TW202200703A - Composite particle, composite particle production method, liquid composition, laminate manufacturing method, and film manufacturing method - Google Patents

Abstract

The present invention addresses the problem of providing a composite particle containing an arbitrary amount of an inorganic substance and having desired physical properties such as high polarity. A composite particle according to the present invention contains: a tetrafluoroethylene-based polymer having a melting temperature of 260-320oC; and an inorganic substance, wherein the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a tetrafluoroethylene-based polymer containing a unit based on perfluoro(alkyl vinyl ether) and having a polar functional group, and a tetrafluoroethylene-based polymer containing, with respect to all units, 2.0-5.0 mol% of a unit based on perfluoro(alkyl vinyl ether) and having no polar functional group.

Description

Composite particle, method for producing composite particle, liquid composition, method for producing layered product, and method for producing film

The present invention relates to a composite particle containing a specific tetrafluoroethylene-based polymer and an inorganic substance, a method for producing the same, a liquid composition using the composite particle, a method for producing a laminate, and a method for producing a film.

As a composite particle of a silicon oxide and a tetrafluoroethylene-type polymer, the aspect of patent document 1 or patent document 2 is known. However, since the tetrafluoroethylene-based polymer has extremely low polarity and low affinity with other components, it is also difficult to highly interact with silicon oxide. Therefore, the composite particles of the above-mentioned documents cannot easily absorb a sufficient amount of silicon oxide. Furthermore, with regard to the composite particles of the above-mentioned documents, since the interaction between silicon oxide and the tetrafluoroethylene-based polymer is low, the stability of itself is not sufficient, and the silicon oxide is easily detached from the composite particles. Therefore, it is necessary to ensure the interaction between silicon oxide and tetrafluoroethylene-based polymer, and the selection range of silicon oxide (the amount of hydroxyl groups of silicon oxide, etc.) is easily limited. Furthermore, due to this limitation, the use of the composite particles of the above-mentioned documents is limited. For example, it is difficult to improve the affinity of the composite particles to the liquid medium, and when preparing a liquid composition in which the composite particles are dispersed, foaming is violent, and it is difficult to ensure the dispersion stability. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2016-124729 Patent Document 2: International Publication No. 2018/212279

[Problems to be Solved by Invention]

As a result of earnest research by the present inventors, it was found that these problems can be solved by using a specific tetrafluoroethylene-based polymer, and the present invention has been completed. An object of the present invention is to provide composite particles containing an arbitrary amount of inorganic substances and having desired physical properties such as high polarity. [Technical means to solve problems]

<1> A composite particle comprising a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an inorganic substance, wherein the tetrafluoroethylene-based polymer is selected from the group consisting of perfluoro(alkyl vinyl ether)-based Units and tetrafluoroethylene-based polymers having polar functional groups, and tetrafluoroethylene-based polymers that contain 2.0 to 5.0 mol % of perfluoro(alkyl vinyl ether)-based units with respect to all units and do not have polar functional groups At least one of the group consisting of polymers. <2> The composite particles according to the above <1>, wherein the powder kinetic friction angle of the composite particles is 40 degrees or less. <3> The composite particle according to the above <1> or <2>, wherein the inorganic substance is silicon oxide or boron nitride. <4> The composite particles according to the above <1> to <3>, wherein the composite particles are spherical or scaly. <5> The composite particle according to any one of the above <1> to <4>, which has the above-mentioned tetrafluoroethylene-based polymer as a core, and has the above-mentioned inorganic substance on the surface of the above-mentioned core. <6> The composite particle according to the above <5>, wherein the core of the tetrafluoroethylene-based polymer and the inorganic substance are each in the form of particles, and the average particle diameter of the core is larger than the average particle diameter of the inorganic substance. <7> The composite particle according to any one of the above <5> or <6>, wherein the ratio of the fluorine element content to the inorganic element content on the surface of the composite particle measured by energy dispersive X-ray spectroscopy less than 1. <8> The composite particle according to any one of the above-mentioned <1> to <4>, which has the above-mentioned inorganic substance as a core and has the above-mentioned tetrafluoroethylene-based polymer on the surface of the above-mentioned core. <9> The composite particle according to the above-mentioned <8>, wherein the mass of the inorganic substance in the composite particle is larger than the mass of the tetrafluoroethylene-based polymer. <10> A method for producing composite particles, which is a method for producing composite particles according to any one of the above-mentioned <1> to <9>, wherein the particles of the tetrafluoroethylene-based polymer and the particles of the inorganic substance are prepared in the above-mentioned The composite particles described above are obtained by colliding in a floating state at a temperature equal to or higher than the melting temperature of the tetrafluoroethylene-based polymer. <11> A method for producing composite particles, which is a method for producing composite particles according to any one of the above <1> to <9>, wherein the particles of the tetrafluoroethylene-based polymer and the particles of the inorganic substance are extruded. The composite particles are obtained by colliding under pressure or shearing state. <12> A liquid composition comprising the composite particles according to any one of the above <1> to <9>, and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid dispersion. <13> The liquid composition according to the above <12>, wherein the liquid dispersion medium is at least one liquid compound selected from the group consisting of water, amides, ketones, and esters. <14> A method for producing a layered product, comprising applying the liquid composition according to the above-mentioned <12> or <13> to the surface of a base material layer, heating, and forming a polymer layer, thereby obtaining the base material layer and the A laminate of the above polymer layers. <15> A method for producing a film, wherein the composite particles according to any one of the above <1> to <9> are melt-kneaded with a fluoroolefin-based polymer, and then extrusion-molded to obtain a film. [Effect of invention]

According to the present invention, composite particles containing an arbitrary amount of inorganic substances and having desired physical properties such as high polarity can be obtained. In addition, according to the present invention, a liquid composition containing composite particles and excellent in dispersion stability, and a laminate having a high degree of excellent properties (electrical properties, low linear expansion, etc.) based on a tetrafluoroethylene-based polymer and an inorganic substance can be obtained body and film.

The following terms have the following meanings. The "average particle diameter (D50)" is the volume-based cumulative 50% diameter of the object (particle) obtained by the laser diffraction-scattering method. That is, the particle size distribution of the object is measured by the laser diffraction-scattering method, the total volume of the particle clusters of the object is taken as 100%, the cumulative curve is obtained, and the cumulative volume is 50% on the cumulative curve. particle size. "D90" is the volume-based cumulative 90% diameter of the object measured in the same way. The "powder kinetic friction angle" is a value obtained by measuring the object by the measurement method specified in JIS Z 8835:2016. The "melting temperature (melting point)" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by differential scanning calorimetry (DSC). "Glass transition point (Tg)" is the value determined by analyzing the polymer by dynamic viscoelasticity (DMA) method. "Viscosity" is a value obtained by measuring the liquid composition using a Brookfield viscometer at 25°C and a rotation speed of 30 rpm. The measurement was repeated three times, and the average value of the three measured values was used. The so-called "thixotropy ratio" is obtained by dividing the viscosity η1 obtained by measuring the liquid composition at _a rotational speed of 30 rpm by the measurement of the liquid composition at a rotational speed of 60 rpm. The value calculated from the viscosity η ₂ (η ₁ /η ₂ ). The "unit" in the polymer may be an atomic group directly formed from a monomer, or an atomic group after a part of the structure is converted by treating the obtained polymer by a specific method. The unit based on the monomer A contained in the polymer is also abbreviated as "monomer A unit".

The composite particles of the present invention (hereinafter, also referred to as "the present particles") are particles containing a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an inorganic substance. In addition, the tetrafluoroethylene-based polymer (hereinafter, also referred to as "F polymer") is selected from a polymer including a unit (PAVE unit) based on perfluoro(alkyl vinyl ether) (PAVE) and having a polar functional group At least one of the group consisting of the product (1) and the polymer (2) which contains 2.0 to 5.0 mol % of PAVE units with respect to all units and does not have a polar functional group.

