it is considered that a similar secondary particle is easily formed between the F powder and the anisotropic filler. As a result, since the dispersed state of the anisotropic filler is stabilized, it is thought that this dispersion liquid is excellent in dispersion stability and handling property.

In addition, if the F powder is melt-fired while removing the liquid dispersion medium from this dispersion liquid, the molded article can be easily molded while suppressing the deformation of the anisotropic filler. In addition, in the process of removing the liquid dispersion medium, while the anisotropic filler is oriented, it is easy to obtain a highly filled molded product. As a result, it is thought that the molded article which was equipped with the physical property of F polymer highly and the physical property of an anisotropic filler from this dispersion liquid was obtained.

For example, when a molded article is formed from the present dispersion containing a flaky or plate-shaped 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 highly expressed. easy to become Therefore, when this dispersion is used, even in a thin-layered molded article, the physical properties of the F polymer and the physical properties of the anisotropic filler are easily expressed to a high degree.

In addition, if the anisotropic filler is flaky or plate-shaped, the anisotropic filler forms a card house structure, so that the liquid physical properties (viscosity, dispersion stability, etc.) of the present dispersion are improved, and the anisotropic filler in the molded article formed therefrom is more highly easy to disperse As a result, the molding tends to be excellent in electrical properties. Moreover, when a molding receives stress, it is easy to disperse|distribute a stress by an anisotropic filler, and mechanical strength (bendability, etc.) improves easily. Moreover, in a molded article, since the path|pass of an anisotropic filler is formed, it is easy to improve the thermal conductivity of a molded article.

It is preferable that the F powder in this dispersion liquid consists of F polymer. 80 mass % or more is preferable and, as for content of F polymer in powder, 100 mass % is more preferable.

Other components that may be included in the F powder include resins or inorganic substances different from those of the F polymer. Examples of different resins include aromatic polyester, polyamideimide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.

Examples of the inorganic substance include silicon oxide (silica), metal oxides (such as beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide), boron nitride, and magnesium metasilicate (steatite).

The F powder containing a resin or inorganic substance different from the F polymer has a core-shell structure with the F polymer as the core and the resin or the inorganic substance as the shell, or the resin or the inorganic substance as the core, and the F polymer as the shell It is preferable to have a core-shell structure having Such F powder is obtained by, for example, bonding (collision, agglomeration, etc.) a powder of an F polymer and the powder of the resin or inorganic substance.

10 micrometers or less are preferable, as for D50 of F powder, 6 micrometers or less are more preferable, and 4 micrometers or less are still more preferable. 0.01 micrometer or more is preferable, as for D50 of F powder, 0.1 micrometer or more is more preferable, and 1 micrometer or more is still more preferable. Moreover, 20 micrometers or less are preferable and, as for D90 of F powder, 10 micrometers or less are more preferable. When the D50 and D90 of the F powder are within these ranges, the affinity with the anisotropic filler is further improved, and the dispersion stability of the present dispersion and the physical properties of the molded product are more likely to improve.

5 mass % or more is preferable, as for content of F powder in this dispersion liquid, 10 mass % or more is more preferable, and 25 mass % or more is still more preferable. 50 mass % or less is preferable, as for content of F powder, 40 mass % or less is more preferable, 30 mass % or less is still more preferable. When the content of the F powder is in such a range, the affinity between the F powder and the anisotropic filler is increased by the densely contained F powder, and the dispersion stability of the present dispersion is more likely to be improved. In addition, the physical properties of the F polymer in the molded product are remarkably easily expressed.

The F polymer in the present dispersion is a polymer containing units based on tetrafluoroethylene (TFE) (TFE units). F polymer may contain both a PAVE unit and an HFP unit, and may contain only either one.

CF2 _{= CFOCF3} , CF2 _{= CFOCF2CF3 ,} or CF2 _{= CFOCF2CF2CF3 (} PPVE) is preferable and, as for PAVE, PPVE is _more preferable.

280-325 degreeC is preferable and, as for the melting temperature of F polymer, 285-320 degreeC is more preferable.

75-125 degreeC is preferable and, as for the glass transition point of F polymer, 80-100 degreeC is more preferable.

The F polymer may have a polar functional group (oxygen-containing polar group). The polar functional group may be contained in the unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter aspect include an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, and the like, and an F polymer having a polar functional group obtained by subjecting the 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 more preferably a carbonyl group-containing group from the viewpoint of dispersion stability of the present dispersion.

The hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, and more preferably -CF ₂ CH ₂ OH or -C(CF ₃ ) ₂ OH.

The carbonyl group-containing group is a group containing a carbonyl group (> C(O)), a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH ₂ ), an acid anhydride residue (-C( O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.) or a carbonate group (-OC(O)O-) is preferable.

The number of carbonyl group-containing groups in the F polymer is preferably from 10 to 5000, more preferably from 100 to 3000, still more preferably from 800 to 1500, per carbon number of 1×10 ⁶ in the main chain. In addition, the number of carbonyl group-containing groups in F polymer can be quantified by a polymer composition or the method described in International Publication No. 2020/145133.

The F polymer is preferably a tetrafluoroethylene-based polymer that contains PAVE units and contains 1.5 to 5.0 mol% of PAVE units based on the total unit, and contains a PAVE unit and a unit based on a monomer having a polar functional group, , a polymer (1) having a polar functional group, or a polymer (2) having no polar functional group including PAVE units and 2.0 to 5.0 mol% of PAVE units relative to all units is more preferable.

