TW202206535A - Powder composition and composite particles - Google Patents

Abstract

To provide: a powder composition which is configured such that inorganic particles that can be used in combination can be flexibly selected, and which is capable of forming a molded article, such as a film, that exhibits excellent physical properties (electrical characteristics, low linear expansion, etc.) that depend on constituents. In addition, to provide: composite particles that have outstanding dispersion stability; and a dispersion that contains the composite particles. The present invention is a powder composition that includes: composite particles that contain a hot-melt tetrafluoroethylene-based polymer and an inorganic substance; and particles of at least one resin selected from the group consisting of a fluorine-based resin and an aromatic resin, and/or inorganic particles. The present invention is also composite particles that include a tetrafluoroethylene-based polymer with a melting temperature of 260-320 DEG C and an aromatic polymer with an aromatic ring content of at least 45% by mass.

Description

Powder composition and composite particles

The present invention relates to a powder composition and composite particles, the powder composition comprising: composite particles containing a hot-melt tetrafluoroethylene-based polymer and an inorganic substance; and at least one of resin particles and inorganic particles, the resin The resin of the particles is at least one selected from the group consisting of fluorine-based resins and aromatic-based resins; the composite particles include the above-described tetrafluoroethylene-based polymer and a specific aromatic polymer.

In recent years, in the field of information and communication, from the viewpoint of increasing the frequency of signals or simplifying them, there has been a demand for higher density of printed circuit boards used therein. As an insulator material in a printed circuit board, a film formed by impregnating a glass cloth with a thermosetting resin, or a film formed from an aromatic resin such as polyimide and liquid crystal polymer is used. Furthermore, tetrafluoroethylene-based polymers having better electrical properties than these aromatic resins have attracted attention, and in order to improve heat dissipation, resin compositions in which boron nitride particles are mixed with tetrafluoroethylene-based polymers have been proposed (see Patent Document 1). Moreover, the powder composition which mixed the powder of both an aromatic resin and a tetrafluoroethylene-type polymer, and the molded object which consists of this powder composition are proposed (refer patent documents 2-5). Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) are excellent in electrical properties, water and oil repellency, chemical resistance, heat resistance and other physical properties, and are used as coating agents for imparting the above-mentioned physical properties to the surface of substrates for various industrial uses. On the other hand, the tetrafluoroethylene-based polymer is required to improve the adhesion to the substrate because of insufficient adhesiveness and adhesiveness. In Patent Document 6, from the viewpoint of improving the adhesiveness with the base material, composite particles are disclosed which are bonded bodies of tetrafluoroethylene-based polymer particles and adhesive polymer particles. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2020/045260 [Patent Document 2] Japanese Patent Laid-Open No. 2002-265729 [Patent Document 3] Japanese Patent Laid-Open No. 2003-171538 [Patent Document 4] Japanese Patent Laid-Open No. 2003-200534 [Patent Document 5] Japanese Patent Laid-Open No. 2019-085061 [Patent Document 6] Japanese Patent Laid-Open No. 2013-227504

[Problems to be Solved by Invention]

The interaction between the tetrafluoroethylene-based polymer and other substances is weak, and it is difficult to uniformly mix with the boron nitride particles. Therefore, in Patent Document 1, the mixing ratio of the tetrafluoroethylene-based polymer and the boron nitride particles or the particle size distribution of the boron nitride particles is adjusted. The inventors of the present invention found that the low linear expansion property of the molded product formed from the powder composition described in Patent Document 1 was insufficient. In addition, the surface tension of the tetrafluoroethylene-based polymer is relatively low, and the molded product formed from the powder composition in which the powder of the tetrafluoroethylene-based polymer and the aromatic resin powder are blended is difficult to fully possess the combination of the two due to layer separation and the like. Of course, the physical properties of such polymers are not necessarily sufficient to have mechanical strength and other physical properties of shape or processability. The inventors of the present invention have found that when other fillers are further blended into the powder composition, this tendency tends to become conspicuous, and the effects of blending other fillers are not easily exhibited. In addition, the present inventors have also found that in a molded product formed from a powder composition containing tetrafluoroethylene-based polymer particles, fluorine-based resin particles, and other fillers, it is difficult to uniformly disperse other fillers, and it is difficult to show that other fillers are mixed with other fillers. the effect produced. On the other hand, when the composite particle described in Patent Document 6 is used as a coating film, the adhesiveness with the base material, especially the heat-resistant adhesiveness, is still insufficient. In addition, when the composite particles are dispersed in a liquid to prepare a liquid coating agent, the dispersibility is still insufficient, and the uniformity of the component distribution in the molded product obtained therefrom tends to decrease.