The particle is a composite of F polymer and inorganic matter, the above-mentioned composite can contain any amount of inorganic matter, and the physical properties such as polarity can be adjusted to the desired level, and the stability is high. The mechanism of action is not clear, but is considered as follows. The F polymer not only has excellent shape stability such as fiber resistance, but also has a configuration with a high degree of freedom that reduces the restriction of molecular motion at the single-molecule level. The F polymer tends to form microscopic spherulites at the molecular aggregate level, and tends to produce microscopic concavo-convex structures on its surface. Therefore, it is considered that the molecular aggregate of the F polymer (particles of the F polymer alone, etc.) is physically and closely adhered to the inorganic substance in a state in which it is stable and does not impair its shape. In addition, it is also considered that the interaction between the closely adhered inorganic substances further promotes the adhesion of the inorganic substances and stabilizes the composite particles. As a result, it is considered that this particle contains an arbitrary amount of inorganic substances, in other words, contains a large amount of inorganic substances, has high stability, and has high physical properties of the F polymer and physical properties of inorganic substances.

The F polymer in this particle is a polymer comprising TFE units and PAVE units. As PAVE, CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ , and CF ₂ =CFOCF ₂ CF ₂ CF ₃ (PPVE) are preferred, and PPVE is more preferred. The melting temperature of the F polymer is 260-320°C, preferably 285-320°C. The glass transition point of the F polymer is preferably 75 to 125°C, more preferably 80 to 100°C. The melt viscosity of the F polymer at 380° C. is preferably 1×10 ² to 1×10 ⁶ Pa·s, more preferably 1×10 ³ to 1×10 ⁶ Pa·s. As long as the melting temperature, glass transition point or melt viscosity of the F polymer is within this range, the above-mentioned mechanism of action is easily enhanced.

The polar functional group possessed by the polymer (1) may be contained in the unit contained in the polymer, or may be contained in the terminal group of the polymer main chain. As the latter polymer, a polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., a polymer having a polar functional group prepared by plasma treatment or ionizing radiation treatment can be exemplified. of polymers. When the F polymer is the polymer (1), in the present particle, the polymer (1) and the inorganic substance are easily attached not only physically but also chemically, and the above-mentioned mechanism of action is easily enhanced. The polar functional group is preferably a hydroxyl group-containing group, a carbonyl group-containing group, and a phosphine group-containing group. In order to easily improve the physical properties such as the dispersibility of the particles, a hydroxyl group-containing group and a carbonyl group-containing group are more preferable. Furthermore, a carbonyl group-containing group is preferable.

The hydroxyl group-containing group is preferably an alcoholic hydroxyl group-containing group, more preferably -CF ₂ CH ₂ OH, -C(CF ₃ ) ₂ OH and 1,2-diol group (-CH(OH)CH ₂ OH). The carbonyl group-containing group is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a urethane group (-OC(O)NH ₂ ), an acid anhydride residue (-C(O)OC) (O)-), imide residues (-C(O)NHC(O)- etc.) and carbonate groups (-OC(O)O-), more preferably acid anhydride residues.

When the polymer (1) has a carbonyl-containing group, the number of carbonyl-containing groups in the polymer (1) is preferably 500 to 5000 per 1×10 ⁶ carbon atoms in the main chain, More preferably, it is 600-3000 pieces, and still more preferably, it is 800-1500 pieces. In addition, the number of carbonyl-containing groups in the polymer (1) can be quantified by the composition of the polymer or the method described in International Publication No. WO 2020/145133. In this case, the chemical interaction between the polymer (1) and the inorganic substance is also improved, and the inorganic substance easily adheres to the surface of the molecular aggregate of the polymer (1) physically and chemically.

The polymer (1) preferably contains 90 to 99 mol % of TFE units, 0.5 to 9.97 mol % of PAVE units, and 0.01 to 3 mol % of a monomer based on a monomer having a polar functional group, respectively, with respect to all units. unit. Further, as the monomer having a polar functional group, itaconic acid anhydride, citraconic acid anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter, also referred to as "NAH") are preferred, and NAH is more preferred . As a specific example of the polymer (1), the polymer described in International Publication No. 2018/16644 can be mentioned.

The polymer (2) is composed of only TFE units and PAVE units, and preferably contains 95.0 to 98.0 mol % of TFE units and 2.0 to 5.0 mol % of PAVE units with respect to all units. The content of the PAVE unit in the polymer (2) is preferably 2.1 mol % or more, more preferably 2.2 mol % or more with respect to all the units. The molecular configuration of the polymer has a higher degree of freedom, and the above-mentioned mechanism of action is easily enhanced. Further, that the polymer (2) does not have polar functional groups means that the number of polar functional groups the polymer has per 1×10 ⁶ carbon atoms constituting the main chain of the polymer is less than 500. The number of the above-mentioned polar functional groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of the above-mentioned polar functional groups is usually zero.

The polymer (2) can also be produced by using a polymerization initiator or a chain transfer agent that does not generate polar functional groups as the terminal groups of the polymer chain, and can also be used for polymers with polar functional groups (at the end of the polymer chain). A polymer having a polar functional group derived from a polymerization initiator, etc.) is produced by subjecting it to a fluorination treatment. As a method of the fluorination treatment, a method of using fluorine gas (refer to Japanese Patent Laid-Open No. 2019-194314, etc.) may be mentioned.

The present particles may also contain other polymers than F polymers. Among them, the ratio of the F polymer contained in the particles to the polymer is preferably 80% by mass or more, more preferably 100% by mass. Examples of polymers other than the F polymer include heat-resistant resins such as aromatic polyester, polyamide imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.

The inorganic substances in the particles are preferably oxides, nitrides, metal elements, alloys and carbon, more preferably silicon oxides (silica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, alkali aluminum oxide, oxide Magnesium, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (mass talc), and preferably inorganic oxides containing at least one element selected from the group consisting of aluminum, magnesium, silicon, titanium, and zinc Compounds, talc and boron nitride, especially silicon oxide and boron nitride, most preferably silicon oxide. In addition, the inorganic substance may be ceramics. One type of inorganic substances may be used, or two or more types may be used in combination. In the case of mixing two or more inorganic substances, two types of silicon oxides may be used, or silicon oxides and metal oxides may be used.

The inorganic matter easily enhances the interaction with the F polymer, and the particle can contain more inorganic matter. Moreover, in the molded object (for example, the following polymer layer and thin film) formed from this particle, the physical property based on an inorganic substance is easy to express remarkably. The inorganic substance in the particle preferably contains silicon oxide. The content of silicon oxide in the inorganic material is preferably 50% by mass or more, more preferably 75% by mass or more. The upper limit of the content of silicon oxide is 100% by mass.

The inorganic substance is preferably surface-treated on at least a part of its surface. As the surface treatment agent used for the surface treatment, polyhydric alcohols (trimethylolethane, pentaerythritol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkanolamines, Amines (trimethylamine, triethylamine, etc.), paraffin, silane coupling agents, silicones, polysiloxanes, oxides of aluminum, silicon, zirconium, tin, titanium, antimony, etc., their hydroxides, and the like The hydrated oxides, their phosphates.

As the silane coupling agent, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane are preferred silane, 3-methacryloyloxypropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane.

The specific surface area (BET method) of the inorganic substance is preferably 1 to 20 m ² /g, more preferably 5 to 8 m ² /g. In this case, the interaction between the inorganic substance and the F polymer is easily enhanced. In addition, in the molded product (polymer layer, etc.), the inorganic substance and the F polymer are more uniformly distributed, and the physical properties of the two are easily balanced.

Specific examples of inorganic substances include silica fillers ("Admafine (registered trademark)" series manufactured by Admatechs, etc.), zinc oxide (Sakai Chemical Industry Co., Ltd.) surface-treated with esters such as propylene glycol diddecanoate. "FINEX (registered trademark)" series manufactured by Co., Ltd., etc.), spherical fused silica ("SFP (registered trademark)" series manufactured by DENKA Corporation, etc.), rutile type coated with polyols and inorganic substances Titanium oxide ("Tipaque (registered trademark)" series manufactured by Ishihara Sangyo Co., Ltd., etc.), rutile-type titanium oxide surface-treated with alkylsilane ("JMT (registered trademark)" series manufactured by Tayca Corporation, etc.), Hollow silica fillers ("E-SPHERES" series manufactured by Taiheiyo Cement Corporation, "SiliNax" series manufactured by Nippon Steel Mining Corporation, "Ecco sphere" series manufactured by Emerson & Cuming Corporation, hydrophobic AEROSIL manufactured by Nippon Aerosil Corporation) series "RX200", etc.), talc filler ("SG" series manufactured by Nippon Talc Corporation, etc.), block talc filler ("BST" series manufactured by Nippon Talc Corporation, etc.), boron nitride filler ("UHP" manufactured by Showa Denko Corporation) " series, "DENKA Boron Nitride" series ("GP", "HGP" grades) manufactured by DENKA Corporation, etc.).