These F polymers not only have excellent dispersion stability of the powder, but are also more densely and more homogeneously distributed in a molded article (such as a polymer layer) formed from the present dispersion. Moreover, it is easy to form microspheres in a molded object, and adhesiveness with another component tends to become high. As a result, it is easier to obtain a molded article having the physical properties of each of the three components to a high degree.

The polymer (1) preferably contains 90 to 98 mol% of TFE units, 1.5 to 9.97 mol% of PAVE units, and 0.01 to 3 mol% of units based on monomers having a polar functional group, respectively, with respect to all units. do.

Moreover, the monomer which has a polar functional group is itaconic acid anhydride, citraconic acid anhydride, or 5-norbornene-2,3-dicarboxylic acid anhydride (Alternative name: hymic acid anhydride; hereafter also described as "NAH".) This is preferable.

As a specific example of the polymer (1), the polymer described in International Publication No. 2018/16644 is mentioned.

It is preferable that the polymer (2) consists only of a TFE unit and a PAVE unit, and contains 95.0-98.0 mol% of TFE units and 2.0-5.0 mol% of PAVE units with respect to all units.

2.1 mol% or more is preferable with respect to all units, and, as for content of the PAVE unit in polymer (2), 2.2 mol% or more is more preferable.

Further, that the polymer (2) does not have a polar functional group means that the number of polar functional groups in the polymer is less than 500 per 1 × 10 ⁶ carbon atoms constituting the polymer main chain. 100 or less are preferable and, as for the number of the said polar functional group, less than 50 are more preferable. The lower limit of the number of the said polar functional groups is 0 normally.

Polymer (2) may be prepared using a polymerization initiator, chain transfer agent, or the like that does not cause a polar functional group as a terminal group of the polymer chain, and F polymer having a polar functional group (a polar functional group derived from the polymerization initiator is a polymer main chain F polymer or the like having a terminal group of ) may be produced by fluorination treatment. As a method of fluorination treatment, a method using fluorine gas (refer to Unexamined-Japanese-Patent No. 2019-194314, etc.) is mentioned.

The Mohs' Hardness of the anisotropic filler in this invention is 4 or less, and 3 or less are preferable. 1 or more are preferable and, as for the Mohs' Hardness of an anisotropic filler, 2 or more are more preferable. Even if it is a soft anisotropic filler having Mohs' Hardness within this range, the dispersion liquid is excellent in dispersion stability due to the affinity of the anisotropic filler and F powder, and the physical properties of the filler in the molded product are likely to be high.

An anisotropic filler may use 1 type, and may use 2 or more types from which an average particle diameter or a type differs.

The shape of the anisotropic filler in the present invention may be any of a granular shape, a needle shape (fibrous shape), and a plate shape. Specific shapes of the anisotropic filler include spherical, scaly, lamellar, lobed, columnar, lanceolate, equiaxed, lobed, mica, and block. , a flat plate shape, a wedge shape, a rosette shape, a mesh shape, and a prismatic shape.

As for the shape of an anisotropic filler, a scale shape or plate shape is preferable. When a flaky or plate-shaped anisotropic filler is used, it forms a card house structure, and it is easy to improve the liquid physical properties (viscosity, dispersion stability, etc.) of the dispersion, as well as the orientation of the filler in the molded product. (mechanical strength, thermal conductivity, electrical characteristics, etc.) is easy to raise.

Examples of the anisotropic filler include a carbon filler, a nitride filler, a mica filler, a clay filler, and a talc filler, preferably a filler containing boron nitride or talc, and more preferably a filler containing boron nitride. The crystal form of boron nitride may be any of hexagonal crystal, rhombohedral crystal, cubic crystal, and wurtzite. This dispersion liquid containing such an anisotropic filler is excellent in dispersion stability and handling property. In addition, in the molded article, the electrical interference imparted by the filler to the F polymer tends to increase, and as a result, the electrical properties (particularly, dielectric loss tangent property) of the molded article are likely to be good. In addition, the thermal conductivity of the molded article tends to be good.

95 mass % or more is preferable, as for content of boron nitride in the filler containing boron nitride, 99 mass % or more is more preferable, and its 99.5 mass % or more is still more preferable. The upper limit of content is 100 mass %. In this case, the molded article tends to be excellent in low linear expansibility and electrical properties.

When an anisotropic filler is added to water, pH of the water may show any of acidity, neutrality, and alkalinity, and it is preferable to show alkalinity.

1-20 m<2>/g is preferable and, as for the specific surface area of an anisotropic filler, 3-8 m<2>/g is more preferable. In this case, the anisotropic filler becomes wet easily in this dispersion liquid, and affinity with F powder tends to be improved. In addition, in the molded article, the anisotropic filler and the F polymer are more uniformly dispersed (distributed), and the physical properties of both are easily expressed in a well-balanced manner.

The surface of the anisotropic filler may be surface-treated.

As a surface treatment agent, polyhydric alcohol (trimethylolethane, pentaerythritol, propylene glycol, etc.), saturated fatty acid (stearic acid, lauric acid, etc.), its ester, alkanolamine, amine (trimethylamine, triethylamine, etc.), Paraffin wax, a silane coupling agent, silicone, polysiloxane, and an inorganic substance (oxides, such as aluminum, silicon, zirconium, tin, titanium, antimony, a hydroxide, a hydrated oxide, or a phosphate) are mentioned.

As a surface treatment agent, a silane coupling agent is preferable. In this case, the anisotropic filler and the F polymer powder are more compatible, and the dispersion stability of the present dispersion is easily improved. It is preferable that a silane coupling agent has an amino group, a thiol group, a vinyl group, an acroyloxy group, or a methacryloyloxy group.