As a result of intensive research by the present inventors, the use of specific composite particles has found that the tetrafluoroethylene-based polymer and the inorganic particles can be uniformly mixed without strictly adjusting the mixing ratio with the inorganic particles and the particle size distribution. In the molded product formed from the composition of the present invention, each component is uniformly dispersed, and the physical properties (electrical properties, low linear expansion, high heat dissipation, etc.) based on each component can be highly expressed. Moreover, the present inventors discovered that these problems can be solved by using a specific composite particle and a specific resin particle in combination. Furthermore, the present inventors discovered that composite particles containing a specific tetrafluoroethylene-based polymer and a specific aromatic polymer have excellent dispersion stability. In addition, it was found that a molded product obtained from a dispersion liquid containing the composite particles, or a film extruded from the composite particles was relatively dense, and was excellent in a low coefficient of linear expansion and the like.

An object of the present invention is to provide a powder composition which has a high degree of freedom of selection of inorganic particles used in combination and can form a molded product such as a film having excellent physical properties (electrical properties, low linear expansion, high heat dissipation, etc.). An object of the present invention is to provide a powder composition capable of forming a molded product such as a film that highly exhibits excellent physical properties (electrical properties, low linear expansion, etc.) based on a tetrafluoroethylene polymer, an inorganic substance, and a specific resin. An object of the present invention is to provide composite particles having excellent dispersion stability, and a dispersion liquid containing the composite particles. [Technical means to solve problems]

The present invention has the following aspects. <1> A powder composition comprising: composite particles comprising a heat-fusible tetrafluoroethylene-based polymer and an inorganic substance; and at least one of resin particles and inorganic particles, the resin particles of which are selected from fluorine-based resins At least one of the group consisting of resin and aromatic resin. <2> The powder composition according to <1>, wherein the tetrafluoroethylene-based polymer is selected from the group consisting of a tetrafluoroethylene-based polymer containing a perfluoro(alkyl vinyl ether)-based unit and having a polar functional group, and at least one of the group consisting of tetrafluoroethylene-based polymers that contain 2.0 to 5.0 mol % of perfluoro(alkyl vinyl ether)-based units and do not have polar functional groups with respect to all units. <3> The powder composition according to any one of <1> or <2>, wherein the inorganic substance is silicon dioxide. <4> The powder composition according to any one of <1> to <3>, wherein at least a part of the surface of the inorganic substance is surface-treated with a silane coupling agent. <5> The powder composition according to any one of <1> to <4>, wherein the composite particles have the above-mentioned tetrafluoroethylene-based polymer as a core and have the above-mentioned inorganic substance on the surface of the core. <6> The powder composition according to any one of <1> to <5>, wherein the composite particles have an average particle diameter of 1 to 30 μm. <7> The powder composition according to any one of <1> to <6>, wherein in the composite particles, the inorganic substance is in the form of particles and spherical or scaly. <8> The powder composition according to any one of <1> to <7>, wherein in the composite particles, the tetrafluoroethylene-based polymer and the inorganic substance are each in the form of particles. <9> The powder composition according to any one of <1> to <8>, comprising the inorganic particles, and the inorganic particles contain at least one selected from the group consisting of silicon dioxide particles and boron nitride particles A sort of. <10> The powder composition according to any one of <1> to <9>, comprising particles of the above at least one resin, and the at least one resin is selected from the group consisting of polyimide, polyimide, At least one aromatic resin in the group consisting of polyester, polyesteramide, polyphenylene ether, polyphenylene sulfide, maleimide resin and epoxy resin. <11> The powder composition according to any one of <1> to 10, comprising particles of the at least one resin described above, wherein the at least one resin is a polytetrafluoroethylene or a hot-melt tetrafluoroethylene-based polymer. <12> Composite particles comprising a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an aromatic polymer having an aromatic ring content of 45% by mass or more. <13> The composite particle according to <12>, wherein the tetrafluoroethylene-based polymer contains a perfluoro(alkyl vinyl ether)-based unit and has a polar functional group, or contains 2.0 to 5.0 mol of all units % of units based on perfluoro(alkyl vinyl ether) without polar functional groups. <14> The composite particle according to <12>, wherein the aromatic polymer is a liquid crystal polyester. <15> The composite particle according to any one of <12> to <14>, wherein the tetrafluoroethylene-based polymer is used as a parent particle, and the parent particle has the aromatic polymer on the surface of the parent particle. [Effect of invention]