The shape of the inorganic substance is preferably a particle shape, preferably a spherical shape, a needle shape (fiber shape), or a plate (column) shape. Specific shapes of inorganic substances include spherical, scale-like, lamellar, leaf-like, almond-like, columnar, cockscomb-like, equiaxed, leaf-like, mica-like, block-like, plate-like, and wedge-like. , rosette-like, net-like, angular column-like, preferably spherical and scaly. When an inorganic substance of this shape is used, the uniformity of the distribution of the inorganic substance in the molded product (polymer layer, etc.) is improved, and its function can be easily improved. The inorganic substances are preferably spherical silicon oxide and scaly boron nitride.

The spherical inorganic substance is preferably substantially spherical. The term "substantially true spherical shape" means that when the particles are observed with a scanning electron microscope (SEM), the ratio of spherical particles having a ratio of a short axis to a long axis of 0.5 or more is 95% or more. In this case, in the inorganic particles, the ratio of the short axis to the long axis is preferably 0.5 or more, more preferably 0.8 or more. The above-mentioned comparison is preferably less than 1. When the inorganic particles having a substantially spherical height are used, the inorganic material and the F polymer are more uniformly distributed in the molded product (polymer layer, etc.), and the physical properties of the two are more easily balanced.

When the shape of the inorganic substance is scaly, it is easy for the inorganic substance to form a path in the molded article, and it is easy to make the molded article excellent in thermal conductivity. The aspect ratio of the scaly inorganic substance is preferably 5 or more, more preferably 10 or more. The aspect ratio is preferably 1000 or less. The average major diameter (average value of the diameter in the longitudinal direction) of the scaly inorganic substance is preferably 1 μm or more, more preferably 3 μm or more. The average major diameter is preferably 20 μm or less, more preferably 10 μm or less. The average short diameter (average value of diameters in the short side direction) is preferably 0.01 μm or more, more preferably 0.1 μm or more. The average short diameter is preferably 1 μm or less, more preferably 0.5 μm or less. In this case, in the molded product (polymer layer, etc.), the inorganic substance and the F polymer are more uniformly distributed, and the physical properties of the two are more easily balanced.

The scaly inorganic substance may have a single-layer structure or a multi-layer structure. As the latter inorganic substance, an inorganic substance having a hydrophobic layer on the surface and a hydrophilic layer on the inside can be exemplified. As a specific example, the inorganic substance provided with a hydrophobic layer, a hydrophilic layer (aqueous layer), and a hydrophobic layer in this order is mentioned. The water content of the hydrophilic layer is preferably 0.3% by mass or more. In this case, not only the dispersion state of the particles in the liquid composition is easily kept stable, but also the orientation of the inorganic substance in the molded product (polymer layer, etc.) is further improved, and it is easy to obtain the physical properties and inorganic substances highly possessing the F polymer. The physical properties of the molded product (polymer layer, etc.).

D50 of this particle is preferably 40 μm or less, more preferably 10 μm or less, still more preferably 6 μm or less, particularly preferably 4 μm or less. D50 of this particle is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 1 μm or more. Moreover, D90 of this particle is preferably 50 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. When the D50 and D90 of the particles are in these ranges, the dispersion stability of the particles in the liquid composition and the physical properties of the molded product (polymer layer, etc.) obtained from the liquid composition are more likely to be improved. The powder kinetic friction angle of the particles is preferably 40 degrees or less, more preferably 30 degrees or less, and still more preferably 20 degrees or less. The powder friction angle of the particles is preferably 5 degrees or more. In this case, the present particles are less likely to agglomerate, and the dispersion stability of the present particles in the liquid composition is likely to be improved. In addition, the present particles are easily dispersed in the liquid composition with less force. When the F polymer is the polymer (1), the particles tend to exhibit the powder dynamic friction angle.

The present particles are preferably produced by a method of causing the particles of the F polymer and the particles of the inorganic substance to collide at a temperature equal to or higher than the melting temperature of the F polymer and in a floating state (hereinafter, also referred to as "dry type"). Method A"); the method of colliding the particles of the F polymer with the particles of the inorganic substance in a state of extrusion or shearing (hereinafter, also referred to as "dry method B"); in a liquid, the particles of the F polymer are made to collide with The method of coagulating the particles of the F polymer by contacting the particles of the inorganic substance (hereinafter, also referred to as "wet method") and the like.

In the dry method A, for example, the particles of the F polymer and the particles of the inorganic substances are supplied into a high-temperature turbulent atmosphere, and by the collision of the particles of the F polymer and the particles of the inorganic substances, stress is applied between them to make them. composite. This dry method A is sometimes referred to as hybrid treatment. The atmosphere is formed by gas. As the gas that can be used, air, oxygen, nitrogen, argon, or a mixed gas thereof can be exemplified. The particles of the F polymer and the particles of the inorganic substance may be supplied to the atmosphere as a premixed mixture at one time, or may be supplied to the atmosphere separately.

When the particles of the F polymer and the particles of the inorganic substance are supplied into a high-temperature atmosphere, it is preferable to be in a state in which the particles do not agglomerate with each other. As this method, a method of floating particles in a medium (gas or liquid) can be used. Furthermore, a mixture of gas and liquid can also be used as the medium. In addition, in the dry method A, after preparing a high-temperature turbulent atmosphere, the particles of the F polymer and the particles of the inorganic substances can be supplied thereto, or the particles of the F polymer and the inorganic substances can be floated in the medium and then heated. The medium forms a high temperature turbulent atmosphere. As a device that can be used for the former, for example, a device that applies stress while sandwiching the particles between the inner wall of the container and the stirring body while stirring the particles by a stirring body (eg, stirring blade) rotating at a high speed in a cylindrical container can be exemplified. Device (eg "Hybridization System" manufactured by Nara Machine Works). The temperature of the atmosphere is preferably equal to or higher than the melting temperature of the F polymer, more preferably 260 to 400°C, and still more preferably 320 to 380°C.

Furthermore, in the case where the particles of the inorganic substance contain a large number of aggregates in which the primary particles are aggregated with each other, the aggregates may be crushed before being supplied to the high-temperature atmosphere. As a method of crushing the aggregate, a method using a jet mill, a pin mill, and a hammer mill can be mentioned.

In the dry method B, for example, the particles of the F polymer and the inorganic particles are pressed against the inner peripheral surface (receiving surface) of the cylindrical rotating body rotating around the central axis by centrifugal force, and the inner peripheral surface is separated from the The cooperation of the inner sheets arranged at a small distance gives the above-mentioned particles a pressing force or a shearing force to make them composite. This dry method B is sometimes referred to as a mechanical fusion process. The atmosphere in the cylindrical rotating body can be set as an inert gas atmosphere or a reducing gas atmosphere. The temperature of the atmosphere is preferably below the melting temperature of the F polymer, more preferably 100°C or below.

The separation distance between the inner peripheral surface of the cylindrical rotating body and the inner sheet can be appropriately set according to the average particle diameter of the particles of the F polymer and the particles of the inorganic substance. The separation distance is usually preferably 1 to 10 mm. The rotational speed of the cylindrical rotating body is preferably 500 to 10,000 rpm. In this case, it is easy to improve the production efficiency of this particle. Furthermore, in the case where the inorganic particles contain a large amount of aggregates formed by agglomerating primary particles thereof, the aggregates may be crushed in the same manner as described in the above-mentioned dry method A before being supplied to the cylindrical rotating body. .

Dry method B can also be carried out using a pulverizing and mixing device including: a rotating tank having a rotating shaft arranged in a horizontal direction and a pulverizing and mixing chamber having an elliptical (different-shaped) cross-section; and a pulverizing and mixing blade , which is rotatably inserted into the pulverizing and mixing chamber of the rotating tank, a rotating shaft is arranged at a position concentric with the rotating shaft of the rotating tank, and has an elliptical (different-shaped) cross-section. In this pulverizing and mixing device, between the short-diameter portion of the pulverizing and mixing chamber and the long-diameter portion of the pulverizing and mixing blade, the particles of the F polymer and the particles of the inorganic substances are pressed against the particles, and a pressing force or a shearing force is applied to the particles. of compounding.