The anisotropic filler may be an anisotropic filler having a hydrophobic portion and a hydrophilic portion. As such an anisotropic filler, it has a hydrophobic layer on the surface, and the anisotropic filler which has a hydrophilic layer inside is mentioned. Specific examples thereof include a plate-shaped multilayer filler including a hydrophobic layer, a hydrophilic layer (water-containing layer), and a hydrophobic layer in this order. As for the moisture content of a hydrophilic layer, 0.3 mass % or more is preferable. In this case, not only the dispersion state of the anisotropic filler in the dispersion is easily stabilized, but also the orientation of the anisotropic filler when molding a molded article from the dispersion is further increased, so that a molded article having high physical properties of the F polymer and the anisotropic filler is obtained. easy to obtain

1 micrometer or more is preferable, as for D50 of an anisotropic filler, 3 micrometers or more are more preferable, and 5 micrometers or more are still more preferable. 25 micrometers or less are preferable and, as for D50 of an anisotropic filler, 20 micrometers or less are more preferable. 10 micrometers or more are preferable and, as for D90 of an anisotropic filler, 15 micrometers or more are more preferable. 30 micrometers or less are preferable and, as for D90 of an anisotropic filler, 20 micrometers or less are more preferable. When D50 and D90 of the anisotropic filler are within these ranges, affinity with F powder is further improved, and dispersion stability of the present dispersion and physical properties of the molded product are more likely to improve. As a specific example of such an anisotropic filler, a flaky boron nitride filler and a plate-shaped talc filler are mentioned.

2 or more are preferable, as for the aspect-ratio of an anisotropic filler, 3 or more are more preferable, 5 or more are still more preferable, 10 or more are especially preferable. As for the aspect-ratio of an anisotropic filler, 10000 or less are preferable. In this case, it is easy to improve the orientation of the filler in a molding more easily, and it is easy to raise the function. Specifically, not only the dispersion state of the anisotropic filler in the dispersion is easily stabilized, but also the orientation of the anisotropic filler when molding a molded article from the dispersion is further increased. This is easy to obtain.

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 value of the length in the width direction) of the anisotropic filler.

As a specific aspect of such an anisotropic filler, an average minor diameter is 1 micrometer or less, or a filler whose average major diameter (average value of length in a longitudinal direction) is 1 micrometer or more is mentioned. As a specific example of such an anisotropic filler, a flat talc filler is mentioned.

A single layer structure may be sufficient as an anisotropic filler, and a multilayer structure may be sufficient as it. As such an anisotropic filler, the talc filler of a three-layer structure is mentioned.

Preferred specific examples of the anisotropic filler include boron nitride fillers (“UHP” series manufactured by Showa Denka Corporation, “HGP” series manufactured by Denka, “GP” series, etc.), talc fillers (“SG” manufactured by Nippon Talc). series, etc.).

In this dispersion, D50 of F powder is smaller than D50 of anisotropic filler. In other words, in the present dispersion, by densely containing the fine F powder, the affinity between the F powder and the anisotropic filler is increased, and the dispersion stability of the present dispersion is improved. Moreover, in a molded article, an anisotropic filler is disperse|distributed more uniformly, and the physical property is remarkably easy to express.

It is specifically, preferable that D50 of F powder is 0.1 micrometer or more and less than 5 micrometers, and it is preferable that D50 of an anisotropic filler is 1 micrometer or more and 25 micrometers or less.

Preferred embodiments of the filler contained in the dispersion include an anisotropic filler (hereinafter also referred to as “anisotropic filler 1”) and an inorganic filler having an average particle diameter smaller than that of the anisotropic filler 1 (hereinafter also referred to as “different filler”). described.) can be exemplified. In this case, the improvement of the dispersion stability of the dispersion liquid due to the interaction between the fillers and the ability to form a dense molded article by different fillers are balanced, and the physical properties of the resulting molded article (water resistance, low linear expansion property, electrical properties, etc.) more likely to be improved. In addition, a different filler should just be an inorganic filler whose average particle diameter is smaller than the anisotropic filler 1, and the material may be the same as or different from the anisotropic filler 1.

This preferred aspect WHEREIN: It is preferable that the average particle diameter of the anisotropic filler 1 is more than 6 micrometers and 15 micrometers or less, Moreover, it is preferable that the average particle diameters of different fillers are 1 micrometer or more and 6 micrometers or less. At this time, it is preferable that the anisotropic filler 1 is a filler containing boron nitride, and a different filler is a filler containing boron nitride or a magnesium metasilicate filler (steatite filler). Moreover, it is preferable that the aspect-ratio of the anisotropic filler 1 is 10 or more, and it is preferable that it is 40 or less, and, as for the aspect-ratio of a different filler, it is more preferable that it is less than 10.

In this case, in the molded article obtained, the random orientation of the anisotropic filler 1 is promoted by different fillers, and the filler physical properties and the molded article physical properties (adhesiveness, rigidity, etc.) are easily balanced.

This preferred aspect WHEREIN: It is also preferable that the average particle diameter of the anisotropic filler 1 is more than 1 micrometer and 15 micrometers or less, and it is also preferable that the average particle diameters of different fillers are 0.01 micrometer or more and less than 1 micrometer. At this time, it is preferable that the anisotropic filler 1 is a filler containing boron nitride, and that a different filler is a filler containing a silicon oxide.

It is preferable that the filler containing this silicon oxide is a silica filler or a magnesium metasilicate filler (steatite filler). Moreover, it is preferable that the surface of the filler containing a silicon oxide is surface-treated by the silane coupling agent.