According to the present invention, a powder composition containing at least any one of a tetrafluoroethylene-based polymer, an inorganic substance, a specific resin, and inorganic particles can be obtained with a high degree of freedom of selection of inorganic particles to be used together, and a powder composition with a high degree of performance can be obtained based on the Formed products such as films with excellent physical properties (electrical properties, low linear expansion, high heat dissipation, etc.) of the same composition. In addition, according to the present invention, composite particles containing a tetrafluoroethylene-based polymer and an arbitrary amount of an aromatic polymer, and a dispersion liquid containing the composite particles and excellent in dispersion stability can be obtained, and a highly tetrafluoroethylene-based polymer can be obtained. Laminates and films of excellent properties (electrical properties, low linear expansion, etc.) of polymers and aromatic polymers.

The following terms have the following meanings. "Average particle size (D50)" is the volume-based cumulative 50% particle size of the object (particle) determined 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 particles at the point where the volume becomes 50% are accumulated on the cumulative curve. path. "D90" is the volume-based cumulative 90% particle size of the object measured in the same way. D50 and D90 of the object were obtained by dispersing particles in water, and using a laser diffraction scattering particle size distribution measuring device (manufactured by Horiba, Ltd., LA-920 measuring device) by laser diffraction The D50 and D90 of the object were obtained by analyzing by the radiation scattering method. "Specific surface area" is a value calculated by measuring particles or powders by the gas adsorption (constant volume method) BET (Brunauer-Emmett-Teller, Beuett) multipoint method, and is determined using NOVA4200e (manufactured by Quantachrome Instruments). ask for. The "melting temperature (melting point)" is the temperature corresponding to the maximum value of the melting peak measured by differential scanning calorimetry (DSC). "Glass transition point (Tg)" is a value measured by analysis of polymers, hardened materials or elastomers by dynamic viscoelasticity (DMA) method. "Viscosity of dispersion" is the viscosity measured using a B-type viscometer at 25°C and a rotational speed of 30 rpm. The measurement was repeated three times, and the average value of the three measurements was taken. The "thixotropic ratio of dispersion" is the value calculated by dividing the viscosity η1 by the viscosity η2. The above viscosity η1 is measured at 30 rpm, and the above viscosity η2 is measured at 60 rpm. The measurement of each viscosity was repeated 3 times, and the average value of the 3 measured values was taken. A "unit" in a polymer refers to an atomic group based on the aforementioned monomer formed by the polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or a unit obtained by converting a part of the above-mentioned unit into another structure by treating the polymer. Hereinafter, the unit based on the monomer a is also abbreviated as "monomer a unit".

The powder composition of the present invention (hereinafter, also referred to as "the present composition") includes composite particles (hereinafter, also referred to as "F polymer") containing a hot-melt tetrafluoroethylene-based polymer and an inorganic substance , also referred to as "this composite particle"); and at least one of resin particles and inorganic particles, the resin of which is at least one selected from the group consisting of fluorine-based resins and aromatic-based resins (hereinafter, Also referred to as "specific resin").