In addition, in the pulverizing and mixing device, the rotation direction of the rotating tank and the rotating direction of the pulverizing and mixing blades are preferably opposite directions, and the rotation speed of the rotating tank is preferably set to be slower than the rotation speed of the pulverizing and mixing blades. According to this pulverizing and mixing device, the pulverizing and mixing chamber and the pulverizing and mixing blades can be set to have a cross-section of a different shape, and in the pulverizing and mixing chamber, the particles of the F polymer and the particles of the inorganic substances that flow due to their own weight are repeatedly given an instantaneous pressing force or Shear force. Therefore, the adverse effects of heat on the particles can be reduced, and the pulverization and mixing can be performed in a short time, so that the particles having the desired characteristics can be easily obtained.

In the wet method, for example, particles of an inorganic substance may be added to a dispersion liquid containing particles of the F polymer and mixed. Specifically, after disperse|distributing the particle|grains of an inorganic substance in a liquid dispersion medium, it is added to the dispersion liquid containing the particle|grains of an F polymer, and it mixes. This method is advantageous for mixing inorganic particles and F polymer particles. If the mixed solution containing the particles of the F polymer and the particles of the inorganic substance is destabilized and solidified, the particles of the F polymer and the particles of the inorganic substance are complexed. When the inorganic substance is silicon oxide, colloidal silicon oxide can be suitably used for the inorganic substance particles.

The dispersion liquid containing the particles of the F polymer may be stirred during the addition of the inorganic particles or after the addition. As an apparatus used for this stirring, the stirring apparatus provided with blades (stirring blades), such as a propeller blade, a turbine blade, a paddle, and a shell blade, is mentioned, for example. Furthermore, the stirring speed at this time may be such that the particles of the inorganic substance can be efficiently dispersed in the dispersion liquid containing the particles of the F polymer, and it is not necessary to impart a high shear force to the particles of the F polymer.

In order to further improve the adhesiveness (adhesion) with the inorganic particles, it is preferable to surface-treat the F polymer particles before mixing with the inorganic particles or simultaneously with the inorganic particles. Examples of the surface treatment include plasma treatment, corona discharge treatment, etching treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, and ozone exposure treatment, and plasma treatment (especially low-temperature plasma treatment) is preferred. In addition, according to the dry method A and the dry method B, when the particles of the F polymer and the particles of the inorganic substance collide, it is easy to uniformly transfer heat to the particles, so that the densification and spheroidization of the particles are easy to be performed. better. In this case, the sphericity of the particles is preferably 0.5 or more.

As a preferable aspect of this particle, the aspect in which the F polymer is used as the core and the inorganic substance is attached to the surface of the core (hereinafter, also referred to as "Aspect I"), the inorganic substance as the core and the The aspect of the F polymer adhered to the surface of the core (hereinafter, also referred to as "Aspect II"). Here, "core" means the core (center part) required for forming the particle shape of the present particle, and does not mean the main component in the composition of the present particle. The attachment (inorganic substance or F polymer) attached to the surface of the core may be attached only to a part of the surface of the core, or may be attached to most or the entire surface of the core. In the former case, it can also be said that it is in a state in which the attachments adhere to the surface of the core like dust, in other words, it is in a state in which most of the surface of the core is exposed. In the latter case, it can also be said that the surface of the core is uniformly coated with the adherents, or the surface of the core is covered, and it can also be said that the above-mentioned particle has a core composed of a core and a shell covering the core- shell structure.

In the case of Aspect I, it is preferable that the core and the inorganic substance of the F polymer are in the form of particles, respectively. In this case, since the inorganic substance having a higher hardness than the F polymer is exposed on the surface, the fluidity of the particle becomes high, and the handleability thereof is easily improved. Furthermore, in the case of Aspect I, the core of the F polymer may be composed of a single particle of the F polymer, or may be composed of an aggregate of the particles of the F polymer. The present particle of Aspect I is preferably produced by dry method A or dry method B. In this case, it is preferable to set the D50 of the particles of the F polymer to be larger than the D50 of the particles of the inorganic substance, and to set the amount of the particles of the F polymer to be larger than the quantity of the particles of the inorganic substance. If this relationship is set and the present particles are produced by the dry method A or the dry method B, the present particles of the aspect I can be easily obtained.

Based on the D50 of the particles of the F polymer, the D50 of the particles of the inorganic substance is preferably 0.0001 to 0.5, more preferably 0.0001 to 0.1, and still more preferably 0.002 to 0.02. As a specific preferred embodiment, the D50 of the particles of the F powder exceeds 20 μm and the D50 of the particles of the inorganic substance is 10 μm or less, or the D50 of the particles of the F powder exceeds 2 μm and the D50 of the particles of the inorganic substance is more than 2 μm. D50 is 1 μm or less, or D50 of F powder particles exceeds 1 μm and D50 of inorganic particles is 0.1 μm or less. Moreover, as for the quantity of the particle|grains of an inorganic substance, 0.1 mass part or more is preferable with respect to 100 mass parts of F polymer particles, and 1 mass part or more is more preferable. The upper limit is preferably 50 parts by mass, more preferably 25 parts by mass, and still more preferably 5 parts by mass. In the present particle of Aspect I thus obtained, the D50 of the core of the F polymer is greater than the D50 of the inorganic particle, and the mass of the F polymer in the inorganic particle is greater than the mass of the inorganic substance. In this case, the surface of the core of the F polymer is coated with a larger amount of inorganic particles, so that the present particles of Aspect I have a core-shell structure. In this case, the aggregation of the particles of the F powder is suppressed, and it is easy to obtain composite particles (the present particles) in which the particles of the inorganic substance adhere to the core composed of the particles of the F powder alone.

In aspect I, the particles of the inorganic substance are preferably spherical or scaly, more preferably spherical, and more preferably substantially true spherical. In this case, in the inorganic particles, the ratio of the short axis to the long axis is preferably 0.6 or more, more preferably 0.8 or more. The above-mentioned comparison is preferably less than 1. Here, the so-called "spherical shape" includes not only a true spherical shape but also a slightly deformed spherical shape. When the inorganic particles having a substantially spherical height are used, the inorganic material and the F polymer are more uniformly distributed in the molded product (polymer layer, etc.), and the physical properties of the two are more easily balanced.

In aspect I, the D50 of the inorganic particles is preferably in the range of 0.001 to 10 μm, more preferably in the range of 0.001 to 0.3 μm, further preferably in the range of 0.005 to 0.2 μm, particularly preferably in the range of 0.01 to 0.1 μm. When D50 is within this range, the handleability and fluidity of the particles are easily improved, and the dispersion stability is easily improved. Moreover, using the value of D90/D10 as an index, the particle size distribution of the inorganic particles is preferably 3 or less, more preferably 2.9 or less. Here, "D10" is the volume-based cumulative 10% diameter of the object measured in the same manner as D50 and D90. When the particle size distribution is narrow, it is easy to control the fluidity of the present particle obtained, which is preferable from this point of view.

In aspect I, it is preferable that at least a part of the surface of the particle|grains of an inorganic substance is surface-treated, More preferably, it is surface-treated with a silazane compound, such as hexamethyldisilazane, or a silane coupling agent. As a silane coupling agent, the above-mentioned compound is mentioned.

In the aspect I, the particles of the inorganic material may be used alone or in combination of two or more. In the case of mixing two kinds of inorganic particles, the average particle size of each inorganic particle can be different from each other, and the mass ratio of the content of each inorganic particle can be appropriately set according to the required function.

Moreover, in the case of Aspect I, a part of the particle of the inorganic substance is preferably embedded in the core of the F polymer. Thereby, the adhesiveness of the particle|grains of an inorganic substance to the core of the F polymer is further improved, and it becomes less likely that the particle|grains of an inorganic substance fall off from this particle|grains. That is, the stability of this particle is further improved. In the present particle of Aspect I, the D50 of the core of the F polymer is preferably 0.1 μm or more, more preferably more than 1 μm. The upper limit is preferably 100 μm, more preferably 50 μm, and still more preferably 10 μm. Moreover, D50 of the particle|grains of an inorganic substance becomes like this. Preferably it is 0.001 micrometer or more, More preferably, it is 0.01 micrometer or more. The upper limit is preferably 10 μm, more preferably 1 μm, and still more preferably 0.1 μm.