It is preferable that the filler containing this silicon oxide is substantially spherical shape. In this case, it is easy to form a dense molding. In addition, when it observes with a scanning electron microscope (SEM), a substantially spherical shape means that the ratio of spherical particle|grains whose ratio of the minor axis with respect to a major axis is 0.7 or more is 95 % or more.

As a specific example of such a filler containing silicon oxide, a substantially spherical silica filler ("Admapine" series manufactured by Admatex, etc.), spherical fused silica ("SFP" series manufactured by Denka, etc.), hollow Phase silica filler (“E-SPHERES” series manufactured by Pacific Cement Co., Ltd., “Silinax” series manufactured by Nittetsu Mining Corporation, “Ecocospurer” series manufactured by Emerson & Carming, etc.), steatite filler (Japan) "BST" series manufactured by Talc, etc.) is mentioned.

In this preferred embodiment, the random orientation of the anisotropic filler 1 in the molded article is promoted by different fillers, and the filler physical properties in the molded article and the molded article physical properties (adhesiveness, surface smoothness, rigidity, etc.) are easily balanced. In short, in the molded article, the orientation of the anisotropic filler 1 is partially disturbed, and the electric properties and low linear expansion resulting from the height of the filler orientation and the rigidity, adhesion and surface smoothness resulting from the disruption of the filler orientation are highly provided in the molded article. easy.

Moreover, the filler in this preferable aspect may be contained in the state which has a multimodal particle size distribution. In this case, it is preferable that the peak resulting from the present filler 1 is the highest among the peaks in the particle size distribution from the viewpoint of facilitating formation of a dense molded product. Specifically, it is preferable that the filler is contained in a state having a bimodal particle size distribution having peaks in a region of 6 µm or less and a region exceeding 6 µm, respectively.

Moreover, as for the filler in this preferable aspect, the at least one part may adhere to the surface of F powder, and may be contained, and at least one part of F powder may adhere and may be contained in the surface. In this case, the present dispersion can also be said to contain a composite body of F powder and anisotropic filler 1, and the dispersion stability thereof is further improved, and various physical properties (water resistance, low linear expansion properties, electrical properties, etc.) of the molded product formed therefrom are improved. more likely to be improved.

Moreover, 0.1 or more are preferable and, as for mass ratio of content of the different filler with respect to content of the anisotropic filler 1 in this preferable aspect, 0.2 or more are more preferable. Moreover, 2 or less are preferable and, as for the said mass ratio, 1 or less is more preferable. In this case, the dispersion stability of the dispersion and the physical properties of the molded product are easily balanced.

5 mass % or more is preferable, as for content of the anisotropic filler in this dispersion liquid, 10 mass % or more is more preferable, and 25 mass % or more is still more preferable. 50 mass % or less is preferable, as for content of F powder, 40 mass % or less is more preferable, 30 mass % or less is still more preferable.

It is preferable that content of F polymer and content of an anisotropic filler in this dispersion liquid are 5 mass % or more, respectively. As for the sum of both content, 60 mass % or less is preferable. Even if each of the F polymer and the anisotropic filler is contained at such a high ratio (content), the dispersion is excellent in dispersion stability as in the above-mentioned mechanism of action, and it is easy to form a molded article having high physical properties of both.

It is preferable that this dispersion liquid further contains surfactant from a viewpoint of improving dispersion stability and handling property.

It is preferable that surfactant is nonionic.

It is preferable that the hydrophilic site|part of surfactant has an oxyalkylene group or alcoholic hydroxyl group.

The oxyalkylene group may be comprised by 1 type, and may be comprised by 2 or more types. In the latter case, the oxyalkylene groups from which a type differs may be arrange|positioned in random form, and may be arrange|positioned in block form.

The oxyalkylene group is preferably an oxyethylene group.

It is preferable that the hydrophobic site|part of surfactant has an acetylene group, a polysiloxane group, a perfluoroalkyl group, or a perfluoroalkenyl group. In other words, the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant, or a fluorine-based surfactant, and more preferably a silicone-based surfactant.

As the fluorine-based surfactant, a fluorine-based surfactant having a hydroxyl group (particularly, an alcoholic hydroxyl group) or an oxyalkylene group, a perfluoroalkyl group, or a perfluoroalkenyl group is more preferable.

Specific examples of surfactants include "Ftergent" series (manufactured by Neos), "Sufflon" series (manufactured by AGC Semi-Chemical, Inc.), "Megapac" series (manufactured by DIC), and "Unidyne" series ( Daikin Kogyo Co., Ltd.), 「BYK-347」, 「BYK-349」, 「BYK-378」, 「BYK-3450」, 「BYK-3451」, 「BYK-3455」, 「BYK-3456」 (Big Chemie - Japan Co., Ltd. make), "KF-6011", "KF-6043" (made by Shin-Etsu Chemical Industry Co., Ltd.) are mentioned.

As for content of surfactant in this dispersion liquid, 1-15 mass % is preferable. In this case, the affinity between the components is enhanced, and the dispersion stability of the present dispersion is more likely to be improved.

The liquid dispersion medium in the present invention is an inactive liquid compound at 25°C that functions as a dispersion medium for F powder and anisotropic filler. The liquid dispersion medium may be water or a non-aqueous dispersion medium may be sufficient as it. One type may be sufficient as a liquid dispersion medium, and 2 or more types may be sufficient as it. In this case, it is preferable that different types of liquid compounds are compatible.

As for the boiling point of a liquid dispersion medium, 125-250 degreeC is preferable. In this case, when forming a molded article from the present dispersion, the anisotropic filler tends to be oriented and the physical properties of the molded article are easily improved.