According to the present composition (hereinafter, referred to as "this composition A") comprising the present composite particles and inorganic particles, the physical properties (electrical properties such as low dielectric loss factor, etc.) based on the F polymer, and the physical properties ( Low linear expansion, etc.), and a formed product such as a film in which the physical properties (low linear expansion, high heat dissipation, etc.) of inorganic particles are balanced. The reason for this is not necessarily clear, but is considered as follows. The F polymer can be described as a thermoplastic polymer with high crystallinity, and is excellent in physical stress resistance and heat resistance. Since the present composite particles obtained from the inorganic material have a specific hardness, when the present composition A is melt-kneaded, the present composite particles collide with the inorganic particles, and each is pulverized and easily micronized. In addition, the present composite particles formed by bonding the F polymer and the inorganic substance are more likely to interact with the inorganic particles than the F polymer alone. Therefore, it is considered that inorganic substances and inorganic particles are uniformly mixed in the melted or softened F polymer. In addition, it is considered that the above-mentioned effects are enhanced because the F polymer is composited with the inorganic substance. As a result, it is thought that the molded object (film etc.) which consists of this composition A has the physical property based on three of F polymer, an inorganic substance, and an inorganic particle to a high degree.

Furthermore, according to the present composition (hereinafter, referred to as "the present composition B") comprising the present composite particles and the specific resin, the physical properties (electrical properties such as low dielectric loss factor, etc.) based on the F polymer, and the properties based on the inorganic substance can be obtained. Physical properties (low linear expansion, etc.), and physical properties (low linear expansion, UV (ultraviolet, ultraviolet) absorption, chemical resistance, heat resistance, processability, optical properties, etc.) based on a balance of specific resin-based films, etc. forming. The reason for this is not necessarily clear, but is considered as follows. The F polymer can be described as a thermoplastic polymer with high crystallinity, and is excellent in physical stress resistance and heat resistance. Since the present composite particles obtained from the inorganic substance have a specific hardness, when the present composition B is melt-kneaded, the present composite particles in which the F polymer is in a softened state are pulverized by shear stress and are easily micronized. In addition, the present composite particles formed by bonding the F polymer and the inorganic substance are more likely to interact with a specific resin than the F polymer alone. Therefore, it is considered that the present composite particles are uniformly mixed with the melted or softened specific resin while being micronized. Moreover, in this case, since the F polymer and the inorganic substance are composited (composited), it is considered that they are integrally mixed with the specific resin in the above state. As a result, it is thought that the molded object (film etc.) which consists of this composition B has the physical property based on the three of F polymer, an inorganic substance, and a specific resin to a high degree.

The F polymer in the present composite particles contained in the present composition is a polymer comprising tetrafluoroethylene (TFE)-based units (TFE units). The F polymer has thermal melting properties, and its melting temperature is preferably 260 to 320°C, more preferably 285 to 320°C. In this case, the composite particles are more likely to be uniformly mixed with the inorganic particles and the specific resin. 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.

Examples of the F polymer include: a polymer containing a TFE unit and an ethylene-based unit, a polymer containing a TFE unit and a propylene-based unit, a TFE unit and a perfluoro(alkyl vinyl ether) (PAVE)-based polymer Polymers of units (PAVE units) (PFA), polymers comprising TFE units and units based on hexafluoropropylene (FEP), polymers comprising TFE units and units based on fluoroalkyl ethylene, polymers comprising TFE units and units based on trifluoroalkyl ethylene The polymer of the unit of chlorofluoroethylene is preferably PFA or FEP, more preferably PFA. The abovementioned polymers may further comprise units based on other comonomers. As PAVE, CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ , or CF ₂ =CFOCF ₂ CF ₂ CF ₃ (hereinafter, also referred to as "PPVE") is preferable, and PPVE is more preferable.