Moreover, 50-99 mass % is preferable, and, as for the ratio of the F polymer in the present particle of Aspect I, it is more preferable that it is 75-99 mass %. 1-50 mass % is preferable, and, as for the ratio of an inorganic substance, 1-25 mass % is more preferable. In addition, the ratio of the fluorine element content on the surface of the present particle of aspect I to the inorganic element content measured by energy dispersive X-ray spectroscopy is preferably less than 1, more preferably 0.5 or less, and still more preferably 0.1 or less. The above-mentioned comparison is preferably 0 or more. In addition, in this case, the target element in the measurement is set to four elements of carbon element, fluorine element, oxygen element and silicon element, and the ratio of each of fluorine element and silicon element to the total of the four elements ( Unit: Atomic%) are respectively set as the content of the element. In other words, the particles of the aspect I of this mass ratio are particles whose surfaces are highly coated with inorganic substances, which are not only excellent in particle physical properties (dispersibility in liquids, etc.) derived from inorganic substances, but also tend to have high physical properties of inorganic substances in the formed product. And the physical properties of F polymer.

The present particle of Aspect I may be further surface-treated according to the physical properties of the inorganic substances attached to the surface. As a specific example of this surface treatment, the method of surface-treating the particle|grains of the aspect I of the inorganic substance containing silicon oxide by siloxanes (polydimethylsiloxane etc.) or a silane coupling agent can be mentioned. The surface treatment can be carried out by mixing the dispersion liquid in which the particles are dispersed with a siloxane or a silane coupling agent, and reacting the siloxane or the silane coupling agent to recover the particles. As a silane coupling agent, the above-mentioned compounds are preferable. According to this method, not only the amount of silicon oxide on the surface of the present particle can be adjusted, but also the physical properties of the surface can be adjusted.

In the case of aspect II, preferably at least a portion of the F polymer is fused to the surface of the inorganic core. Thereby, the adhesiveness of the F polymer to the core of the inorganic substance is further improved, so that the F polymer is less likely to fall off from the particles. That is, the stability of this particle is further improved. Moreover, it is preferable that the core of an inorganic substance is a particle form. In this case, the surface of the core of the inorganic material of the particle is easily covered with the F polymer, and thus the aggregation of the particle is easily prevented. The present particle of Aspect II is also preferably produced by dry method A or dry method B. In this case, it is preferable to set the D50 of the inorganic particles to be greater than the D50 of the F polymer particles, and to set the amount of the inorganic particles to be larger than the F polymer particles. If this relationship is set and the present particles are produced by the dry method A or the dry method B, the present particles of the aspect II can be easily obtained.

The D50 of the particle of the F polymer is preferably 0.0001 to 0.02, more preferably 0.002 to 0.1, based on the D50 of the particle of the inorganic substance. Moreover, it is preferable that the quantity of the particle|grains of F polymer is 0.1 mass part or more with respect to 100 weight part of inorganic particles, and it is more preferable that it is 1 mass part or more. The upper limit is preferably 50 parts by mass, more preferably 10 parts by mass, and still more preferably 3 parts by mass. In the present particle of Aspect II thus obtained, the D50 of the inorganic core is greater than the D50 of the F polymer particle, and the inorganic matter occupies more mass in the present particle than the F polymer. In this case, the surface of the inorganic core is coated with a larger amount of particles of the F polymer, so that the present particles of Aspect II have a core-shell structure.

In the present particle of aspect II, the D50 of the inorganic core is preferably 0.1 μm or more, more preferably more than 1 μm. The upper limit thereof is preferably 30 μm, more preferably 6 μm. Moreover, 50-99 mass % is preferable, and, as for the ratio which an inorganic substance occupies in the present particle of Aspect II, it is more preferable that it is 60-90 mass %. The ratio of the F polymer is preferably from 1 to 50 mass %, more preferably from 10 to 40 mass %.

The liquid composition of the present invention (hereinafter, also referred to as "the present composition") is a composition comprising the present particles and a liquid dispersion medium, and wherein the present particles are dispersed in the liquid dispersion medium. The particles can exhibit sufficiently high polarity, and can be stably dispersed even if a large amount of a liquid dispersion medium is added. In addition, in the molded product (polymer layer, film, etc.) formed from the liquid composition, the F polymer and the inorganic substance are more uniformly distributed, and the physical properties (electrical properties, adhesiveness, etc.) of the F polymer are easily expressed at a high level. And inorganic physical properties (low linear expansion, etc.). The liquid dispersion medium in the present invention is a liquid compound that functions as a dispersion medium of the particles and is inert at 25°C. The liquid dispersion medium may be water or a non-aqueous dispersion medium. The liquid dispersion medium may be one type or two or more types. In this case, it is preferable that different kinds of liquid compounds are compatible.

The boiling point of the liquid dispersion medium is preferably 125 to 250°C. In this range, when the liquid dispersion medium is removed from the liquid composition, the particles are highly fluid and densely packed, and as a result, a dense molded product (polymer layer, etc.) is easily formed. As the liquid dispersion medium, in order to improve the dispersion stability of the particles in the composition, at least one liquid compound selected from the group consisting of water, amides, ketones and esters is preferred, and water, N-methyl-2-pyrrolidone, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone and cyclopentanone.

When the liquid dispersion medium contains an aprotic polar solvent such as N-methyl-2-pyrrolidone, the inorganic substance in the particle is preferably at least a part of its surface by having a compound selected from the group consisting of amine group, vinyl group and The surface treatment is carried out with a silane coupling agent having at least one group in the group consisting of (meth)acryloyloxy groups, and it is more preferable to carry out the surface treatment with phenylaminosilane. When the liquid dispersion medium contains a non-polar solvent such as toluene, the inorganic matter in the particle is preferably at least a part of the surface of which is hydrophobized, preferably by having a compound selected from the group consisting of an alkyl group and a phenyl group. At least one type of silane coupling agent is subjected to surface treatment. Furthermore, when the liquid dispersion medium contains a protic polar solvent such as water, it is preferable that the inorganic substance in the particle is not surface-treated. In the case of a combination of the liquid dispersion medium and an inorganic substance, it is easy to make the present composition excellent in dispersion stability.

The content of the present particles in the present composition is preferably 1 to 50% by mass, more preferably 10 to 40% by mass. The content of the liquid dispersion medium in the composition is preferably 50 to 99% by mass, more preferably 60 to 90% by mass.

In order to further improve the dispersion stability of the particles, suppress particle precipitation, and improve handling properties, the composition preferably further contains a surfactant. The surfactant is preferably nonionic. The hydrophilic part of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group. The hydrophobic portion of the surfactant preferably has an alkyl group, an ethynyl group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group. The surfactant is preferably a polyoxyalkylene alkyl ether, an acetylene-based surfactant, a silicone-based surfactant and a fluorine-based surfactant, more preferably a silicone-based surfactant. Silicone-based surfactants can also be used with polyoxyalkylene alkyl ethers.

Specific examples of the surfactant include "Ftergent" series (manufactured by NEOS), "Surflon" series (manufactured by AGC Seimi Chemical), "MEGAFAC" series (manufactured by DIC), "Unidyne" series ( Daikin Industries Co., Ltd.), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (BYK -Manufactured by Chemie Japan Co., Ltd.), "KF-6011", "KF-6043" (manufactured by Shin-Etsu Chemical Co., Ltd.). When the present composition contains a surfactant, the content thereof is preferably 1 to 15% by mass. In this case, the dispersion stability of the present particles in the present composition can be more easily improved.

The viscosity of the composition is preferably 50 mPa·s or more, more preferably 100 mPa·s or more. The viscosity of the composition is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less. In this case, since the present composition is excellent in coatability, it is easy to form a molded product (polymer layer, etc.) having an arbitrary thickness. The thixotropy ratio of the present composition is preferably 1.0 or more. The thixotropy ratio of the present composition is preferably 3.0 or less, more preferably 2.0 or less. In this case, since the present composition is excellent not only in coatability but also in homogeneity, it is easy to form a denser molded product (polymer layer, etc.).