As the liquid dispersion medium, at least one liquid compound selected from the group consisting of amides, ketones and esters is preferable from the viewpoint of dispersion stability of the present dispersion, N-methyl-2-pyrrolidone, γ-butyrolactone, Cyclohexanone or cyclopentanone is more preferable.

50 mass % or more is preferable and, as for content of the liquid dispersion medium in this dispersion liquid, 60 mass % or more is more preferable. 90 mass % or less is preferable and, as for content of a liquid dispersion medium, 80 mass % or less is more preferable.

50 mPa*s or more is preferable and, as for the viscosity of this dispersion liquid, 100 mPa*s or more is more preferable. The viscosity of the dispersion liquid is preferably 10000 mPa·s or less, more preferably 1000 mPa·s or less, and still more preferably 800 mPa·s or less.

The thix ratio of this dispersion liquid is preferably 1.0 or more. 3.0 or less is preferable and, as for the thix ratio of this dispersion liquid, 2.0 or less are more preferable.

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 refers to the total height and components of the dispersion liquid (18 mL) in the screw tube before and after standing when the dispersion liquid (18 mL) is placed in a screw tube (internal volume: 30 mL) and left still at 25°C for 14 days. It is a value computed by the following formula from the height of a dispersion layer.

Component dispersion layer ratio (%) = (height of the component dispersion layer) / (the total height of the present dispersion liquid) x 100

In addition, when the component dispersion layer is not confirmed after standing still and there is no change in the state, it is assumed that there is no change in the overall height of the present dispersion liquid, and the component dispersion layer ratio is 100%.

This dispersion liquid is easy to adjust to the viscosity, thixotropy, or component dispersion layer ratio within these ranges by the above-mentioned action mechanism, and it is excellent in handling property.

The dispersion liquid may further contain another resin (polymer) different from the F polymer. A thermosetting resin may be sufficient as another resin, and a thermoplastic resin may be sufficient as it.

Examples of other resins include epoxy resins, maleimide resins, urethane resins, elastomers, polyimides, polyamic acids, polyamideimides, polyphenylene ethers, polyphenylene oxides, liquid crystal polyesters, and fluoropolymers other than F polymers. can

As a preferable aspect of another resin, the varnish of an aromatic polymer is mentioned. An aromatic polyimide or an aromatic polyamic acid is preferable and, as for an aromatic polymer, a thermoplastic aromatic polyimide is more preferable. In this case, in the molded article, the physical properties of the F polymer and the anisotropic filler are remarkably easily expressed. Moreover, when forming a molded object from this dispersion liquid, the powder fall of F powder is also suppressed, and the adhesiveness is also easy to improve more.

1-30 mass % is preferable and, as for content of the aromatic polymer in this dispersion liquid, 5-25 mass % is more preferable. 1.0 or less is preferable and, as for ratio in the mass of content of aromatic polymer with respect to content of F polymer, 0.1-0.7 are more preferable.

As a preferable aspect of another resin, the powder of polytetrafluoroethylene (PTFE) is mentioned. In this case, in the molded article, physical properties (electrical properties, such as low dielectric loss tangent property) based on PTFE are remarkably easily expressed. Moreover, PTFE becomes a nucleating agent, F polymer in a molding becomes easy to form microcrystals, the adhesiveness in the surface of a molding improves, and the adhesiveness becomes high easily. Moreover, it is easy to improve the orientation of the filler in a molded object, and the function is easy to improve.

PTFE (low molecular weight PTFE) whose number average molecular weight (Mn) computed based on following formula (1) is 200,000 or less is preferable as for PTFE.

Mn = 2.1 × 10 ¹⁰ × ΔHc ^-5.16 ... (1)

In formula (1), ΔHc represents the crystallization calorific value (cal/g) of PTFE measured by differential scanning calorimetry.

100,000 or less are preferable and, as for Mn of low molecular weight PTFE, 50,000 or less are more preferable. As for Mn of low molecular weight PTFE, 10,000 or more are preferable.

1-30 mass % is preferable and, as for content of PTFE in this dispersion liquid, 5-20 mass % is more preferable. 1.0 or less is preferable and, as for ratio in mass of content of PTFE with respect to content of F polymer, 0.1-0.4 are more preferable.

In the case of containing another resin, this dispersion liquid may be manufactured by mixing this dispersion liquid and the powder of another resin, and may mix and manufacture this dispersion liquid and the varnish containing another resin.

In addition to the components described above, the present dispersion contains a thixotropic agent, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a brightener, a colorant, a conductive agent, a mold release agent, and a surface. You may contain additives, such as a processing agent, a viscosity modifier, a flame retardant, and an isotropic filler.

This dispersion can be prepared by mixing F powder, anisotropic filler, and liquid dispersion medium, and it is preferable to prepare a liquid composition containing F powder and a liquid composition containing an anisotropic filler, respectively, and mix both. .

As a specific manufacturing method of this dispersion liquid, the manufacturing method of mixing F powder, anisotropic filler 1, a different filler, and a liquid dispersion medium is mentioned. At the time of this mixing, F powder and a liquid dispersion medium may be mixed beforehand, and a liquid composition may be formed, and the anisotropic filler 1 and the said different filler may be mixed previously.

Examples of the mixer used for mixing include a mixer using a stirring blade, a Henschel mixer, a ribbon blender, a oscillating mixer, a vibrating mixer, and a rotary mixer, and specifically, a homodisper, a homogenizer, and a ball mill. can be heard

The mixing method may be either batch type or continuous type. As for the mixer used for batch mixing, a Henschel mixer, a pressure kneader, a Banbury mixer, or a planetary mixer is preferable.