The F polymer preferably has polar functional groups. In this case, the physical properties such as electrical properties and surface smoothness of the molded product formed from the present composition are likely to be excellent. The polar functional group may be included in the unit contained in the F polymer, or may be included in the terminal group of the F polymer main chain. As the latter F polymer, a polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., or a polymer having a polar functional group prepared by plasma treatment or ionizing radiation treatment can be exemplified thing. When the F polymer has a polar functional group, in the present composite particle, the F polymer and the inorganic substance are easily attached not only physically but also chemically, and the above-mentioned effects are easily enhanced.

The polar functional group is preferably a hydroxyl group-containing group, a carbonyl group-containing group, and a phosphonic acid group-containing group, more preferably a hydroxyl group-containing group and a carbonyl group-containing group, and still more preferably a carbonyl group-containing group. 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-ethylene glycol (-CH(OH)CH _2OH ). 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.

As a preferable aspect of the F polymer, a polymer (1) containing a TFE unit and a PAVE unit and having a polar functional group, or a polymer (1) containing a TFE unit and a PAVE unit and containing 2.0 to 5.0 mol with respect to all monomer units can be mentioned % of PAVE units and a polymer (2) without polar functional groups. These polymers form microspherulites in the molded product, and therefore, the physical properties of the obtained molded product can be easily improved.

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 having a polar functional group based on the total units, respectively. unit. Moreover, as a monomer which has a polar functional group, itaconic acid anhydride, citraconic acid anhydride, and 5-norene-2,3-dicarboxylic acid anhydride (hereinafter, also referred to as "NAH") are preferable. Specific examples of the polymer (1) include the polymer described in International Publication No. 2018/16644.

The polymer (2) is preferably composed of only TFE units and PAVE units, and contains 95.0 to 98.0 mol % of TFE units and 2.0 to 5.0 mol % of PAVE units with respect to all units. In the polymer (2), the content of the PAVE unit is preferably 2.1 mol % or more, more preferably 2.2 mol % or more, based on the entire unit. Furthermore, the fact that the polymer (2) does not have polar functional groups means that the number of polar functional groups contained in the polymer is less than 500 per 1×10 ⁶ carbon atoms constituting the main chain of the polymer. 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 be produced using a polymerization initiator or a chain transfer agent that does not generate a polar functional group as the terminal group of the polymer chain. The terminal group has a polar functional group derived from a polymerization initiator, etc.) and is produced by fluorination treatment. As a method of the fluorination treatment, a method using fluorine gas (refer to Japanese Patent Laid-Open No. 2019-194314, etc.) can be mentioned.

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

The inorganic substances in the composite particles contained in the composition are preferably oxides, nitrides, metal elements, alloys and carbon, more preferably silicates (silica (silica), wollastonite, talc, mica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, alkali aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (mass talc), and more preferably containing Inorganic oxides of at least one element selected from aluminum, magnesium, silicon, titanium, and zinc, especially silicon dioxide, titanium oxide, zinc oxide, talc and boron nitride, and most preferably silicon dioxide. In addition, the inorganic substance may be ceramics. One type of inorganic substances may be used, or two or more types may be used. When two or more kinds of inorganic substances are mixed, two kinds of silica may be used, or silica and metal oxide may be used.

The interaction between the inorganic substance and the F polymer is easily enhanced, and the composite particles can contain more inorganic substances. Moreover, in the molded object formed from this composition, the physical property based on an inorganic substance is easy to express remarkably. The inorganic substance in the composite particles preferably contains silica. The content of silica in the inorganic substance is preferably 50% by mass or more, more preferably 75% by mass or more. The content of silicon dioxide is preferably 100 mass % or less, more preferably 90 mass % or less.

It is preferable that at least a part of the surface of the inorganic substance is surface-treated. The surface treatment agent used in the surface treatment is preferably a silane coupling agent, as the silane coupling agent, more preferably 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-glycidyloxypropylmethyldiethoxysilane, 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, the inorganic substance, the F polymer and the inorganic particles, or the inorganic substance, the F polymer and the specific resin are more uniformly distributed, and the physical properties of the three are easily balanced.