The present composition may further comprise polymers other than F polymers or their precursors. As the polymer or its precursor, polytetrafluoroethylene (PTFE), a polymer (PFA) containing a TFE unit and a PAVE unit, a polymer (FEP) containing a TFE unit and a hexafluoropropylene-based unit can be exemplified , Polymers containing TFE units and ethylene-based units (ETFE), polyvinylidene fluoride (PVDF), polyimide, polyarylate, polyamide, polyarylene, polyamide, polyetheramide, Polyphenylene ether, polyphenylene sulfide, polyaryl ether ketone, polyamide imide, liquid crystal polyester, liquid crystal polyester imide, epoxy resin, maleimide resin, etc. Furthermore, the PFA may be an F polymer or a PFA other than the F polymer. These polymers or their precursors can be dispersed or dissolved in the composition. In addition, these polymers or their precursors may be thermoplastic or thermosetting. In addition to the above-mentioned components, the composition may further include a thixotropy imparting agent, a viscosity modifier, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, Antistatic agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, various fillers and other ingredients.

In the method for producing a layered product of the present invention (hereinafter, also referred to as "this method 1"), the composition is applied to the surface of the base material layer and heated to form a polymer layer, thereby obtaining a base material layer and a polymer layer. A laminate of polymer layers. More specifically, in this method 1, the composition is applied to the surface of the base material layer to form a liquid coating, the liquid coating is heated to remove the liquid dispersion medium to form a dry coating, and the coating is further heated and dried. By calcining the F polymer, a laminate having a polymer layer containing the F polymer and an inorganic substance on the surface of the base material layer can be obtained. The temperature during heating of the liquid coating is preferably 120°C to 200°C. On the other hand, the temperature during heating for drying the film is preferably 250 to 400°C, more preferably 300 to 380°C. As each heating method, the method of using an oven, the method of using a ventilation drying furnace, and the method of irradiating heat rays, such as infrared rays, are mentioned.

Examples of the base material layer include metal substrates (metal foils such as copper, nickel, aluminum, titanium, and alloys thereof, etc.), resin films (PTFE, polyimide, polyarylate, polyarylene, polyarylene, etc.) , polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystal polyester, liquid crystal polyesteramide and other films), prepreg (fiber-reinforced resin substrate previous drive). The provision of the present composition is preferably carried out by coating. As a coating method, a spray method, a roll coating method, a spin coating method, a gravure coating method, a microgravure coating method, a gravure offset method, a blade coating method, a contact coating method, a bar coating method can be mentioned. Cloth method, die nozzle coating method, injection Meyer rod method, slot die nozzle coating method.

The thickness of the polymer layer is preferably 0.1-150 μm. Specifically, when the base material layer is a metal foil, the thickness of the polymer layer is preferably 1-30 μm. When the base material layer is a resin film, the thickness of the polymer layer is preferably 1-150 μm, more preferably 10-50 μm. The composition may be applied to only one surface of the substrate layer, or may be applied to both surfaces of the substrate layer. In the former case, a laminate having a base material layer and a polymer layer on a single surface of the base material layer can be obtained, and in the latter case, a base material layer with a polymer layer on both surfaces of the base material layer can be obtained. A laminate of polymer layers. The latter layered body is more difficult to warp, and therefore has excellent handleability during processing. Specific examples of the laminate include a metal foil laminate having a metal foil and a polymer layer on at least one surface of the metal foil, and a polyimide film having a polyimide film on both sides of the polyimide film. A multilayer film with a polymer layer on each surface.

Moreover, the metal foil with a carrier which consists of 2 or more layers of metal foils can also be used as a metal foil. The metal foil with a carrier includes, for example, a carrier copper foil (thickness: 10 to 35 μm) and an ultra-thin copper foil (thickness: 2 to 5 μm) laminated on the carrier copper foil via a release layer. The copper foil with carrier. If the copper foil with the carrier is used, a fine pattern can be formed by the MSAP (modified semi-additive method) process. The peeling layer is preferably a metal layer containing nickel or chromium, or a multi-layer metal layer in which the metal layer is laminated. As a specific example of the metal foil with a carrier, the product called "FUTF-5DAF-2" manufactured by Futian Metal Foil Powder Industry Co., Ltd. can be mentioned.

The outermost surface of the layered product in this method 1 (the surface on the opposite side of the polymer layer and the base material layer) may be further surface-treated in order to further improve the adhesiveness. As a method of surface treatment, annealing treatment, corona treatment, plasma treatment, ozone treatment, excimer treatment, and silane coupling treatment can be mentioned. The conditions in the annealing treatment are preferably 120 to 180° C. for temperature, 0.005 to 0.015 MPa for pressure, and 30 to 120 minutes for time. As a gas used for plasma processing, oxygen gas, nitrogen gas, rare gas (argon gas etc.), hydrogen gas, ammonia gas, and vinyl acetate are mentioned. One type of these gases may be used, or two or more types may be used.

Other substrates may be further laminated on the outermost surface of the laminated body in this method 1. Examples of other substrates include a heat-resistant resin film, a prepreg as a precursor of a fiber-reinforced resin sheet, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer. Furthermore, the prepreg system is a sheet-like substrate obtained by impregnating a base material (tow, woven cloth, etc.) of a reinforcing fiber (glass fiber, carbon fiber, etc.) with a thermosetting resin or a thermoplastic resin. The heat-resistant resin film is a film containing one or more types of heat-resistant resins. As the heat-resistant resin, polyimide, polyarylate, polyamide, polyarylene, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamide may, for example, be mentioned. The amine imide, liquid crystal polyester, and liquid crystal polyester imide are preferably polyimide (especially aromatic polyimide).

As a method of lamination, the method of heat-pressing a laminated body and another board|substrate is mentioned. When the other substrates are prepregs, the hot pressing conditions are preferably set to a temperature of 120 to 400° C., a pressure of the atmosphere to a vacuum of 20 kPa or less, and a pressing pressure of 0.2 to 10 MPa. Since the laminate in this method 1 has a polymer layer having excellent electrical properties, it is suitable as a printed circuit board material. Specifically, the laminate in the present invention can be used as a flexible metal foil laminate or a rigid metal foil laminate to manufacture a printed circuit board, and in particular, it can be suitably used as a flexible metal foil laminate to manufacture a flex print substrate.

The metal foil of which the base material layer is a laminate of metal foil (metal foil with polymer layer) is etched to form a transmission circuit, and a printed circuit board can be obtained. Specifically, a printed circuit board can be manufactured by a method of etching a metal foil to process it into a specific transmission circuit, or by an electrolytic plating method (semi-additive method (SAP method), MSAP method) etc.) A method of processing metal foils into specific transmission circuits. A printed circuit board made of a metal foil with a polymer layer has a transmission circuit formed of the metal foil and a polymer layer in this order. As a specific example of the structure of a printed circuit board, a transmission circuit/polymer layer/prepreg layer, transmission circuit/polymer layer/prepreg layer/polymer layer/transmission circuit may be mentioned. In the manufacture of the printed circuit board, an interlayer insulating film may be formed on the transmission circuit, a solder resist may be laminated on the transmission circuit, and a coverlay film may be laminated on the transmission circuit. These interlayer insulating films, solder resists and coverlay films can also be formed by the present composition.

In the film production method of the present invention (hereinafter, also referred to as "this method 2"), after melt-kneading the particles and the fluoroolefin-based polymer, extrusion molding is performed to obtain a film. Since this particle contains the F polymer with high interaction (compatibility) with the fluoroolefin-based polymer, the two can be melt-kneaded uniformly. In the obtained film, the F polymer, the fluoroolefin-based polymer, the The inorganic matter is uniformly distributed, and the physical properties (especially electrical properties) of the F polymer and the fluoroolefin-based polymer and the physical properties (low linear expansion, etc.) of the inorganic matter are easily expressed. The fluoroolefin-based polymer to be melt-kneaded with the particles may be either the F polymer or a polymer containing a fluoroolefin-based unit other than the F polymer.