It is preferable to perform mixing by stirring, and it is more preferable to implement by rotation stirring by a stirring blade.

800 rpm or more is preferable and, as for the speed of stirring, 2000 rpm or more is more preferable. 10000 rpm or less is preferable and, as for the speed of stirring, 8000 rpm or less is more preferable. In this case, shear is applied to the F powder and the anisotropic filler, so that the aggregate is easily crushed, and the present dispersion excellent in dispersibility is easily obtained.

In addition, when the anisotropic filler is flaky or plate-shaped, the present dispersion excellent in dispersibility is easily formed because the layered aggregate (secondary particles) of the formed anisotropic filler is effectively disintegrated to form a card house structure. .

The molded article of the present invention (hereinafter also referred to as “the present molded article”) comprises a tetrafluoroethylene-based polymer (hereinafter also referred to as “PFA-based polymer”) containing a PAVE unit, and an anisotropy having a Mohs hardness of 4 or less. including fillers. In addition, the PFA-based polymer is a polymer having a polar functional group, or a polymer containing 2.0 to 5.0 mol% of a PAVE unit with respect to the total unit and not having a polar functional group, and the proportion (content) of the anisotropic filler in the present molding is It is 10 mass % or more.

As a shape of this molding, a layered shape, a plate shape, and a block shape are mentioned, It is preferable that it is layered. As for the thickness of a layered molding, 150 micrometers or less are preferable. Such a layered molding is useful for the manufacture of impregnated substances, such as a film and a prepreg, and a laminated board.

The definition and range of the anisotropic filler in this molding are the same as those of the anisotropic filler in this dispersion liquid, including a preferable aspect.

In this molded article, the type and range of the polar functional group of the PFA-based polymer are the same as those of the F-polymer, including preferred embodiments. Moreover, as for a PFA-type polymer, a polymer (1) or a polymer (2) is preferable.

15 mass % or more is preferable and, as for content of the anisotropic filler in this molding, 25 mass % or more is more preferable. 50 mass % or less is preferable and, as for content of an anisotropic filler, 40 mass % or less is more preferable.

40 mass % or more is preferable, as for content of the PFA type polymer in this molding, 50 mass % or more is more preferable, and its 60 mass % or more is still more preferable. 95 mass % or less is preferable, as for content of a PFA-type polymer, 80 mass % or less is more preferable, and its 70 mass % or less is still more preferable. When the content of the PFA-based polymer is within such a range, the physical properties of the PFA-based polymer are remarkably exhibited in the present molded article. Moreover, the powder fall-off of the anisotropic filler from this molding is suppressed.

It is preferable that this molding further contains an aromatic polymer (especially aromatic polyimide) or PTFE. In this molded article, the definitions and ranges of each of the aromatic polymer and PTFE, and the ratios in the mass of each content to the content of the F polymer are the same as those in the present dispersion.

It is preferable to form this molding from this dispersion liquid. Specifically, when this 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 as the molded product (hereinafter, also referred to as “this layer”) is formed on the substrate. It can be easily formed on the surface. More specifically, when the present dispersion is applied to the surface of the substrate, the substrate is heated to remove the liquid dispersion medium, and further heated to melt and bake the PFA-based polymer, a laminate having a substrate and the main layer formed on the surface of the substrate is obtained As for the temperature in the former heating, 120 degreeC - 200 degreeC are preferable. On the other hand, 250 degreeC - 400 degreeC are preferable and, as for the temperature in the latter heating, 300-380 degreeC are more preferable.

As the substrate, a metal substrate (metal foil such as copper, nickel, aluminum, titanium, alloys thereof, etc.), a resin film (polyimide, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, polyphenylenesulfone) Films, such as a phide, polyallyl ether ketone, polyamideimide, liquid crystalline polyester, and liquid crystalline polyester amide), and a prepreg (precursor of a fiber reinforced resin substrate) are mentioned.

It is preferable to apply|coat this dispersion liquid. Application methods include spray method, roll coat method, spin coat method, gravure coat method, micro gravure coat method, gravure offset method, knife coat method, kiss coat method, bar coat method, die coat method, Fountain Mayer bar method, slot method A die-coating method is mentioned.

As a method of each heating, the method of using an oven, the method of using a ventilation drying furnace, and the method of irradiating heating rays, such as infrared rays, are mentioned.

As for the thickness of this layer, 0.1-150 micrometers is preferable. Specifically, as for the thickness of this layer, if a board|substrate is metal foil, 1-30 micrometers is preferable. When a board|substrate is a resin film, 1-150 micrometers is preferable and, as for the thickness of this layer, 10-50 micrometers is more preferable.

This dispersion liquid may be provided only on one surface of a board|substrate, and may be provided on both surfaces of a board|substrate. In the former, the laminated body which has a board|substrate and this layer on one surface of a board|substrate is obtained, and in the latter, the laminated body which has a board|substrate and this layer on both surfaces of a board|substrate is obtained. Since the latter laminate is less prone to warping, it is excellent in handling properties at the time of processing.

Specific examples of such a laminate include a metal foil, a metal-clad laminate having a main layer on at least one surface of the metal foil, and a polyimide film and a multilayer film having a main layer on both surfaces of the polyimide film. can

These laminates are excellent in physical properties, such as electrical properties, and are preferable as a printed circuit board material etc. Specifically, such a laminate can be used for manufacture of a flexible printed circuit board or a rigid printed circuit board.