Specific examples of inorganic substances include silica fillers ("ADMAFINE (registered trademark)" series manufactured by Admatechs, Inc.), zinc oxide surface-treated with esters such as propylene glycol diddecanoate (Sakai Chemical Industry Co., Ltd.) "FINEX (registered trademark)" series, etc.), spherical fused silica ("SFP (registered trademark)" series, etc. manufactured by DENKA), and rutile titanium oxide coated with polyols and inorganic substances ("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 bismuth Silica fillers ("E-SPHERES" series manufactured by Pacific Cement Corporation, "SiliNax" series manufactured by Nippon Steel Mining Corporation, "Eccosphere" series manufactured by Emerson & Cuming Corporation, hydrophobic AEROSIL series "RX200" manufactured by Nippon Aerosil Corporation) ", etc.), talc fillers ("SG" series manufactured by NIPPON TALC Corporation, etc.), block talc fillers ("BST" series manufactured by NIPPON TALC Corporation, etc.), boron nitride fillers ("UHP" series manufactured by Showa Denko Corporation, "Denka Boron Nitride" series ("GP", "HGP" grade), etc., manufactured by DENKA Corporation.

The shape of the inorganic substance is preferably granular, preferably spherical, needle-like (fibrous), or plate (column). Specific shapes of inorganic substances include spherical, scale-like, lamellar, leaf-like, almond-like, columnar, cockscomb, equiaxed, leaf-like, mica-like, block-like, plate-like, wedge-like, rose Flower-like, net-like, angular column-like, preferably spherical or scale-like. If the inorganic substance of this shape is used, the uniformity of the distribution of the inorganic substance in the molded product is improved, and the function thereof can be easily improved.

The spherical inorganic substance is preferably approximately true spherical. In the inorganic particles in this case, 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. If such highly spherical inorganic particles are used, the inorganic matter, F polymer and inorganic particles, or inorganic matter, F polymer and specific resin are more uniformly distributed in the molded product, and the physical properties of the three are more easily balanced. 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.

D50 of the present composite particles is preferably 30 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, particularly preferably 6 μm or less. D50 of the composite particles 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 composite particle becomes like this. Preferably it is 50 micrometers or less, More preferably, it is 20 micrometers or less, More preferably, it is 10 micrometers or less. If the D50 and D90 of the present composite particles are within this range, the physical properties of the obtained molded product are more likely to be improved.

Examples of the shape of the composite particles include spherical, scale-like, lamellar, leaf-like, almond-like, columnar, cockscomb-like, equiaxed, leaf-like, mica-like, block-like, plate-like, wedge-like, Rose-shaped, net-shaped, angular column-shaped, preferably spherical or scaly. If the present composite particles of this shape are used, the inorganic particles or the specific resin can be more uniformly mixed, so that the distribution uniformity of each component in the obtained molded product is improved, and the function thereof can be easily improved. Furthermore, when the present composite particles are scaly, the average major diameter (average value of the diameter in the longitudinal direction) is preferably within the range of the above-mentioned D50.

The present composite particles are preferably produced by a method such as causing F polymer particles (hereinafter, also referred to as "F powder") and inorganic particles to collide in a suspended state at a temperature equal to or higher than the melting temperature of the F polymer (hereinafter referred to as "F powder"). , also referred to as "dry method A"); make the F powder and inorganic particles collide in a state of extrusion or shearing (hereinafter, also referred to as "dry method B"); for the liquid combination containing F powder and inorganic particles The material is subjected to shearing treatment (hereinafter, also referred to as "wet method").

In the dry method A, for example, the F powder and the inorganic particles are supplied in a high-temperature turbulent gas atmosphere, and by the collision between the F powder and the inorganic particles, stress is applied between them and the particles are combined. This dry method A is sometimes referred to as hybrid treatment. The gas atmosphere is formed of gas. As the gas that can be used, air, oxygen, nitrogen, argon, or a mixed gas thereof can be mentioned. The F powder and the inorganic particles may be supplied together in the form of a premixed mixture under the gas atmosphere, or may be supplied separately under the gas atmosphere.