As a fluoroolefin type polymer, PTFE, PFA, FEP, ETFE, PVDF are mentioned. The PFA may be an F polymer or a PFA other than the F polymer. The melting temperature (melting point) of the fluoroolefin-based polymer is preferably 160 to 330°C. The glass transition point of the fluoroolefin-based polymer is preferably 45 to 150°C. The fluoroolefin-based polymer preferably has a polar functional group. It is preferable that the F polymer and the fluoroolefin-based polymer have a polar functional group in common. In addition, the kind and introduction method of polar functional groups are the same as those in the above-mentioned F polymer, including preferable ones.

The melt-kneading of the present particles and the TFE-based polymer can be performed, for example, using a uniaxial kneader. The single-shaft kneader has a barrel and one screw rotatably provided in the barrel. When a uniaxial kneader is used, it is easy to prevent the deterioration of the F polymer and the TFE-based polymer during melt-kneading. In this case, when the total length of the screw is L (mm) and the diameter is D (mm), the effective length (L/D) represented by the ratio of the total length L to the diameter D is better. 30 to 45. When the effective length is in the above range, the deterioration of the F polymer and the TFE-based polymer can be prevented, sufficient shear stress can be imparted to them, and the temperature unevenness of the melt-kneaded product can be easily reduced. The rotation speed of the screw is preferably 10-50 ppm.

The melt-kneaded product is ejected from the T-die arranged at the front end of the barrel. After that, the melt-kneaded product ejected from the T-die is brought into contact with a plurality of cooling rolls, solidified, and formed into a thin film. The obtained long film is wound up to a take-up roll. The thickness of the film is preferably 5-150 μm, more preferably 10-100 μm. The shape of the film can be elongated or leaf-shaped. The length in the longitudinal direction of the elongated film is preferably 100 m or more. The upper limit of the length in the longitudinal direction is usually 2000 m. In addition, the length in the short-side direction of the elongated shape is preferably 1000 mm or more. The upper limit of the length in the short side direction is usually 3000 mm.

After superimposing the obtained film on the base material layer, hot pressing is performed to obtain a laminate having a polymer layer formed of the film and a base material layer. The conditions of the hot pressing are preferably a temperature of 120 to 300° C., an atmosphere pressure of a vacuum of 20 kPa or less, and a pressurized pressure of 0.2 to 10 MPa. In addition, the aspect of a base material layer, the printed circuit board using a laminated body, and a multilayer printed circuit board is the same as that in the above-mentioned method 1, including preferable aspect. In addition, a circular die may be used instead of a T-die to manufacture an blown film.

The composite particles, the method for producing composite particles, the method for producing a liquid composition, the method for producing a layered product, and the method for producing a film of the present invention have been described above, but the present invention is not limited to the configurations of the above-described embodiments. For example, the composite particles and the liquid composition of the present invention may each add other arbitrary structures to the structures of the above-described embodiments, or may be replaced with arbitrary structures that exhibit the same function. In addition, the method for producing composite particles, the method for producing a layered product, and the method for producing a thin film of the present invention may be added to the configuration of the above-described embodiments to have other optional steps, or may be replaced by any optional steps that produce the same effect. step. [Example]

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. 1. Preparation of each component [Particles of polymer] Particle 1 of F polymer 1: contains 97.9 mol % of TFE units, 0.1 mol % of NAH units and 2.0 mol % of PPVE units and has polar functionalities Particles (D50: 2.0 μm) of F polymer 1 (melting temperature: 300° C.) of the base Particles of F polymer 2: contain 97.5 mol % of TFE units and 2.5 mol % of PPVE units and have no polarity Particles of functional group F polymer 2 (melting temperature: 300°C) (D50: 2.6 μm) ∙ Particles of non-F polymer: contain 98.7 mol% of TFE units and 1.3 mol% of PPVE units and do not have Particles of polar functional group non-F polymer (melting temperature: 305°C) (D50: 2.1 μm) Particles of PTFE: Particles of non-heat-melting PTFE containing fibrils (D50: 2.4 μm) F polymer Particle 2 of 1: Particle containing F polymer 1 (D50: 25 μm) Furthermore, the number of carbonyl-containing groups per 1×10 ⁶ carbon atoms in the main chain is calculated as 1000 in F polymer 1, 40 pieces are counted as F polymer 2. The melt viscosity of F polymer 1 and F polymer 2 at 380℃ is in the range of 1×10 ³ ～1×10 ⁶ Pa·s, and the glass transition point of F polymer 1 and F polymer 2 is in the range of 80～ 100°C range. [Particles of Inorganic Substances] Silica Particles 1: Spherical particles containing silica (D50: 0.5 μm, approximately true spherical) Silica Particles 2: Silicon oxide surface-treated with a silane coupling agent spherical particles (D50: 0.03 μm, approximately true spherical) Boron nitride particles: scaly particles containing boron nitride (D50: 7.0 μm, aspect ratio: 1000 or less)

2. Production of composite particles (example 1) A mixture of 98 parts by mass of particles 1 of F polymer 1 and 2 parts by mass of particles 1 of silicon oxide was prepared. Next, the mixture is put into a powder processing apparatus (mechanical fusion apparatus) including: a cylindrical rotating body having a receiving surface on its inner peripheral surface; and an inner sheet disposed at a slight distance from the receiving surface . After that, the cylindrical rotating body is rotated at a high speed around the central axis. By the centrifugal force generated at this time, the particles are pressed against the receiving surface, and the mixture is introduced into the narrow space (extrusion space) between the receiving surface and the inner sheet, so that the particles collide in a sheared state for processing. In addition, the temperature of the atmosphere of the cylindrical rotating body being processed was kept below 100 degreeC, and the processing time was made into 15 minutes. The obtained treated product was a fine powder. Further, the powder was analyzed by an optical microscope, and as a result, it was a composite particle 1 having a core-shell structure having a shell with F polymer 1 as a core and particles 1 of silicon oxide adhered to the surface of the core. The ratio of the fluorine element content to the silicon element content on the surface of the composite particles measured by energy dispersive X-ray spectroscopy (hereinafter, also referred to as "F/Si ratio") was 0.006. In addition, the target element in the measurement is set to four elements of carbon element, fluorine element, oxygen element and silicon element, and the ratio of each of fluorine element and silicon element to the total of the four elements (unit: Atomic%) respectively set the content of the element. The shape of the composite particle 1 is spherical, its D50 is 20 μm, and the powder dynamic friction angle is 18 degrees. Furthermore, composite particles 1 were produced, and then, without cleaning the mechanical fusing device, a mixture of 98 parts by mass of particles 1 of F polymer 1 and 2 parts by mass of particles 1 of silicon oxide was put into the mechanical fusing device In the process, a processed product was obtained, and as a result, it was the same particle as the composite particle 1 described above.

(Example 2) Composite particles 2 were obtained in the same manner as in Example 1, except that the mixture was prepared by using 95 parts by mass of particles 1 of F polymer 1 and 5 parts by mass of particles 1 of silicon oxide. The F/Si ratio of the composite particle 2 was 0.337, and its D50 was 30 μm. (Example 3) Composite particles 3 were obtained in the same manner as in Example 1, except that the mixture was prepared by using 75 parts by mass of particles 1 of F polymer 1 and 25 parts by mass of particles 1 of silicon oxide. The F/Si ratio of the composite particle 3 was 0.672, and its D50 was 40 μm.

(Example 4) A composite particle 4 was obtained in the same manner as in Example 2, except that the particle 1 of the F polymer 1 was changed to the particle of the F polymer 2. The F/Si ratio of the composite particles 4 was 0.555, the D50 was 35 μm, and the powder friction angle was 25 degrees. (Example 5) Composite particles 5 were obtained in the same manner as in Example 1, except that the particles 1 of the F polymer 1 were changed to those of the non-F polymer. The F/Si ratio of the composite particles 5 exceeds 1, the D50 thereof is 50 μm, and the powder friction angle is 45 degrees. (Example 6) It processed in the same manner as in Example 1, except that the particle 1 of the F polymer 1 was changed to the particle of PTFE. The obtained processed product was a non-particulate mass.

(Example 7) Composite particles 7 were obtained in the same manner as in Example 1, except that the mixture was prepared by using 10 parts by mass of particles 1 of F polymer 1 and 90 parts by mass of particles 1 of silicon oxide. The composite particle 7 was analyzed by an optical microscope, and as a result, it was a composite particle having a core-shell structure having a shell by using silicon oxide as a core and adhering the F polymer 1 to the surface of the core. (Example 8) A composite particle 8 was obtained in the same manner as in Example 1 except that the silicon oxide particle 1 was changed to the silicon oxide particle 2 . The F/Si ratio of the composite particles 8 was 0.005, the D50 was 5.5 μm, and the powder kinetic friction angle was 16 degrees.