Example

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

1. Preparation of each ingredient

[powder]

Powder 1: TFE unit, NAH unit and PPVE unit, in this order, 97.9 mol%, 0.1 mol%, 2.0 mol%, PFA-based polymer 1 having 1000 carbonyl groups per 1 × 10 ⁶ carbon atoms in the main chain (melted Temperature: 300°C) powder (D50: 2.1 µm)

Powder 2: Powder consisting of PFA-based polymer 2 (melting temperature 305° C.) containing 97.5 mol% and 2.5 mol% of TFE units and PPVE units in this order, and having 40 carbonyl groups per 1×10 ⁶ carbon atoms in the main chain (D50: 1.8 μm)

Powder 3: Powder consisting of PFA-based polymer 2 (D50: 5.3 μm)

Powder 4: Powder consisting of PTFE with a number average molecular weight of 20,000 (D50: 3.2 μm)

[Anisotropic filler]

Filler 1: flaky filler made of boron nitride (D50: 7.0 µm)

Filler 2: flaky filler made of boron nitride (D50: 3.7 µm)

Filler 3: flaky filler made of boron nitride (D50: 7.3 µm)

Filler 4: A plate-shaped talc filler having a three-layer structure having a hydrophobic layer, a hydrophilic layer, and a hydrophobic layer in this order (D50: 4.5 μm, average major diameter: 5.1 μm, average minor diameter: 0.2 μm, aspect ratio: 25, manufactured by Nippon Talc “SG” -95")

In addition, Mohs' Hardness of Fillers 1-3 is 2, and Mohs' Hardness of Filler 4 is 1. Fillers 1, 2 and 4 are surface-treated with a silane coupling agent.

[Liquid dispersion medium]

NMP: N-methyl-2-pyrrolidone

[Surfactants]

Surfactant 1: Copolymer of 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 and a nonionic polymer having a fluorine content of 35% by mass

[Varnish of aromatic polymer]

Varnish 1: Varnish in which thermoplastic aromatic polyimide (PI1) was dissolved in NMP (solid content concentration: 18 mass%)

2. Preparation example of dispersion

(Example 1)

First, the powder 1, the varnish 1, the surfactant 1, and NMP were thrown into the pot, and the zirconia ball|bowl was thrown in. Then, the pot was rolled at 150 rpm for 1 hour, and the composition was prepared. Filler 1, surfactant 1, and NMP were put into another pot, and zirconia balls were put therein. Then, the pot was rolled at 150 rpm for 1 hour, and the composition was prepared.

In another pot, both compositions were put, and zirconia balls were put there. Thereafter, the pot is rolled at 150 rpm for 1 hour, 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) ) containing dispersion 1 (viscosity: 400 mPa·s) was obtained.

(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 liquid 10 was obtained in the same manner as in Example 1 except that 3 parts by mass of the filler 1 and 8 parts by mass of the filler 2 were used instead of 11 parts by mass of the filler 1.

3. Manufacturing example of molded article

The dispersion liquid 1 was apply|coated on the surface of the long copper foil (18 micrometers in thickness) using the bar coater, and the wet film was formed. Next, this metal foil with a wet film was passed through a drying furnace at 120 degreeC for 5 minutes, it was made to dry by heating, and the dry film was obtained. Then, the dry film was heated at 380 degreeC for 3 minute(s) in nitrogen oven. Thereby, the laminated body 1 which has a metal foil and the polymer layer (thickness 5 micrometers) as a molded object containing the melt-fired material of the powder 1, and the filler 1 on the surface was manufactured.

Except having changed the dispersion liquid 1 into each of the dispersion liquids 2-10, it carried out similarly to the laminated body 1, and manufactured the laminated bodies 2-10, respectively.

4. Evaluation

4-1. Dispersion stability of dispersion

After the dispersion liquids 1-10 were stored at 25 degreeC in a container, the dispersibility was visually confirmed, and dispersion stability was evaluated according to the following reference|standard.

[Evaluation standard]

(double-circle) : Aggregate is not visually recognized.

(circle): Adherence of a fine aggregate to a container side wall is visually recognized. It was redispersed uniformly with gentle stirring.

(triangle|delta): It is visually recognized that the aggregate has precipitated also in the container bottom. When agitated by applying shear, it is uniformly redispersed.

x: It is visually recognized that the aggregate is also precipitated in the container bottom. It is difficult to redisperse even if it is stirred by applying shear.

4-2. Physical properties of the laminate

4-2-1. surface smoothness

About the polymer layers of the laminated bodies 1-9, the surface smoothness was visually confirmed, and the surface smoothness was evaluated according to the following reference|standard.

[Evaluation standard]

○: The entire surface of the polymer layer is smooth.

(triangle|delta): The unevenness|corrugation by the loss|missing of a polymer or a filler is visually recognized by the edge part of the surface of a polymer layer.

x: The unevenness|corrugation by missing|missing of a polymer or an inorganic filler is visually recognized by the whole surface of a polymer layer.

4-2-2. coefficient of linear expansion

For each of the laminates 1 to 4, 9 and 10, a 180 mm square test piece is cut out, and according to the measurement method specified in JIS C 6471: 1995, in the range of 25°C or more and 260°C or less, The coefficient of linear expansion of the test piece was measured.

[Evaluation standard]

(circle): 30 ppm/degreeC or less.

x: It is more than 30 ppm/degreeC.

4-2-3. hereditary tangent

For each of the laminates 1 to 4, 9 and 10, the copper foil of the laminate was removed by etching with an aqueous ferric chloride solution to prepare a single polymer layer, and by SPDR (split post dielectric resonance) method, the polymer The dielectric loss tangent (measurement frequency: 10 GHz) of the layer was measured.