When the F powder and the inorganic particles are supplied to a high-temperature gas atmosphere, it is preferable that the particles are in a state in which they do not agglomerate with each other. As this method, a method of suspending particles in a medium (gas or liquid) can be used. Furthermore, a mixture of gas and liquid can also be used as the medium. Furthermore, in the dry method A, the high-temperature turbulent gas atmosphere can be prepared, and then the F powder and inorganic particles can be supplied therein, or the F powder and the inorganic particles can be suspended in a medium, and then the medium can be heated to form a high-temperature turbulent gas atmosphere. . As a device that can be used for the former, for example, a stirring body (for example, a stirring blade) rotating at a high speed in a cylindrical container is used to agitate the particles, and at the same time, the particles are sandwiched between the inner wall of the container and the stirring body to apply stress. Device (eg, "Hybridization System" manufactured by Nara Machinery Manufacturing Co., Ltd.). The temperature of the gas 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 a large amount of the inorganic particles includes an aggregate formed by agglomerating the primary particles thereof, the aggregate may be crushed before being supplied to a high-temperature gas atmosphere. As the method for 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 F powder and 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 are separated from the inner peripheral surface by a small distance. And the cooperation of the arranged internal parts applies a pressing force or a shearing force to the above-mentioned particles to combine them. This dry method B is sometimes referred to as mechanofusion treatment. The gas atmosphere in the cylindrical rotating body can be set as an inert gas atmosphere or a reducing gas atmosphere. The temperature of the gas atmosphere is preferably not more than the melting temperature of the F polymer, more preferably not more than 100°C.

The distance between the inner peripheral surface of the cylindrical rotating body and the inner part can be appropriately set according to the D50 of the F powder and inorganic particles. 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 the composite particles. Furthermore, in the case where a large amount of inorganic particles includes 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 (for example, "NOBILTA" manufactured by Hosokawa Micron) equipped with a rotating tank and a pulverizing and mixing blade, wherein the rotating tank is arranged with the rotation axis as the horizontal direction and has an elliptical shape ( A pulverizing and mixing chamber with a cross-section of a different shape), the pulverizing and mixing blades are rotatably inserted into the pulverizing and mixing chamber of the rotating tank, and are arranged so that the rotating shaft is located at the concentric position of the rotating axis of the rotating tank, and has an elliptical shape (different shape). ) of the section. In the pulverizing and mixing device, the F powder and the inorganic particles are pressed between the short-diameter part of the pulverizing and mixing chamber and the long-diameter part of the pulverizing and mixing blade, and the above-mentioned particles are subjected to a pressing force or a shearing force to combine them. .

Further, 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 lower than the rotation speed of the pulverizing and mixing blades. According to the pulverizing and mixing device, the pulverizing and mixing chamber and the pulverizing and mixing blades have a cross-section of a different shape, and the instantaneous pressing force or shearing force can be repeatedly applied to the F powder and the inorganic particles that flow due to their own weight in the pulverizing and mixing chamber. Therefore, the adverse effects of heat on the particles can be reduced, and the particles can be pulverized and mixed in a short time, so that the present composite particles having the desired physical properties can be easily obtained.

In the wet method, F powder, inorganic particles, and a dispersion medium can be mixed to prepare a liquid composition. Examples of mixing methods include: a method of simultaneously adding F powder and inorganic particles to a dispersion medium and mixing; a method of sequentially adding F powder and inorganic particles to a dispersion medium and mixing at the same time; preliminarily mixing F powder and inorganic fillers The method of mixing the obtained mixed particles with the dispersion medium; the method of mixing the F powder and the dispersion medium, the inorganic particles and the dispersion medium separately in advance, and then mixing the obtained two kinds of mixed solutions. ;Wait.

In the wet method, from the viewpoint of mixing the F powder and the inorganic particles to disperse them more uniformly, the following two methods are more advantageous and preferable, namely: dispersing the F powder in the dispersion medium in advance. Then, inorganic particles are added and mixed as they are (directly) or dispersed in a dispersion medium, and a liquid composition is prepared in this order; or inorganic particles are dispersed in a dispersion medium in advance, as is (direct) or dispersed The F powder was added and mixed in the state of the dispersion medium, and a liquid composition was prepared in this order.