(Example 9) First, a mixture of 70 parts by mass of particles 2 of F polymer 1 and 30 parts by mass of particles of boron nitride was prepared. Next, while the particles are stirred by the stirring blades rotating at high speed in the cylindrical container, the mixture is put into the powder processing device (Nara Hybridization System) which clamps the particles between the inner wall of the container and the stirring body and applies stress. Then, the particles 2 of the F polymer 1 and the particles of boron nitride are floated and collided in a high-temperature turbulent atmosphere, and a stress is applied between them to perform a composite treatment. In addition, the temperature in the apparatus during processing was kept below 100 degreeC under nitrogen atmosphere, and the processing time was made into 15 minutes. The obtained treated product was a fine powder. Furthermore, the powder was analyzed by an optical microscope, and as a result, it was a composite particle 9 having a core-shell structure having a shell with F polymer 1 as a core and particles of boron nitride adhered to the surface of the core. Furthermore, the shape of the composite particles 9 is spherical, the D50 thereof is 35 μm, and the powder kinetic friction angle is 26 degrees.

3. Evaluation 3-1. Evaluation of dispersion stability The composite particles 1 to 5 and 7 to 9 were dispersed in water to prepare a dispersion liquid, and were left to stand for a predetermined time, and the dispersion stability was evaluated according to the following criteria. [Evaluation Criteria] ○: Foaming was suppressed during preparation, and no precipitate was generated even if it was left to stand at 25°C for 3 days after preparation. Δ: Foaming occurs during preparation, but after preparation, even if it is left to stand at 25° C. for 3 days, no precipitate is generated. ×: When left to stand at 25°C for 3 days, a precipitate was generated. As a result, the composite particles 1, 2, and 7 to 9 were "0", the composite particles 3 and 4 were "△", and the composite particle 5 was "x". Furthermore, the time required for the composite particles 8 is the longest until a precipitate is generated.

3-2. Evaluation of powder falling and warpage First, each of composite particles 1 to 4, 7 to 9, and N-methyl-2-pyrrolidone (NMP) were put into a crucible, and then zirconia balls were put into the crucible. Thereafter, the crucible was rotated at 150 rpm for 1 hour, thereby preparing a liquid composition. Next, the liquid composition is applied to the surface of the long copper foil using a bar coater to form a liquid coating. Next, the metal foil on which the liquid coating was formed was passed through a drying furnace at 120° C. for 5 minutes, and dried by heating to obtain a dry coating. After that, the dry film was heated in a nitrogen oven at 380° C. for 3 minutes. Thereby, the laminated body which has a copper foil, and the polymer layer which consists of the melt-fired product of a polymer and an inorganic substance located on the surface is obtained.

Then, the powder falling of the dry coating and the warpage of the laminate were evaluated. The powder falling of the dry film was evaluated by visually checking the edge portion of the dry film and according to the following criteria. [Evaluation criteria for falling powder] ○: No peeling was observed at the edge of the dry film. △: Peeling was observed in a part of the edge portion of the dry film. ×: Peeling was confirmed in a wide range of the edge portion of the dry film.

In addition, the warpage of the laminated body was obtained by cutting out a square test piece of 180 mm square from the laminated body, measuring the test piece by the measurement method prescribed in JIS C 6471:1995, and evaluating it according to the following criteria. [Evaluation criteria for warpage] ○: The coefficient of linear expansion is less than ±20 ppm/°C. ×: The linear expansion coefficient is ±20 ppm/°C or more. These results are shown in Table 1 below.

[Table 1] powder warping composite particle 1 〇 〇 Composite particle 2 △ 〇 Composite particle 3 △ × Composite particle 4 × × Composite particles 7 〇 〇 Composite particles 8 〇 〇 composite particles 9 〇 〇

4. Film making (Example 10) The composite particles 1 (50 parts by mass) and the particles 1 (50 parts by mass) of the F polymer 1 were stirred by a stirrer to prepare a mixture. If a uniaxial extruder (a 30 mmϕ uniaxial extruder with a 700 mm wide coat hanger die) is used to extrude the mixture at a die temperature of 340°C, a width of 500 mm, a length of 100 m, Film 1 with a thickness of 25 μm. The film 1 has a lower coefficient of linear expansion than the film composed of the F polymer 1 alone. [Industrial Availability]

The composite particles of the present invention are excellent in dispersion stability in a liquid composition. This liquid composition can be used for the manufacture of molded articles (laminates, films, etc.) having properties based on F polymer and properties based on inorganic materials. The molded article of the present invention is useful as antenna parts, printed circuit boards, parts for aircraft, parts for automobiles, sporting goods, food industry products, paints, cosmetics, etc. ), wire covering materials (aircraft wires, etc.), electrical insulating tapes, insulating tapes for oil mining, 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.), replica rolls, housings for furniture, automobile dashboards, home appliances, etc., sliding members (load bearings, sliding shafts, valves, bearings, Gears, cams, belt conveyors, belts for food conveying, etc.), tools (shovels, files, awls, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, molds, toilets, container coverings, The outer surface coating material of heat exchangers (radiating fins, heat transfer tubes, etc.) such as cooling and heating equipment is useful.

Claims (15)

A composite particle containing a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an inorganic substance, wherein the tetrafluoroethylene-based polymer is selected from the group consisting of units based on perfluoro(alkyl vinyl ether) and has Polar functional group tetrafluoroethylene-based polymer and tetrafluoroethylene-based polymer containing 2.0 to 5.0 mol% of perfluoro(alkyl vinyl ether)-based units with respect to all units and having no polar functional group At least 1 species in the group formed. The composite particle according to claim 1, wherein the powder kinetic friction angle of the composite particle is 40 degrees or less. The composite particle according to claim 1 or 2, wherein the inorganic substance is silicon oxide or boron nitride. The composite particle according to any one of claims 1 to 3, wherein the composite particle is spherical or scaly. The composite particle according to any one of claims 1 to 4, wherein the tetrafluoroethylene-based polymer is used as a core, and the surface of the core has the inorganic substance. The composite particle according to claim 5, wherein the core of the tetrafluoroethylene-based polymer and the inorganic substance are each in the form of particles, and the average particle size of the core is larger than the average particle size of the inorganic substance. The composite particle according to claim 5 or 6, wherein the ratio of the fluorine element content to the inorganic element content on the surface of the composite particle measured by energy dispersive X-ray spectroscopy is less than 1. The composite particle according to any one of claims 1 to 4, wherein the inorganic substance is used as a core, and the tetrafluoroethylene-based polymer is provided on the surface of the core. The composite particle according to claim 8, wherein the mass of the inorganic substance in the composite particle is larger than the mass of the tetrafluoroethylene-based polymer. A method for producing composite particles, which is a method for producing composite particles as claimed in any one of Claims 1 to 9, and wherein particles of the above-mentioned tetrafluoroethylene-based polymer and particles of the above-mentioned inorganic substance are prepared in the above-mentioned tetrafluoroethylene-based polymer The above-mentioned composite particles are obtained by colliding in a floating state at a temperature above the melting temperature. A method for producing composite particles, which is a method for producing composite particles as claimed in any one of claims 1 to 9, wherein the particles of the above-mentioned tetrafluoroethylene-based polymer and the particles of the above-mentioned inorganic substances are extruded or sheared A collision occurs, thereby obtaining the above-mentioned composite particles. A liquid composition comprising the composite particles according to any one of claims 1 to 9, and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid dispersion. The liquid composition according to claim 12, wherein the liquid dispersion medium is at least one liquid compound selected from the group consisting of water, amides, ketones and esters. A method for producing a layered product, comprising applying the liquid composition according to claim 12 or 13 to the surface of a base material layer, heating it to form a polymer layer, and thereby obtaining a layered layer having the above-mentioned base material layer and the above-mentioned polymer layer body. A method for producing a film, wherein the composite particles according to any one of claims 1 to 9 are melt-kneaded with a fluoroolefin-based polymer, and then extrusion-molded to obtain a film.