[Evaluation standard]

(circle): The dielectric loss tangent is less than 0.0010.

(triangle|delta): The dielectric loss tangent is 0.0010 or more and 0.0025 or less.

x: The dielectric loss tangent is more than 0.0025.

Each evaluation result is put together in Table 2 below, and is shown.

5. Preparation example of dispersion (Part 2)

(Example 11)

First, powder 1, surfactant 1, and NMP were added to a pot and mixed, and the composition was adjusted by stirring at 2000 rpm with a homodisper for 1 hour. Filler 1, surfactant 1, and NMP were put into another pot, and the composition was adjusted by stirring at 2000 rpm with a homodisper for 1 hour. In another pot, put both compositions, and stirred for 1 hour at 2000 rpm with a homodisper, powder 1 (11 parts by mass), filler 1 (11 parts by mass), surfactant 1 (4 parts by mass) and NMP A dispersion liquid 11 (viscosity: 300 mPa·s, component dispersion layer rate: 80%) containing (74 parts by mass) was obtained.

(Example 12)

A dispersion liquid 12 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 homodisper (viscosity: 300 mPa·s, component dispersion layer rate: 50%) .

6. Preparation example of laminate (Part 2)

The dispersion liquid 11 was coated on the surface of an 18-micrometer-thick aluminum foil by the roll-to-roll method by the gravure reverse method, and the liquid film was formed. Next, this aluminum foil with a liquid film was made to pass through a 120 degreeC drying furnace for 5 minutes, and it was dried by heating. Then, in the far-infrared oven in nitrogen atmosphere, the dry film was heated at 340 degreeC for 3 minute(s). Thereby, the laminated body 11 in which the polymer layer (thickness: 10 micrometers) was formed on the surface of aluminum foil was manufactured. In addition, it carried out similarly to the laminated body 11 except having used the dispersion liquid 12 instead of the dispersion liquid 11, and the laminated body 12 was manufactured.

As a result of observing the cross section of each laminated body by SEM, the distribution state of the filler 1 was denser in the polymer layer of the laminated body 11 than the polymer layer of the laminated body 12. Moreover, the polymer layer of the laminated body 11 had a dielectric loss tangent lower than the polymer layer of the laminated body 12. The laminate 11 was superior to the laminate 12 in thermal conductivity and bendability.

The dispersion liquid of the present invention is excellent in dispersion stability and has properties based on F polymer (PFA-based polymer) and properties based on anisotropic filler (film, impregnated material such as prepreg, laminate, covering material, etc.) can be used for manufacturing. The molded article of the present invention is useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food and industrial products, paints, cosmetics, etc., specifically, heat dissipation members, electric wire covering materials (aircraft electric wires, etc.) , electrical insulating tape, insulating tape for petroleum excavation, materials for printed circuit boards, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrode binders (for lithium secondary batteries, fuel cells, etc.), Copy rolls, furniture, automobile dash boats, covers of home appliances, etc., sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, food conveying belts, etc.), tools (shovels, files, awls, saw), boilers, hoppers, pipes, ovens, grills, chutes, dies, toilet bowls, container coverings, and heat exchangers (fins, heat transfer tubes, etc.)

Claims (15)

A powder of a tetrafluoroethylene polymer comprising a unit based on perfluoro (alkyl vinyl ether) or a unit based on hexafluoropropylene, an anisotropic filler having a Mohs hardness of 4 or less, and a liquid dispersion medium; The dispersion liquid, wherein the average particle diameter of the powder is smaller than the average particle diameter of the anisotropic filler. The method of claim 1,
The dispersion liquid, wherein the content of the tetrafluoroethylene-based polymer and the content of the anisotropic filler are 5 mass% or more, respectively. 3. The method according to claim 1 or 2,
The dispersion liquid, wherein the shape of the anisotropic filler is flaky or plate-like. 4. The method according to any one of claims 1 to 3,
The dispersion liquid, wherein the aspect ratio of the anisotropic filler is 2 or more. 5. The method according to any one of claims 1 to 4,
The dispersion liquid, wherein the anisotropic filler is an anisotropic filler containing boron nitride or talc. 6. The method according to any one of claims 1 to 5,
Further comprising a powder or an aromatic polymer of polytetrafluoroethylene. 7. The method according to any one of claims 1 to 6,
A dispersion liquid having a component dispersion layer ratio of 60% or more. A method for producing the dispersion according to any one of claims 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. Way. 9. The method of claim 8,
The manufacturing method which performs the said mixing by stirring. A molded article comprising a tetrafluoroethylene-based polymer containing units based on perfluoro (alkyl vinyl ether) and an anisotropic filler having Mohs hardness of 4 or less,
The tetrafluoroethylene-based polymer is a polymer having a polar functional group, or a polymer containing 2.0 to 5.0 mol% of units based on perfluoro (alkylvinyl ether) with respect to all units, and having no polar functional group, , The molded article, wherein the proportion of the anisotropic filler in the molded article is 10 mass% or more. 11. The method of claim 10,
The aspect ratio of the said anisotropic filler is 2 or more, The molded object. 12. The method of claim 11,
The molded article, wherein the anisotropic filler is a flaky anisotropic filler containing boron nitride or a plate-shaped anisotropic filler containing talc. 13. The method according to any one of claims 10 to 12,
The molded article, wherein the average particle diameter of the anisotropic filler is 1 µm or more. 14. The method according to any one of claims 10 to 13,
Further comprising polytetrafluoroethylene or an aromatic polymer. 15. The method according to any one of claims 10 to 14,
The molding is a layered molding having a thickness of 150 µm or less.