In the method of shearing the liquid composition, for example, the following dispersers can be used: a single-shaft or multi-shaft equipped with a propeller blade (Propeller Blade), a turbine blade (Tubine Balde), a paddle blade (paddle blade), a shell or a ball mill, attritor, basket mill, sand mill, sand grinder, DYNO-MILL, DISPERMAT, SC-MILL, Spike Mill or Agitator mill and other dispersers that use media; or micro-spray homogenizers, NANOMIZER, ULTIMAIZER and other dispersers that do not use media.

The shear treatment is preferably a high shear condition. "High shear" in the context of stirring means stirring at speeds in excess of 300 rpm. The shearing treatment may be started in the middle of adding the inorganic particles to the dispersion liquid containing the F powder (when the liquid composition is prepared), or may be performed after the addition is completed (after the liquid composition is prepared). By continuing these shearing treatments for a sufficient period of time, the desired present composite particles can be produced.

From the viewpoint of further improving the adhesiveness (adhesion) with the inorganic particles, it is preferable to surface-treat the F powder before mixing with the inorganic particles, or simultaneously with the mixing. The surface treatment includes 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. Moreover, according to the dry method A and the dry method B, when the F powder collides with the inorganic particles, heat is easily uniformly transferred to these particles, and the present particles are easily densified and spherical. In this case, the sphericity of the present composite particles is preferably 0.5 or more.

As a preferable aspect of this composite particle, there may be mentioned an aspect in which the F polymer is used as a core and an inorganic substance is attached to the surface of the core (hereinafter, also referred to as "Aspect I"), an inorganic substance is used as a core and an inorganic substance is attached to the surface of the core. An 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 composite particle, and does not mean the main component in the composition of the present composite particle. The adherents (inorganic matter or F polymer) attached to the core surface may be attached only to a part of the core surface, or may be attached to most or the entire surface thereof. In the former case, it can also be said that the attached matter is in a state in which it adheres to the surface of the nucleus as if it were dust, in other words, it is in a state in which most of the surface of the nucleus is exposed. In the latter case, it can also be said that the adherents are dispersed on the core surface without exception or cover the core surface, and the composite particle can also be said to have a core-shell structure including a core and a shell covering the core.

In the case of Aspect I, the core and the inorganic substance of the F polymer are preferably in the form of particles, respectively. In this case, since the inorganic substance having a hardness higher than that of the F polymer is exposed to the surface of the composite particle, the fluidity is improved, and the handleability thereof is easily improved. In addition, it is easy to prepare a powder composition with high uniform dispersibility. 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 F powder. In the production of the present composite particles of Aspect I, it is preferable to set the D50 of the F powder to be larger than the D50 of the inorganic particles, and to set the amount of the F powder to be larger than the amount of the inorganic particles. If the present composite particles are produced in such a relationship, the present composite particles of Aspect I can be easily obtained.

In the case of Aspect I, the D50 of the F powder used in the production is preferably 20 μm or less, more preferably 8 μm or less. D50 of the F powder is preferably 0.1 μm or more, more preferably 1 μm or more. In the case of Aspect I, the D50 of the inorganic particles used in the production is preferably 0.001 to 0.5 times, more preferably 0.001 to 0.3 times, the D50 of the F powder. Specifically, it is preferable that the D50 of the F powder exceeds 1 μm, and the D50 of the inorganic particles is 0.1 μm or less. Moreover, 0.1 mass part or more is preferable with respect to 100 mass parts of F polymers, and, as for the quantity of an inorganic substance particle, 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 composite particle of Aspect I obtained in this way, the above relationship is maintained, the D50 of the core of the F polymer is greater than the D50 of the inorganic particle, and the F polymer occupies therein more mass than the inorganic substance. In this case, the surface of the core of the F polymer is covered with a larger amount of inorganic particles, so that the present particle of Aspect I has a core-shell structure. In addition, in this case, the aggregation of F powders is suppressed, and the present composite particle in which the inorganic particles are attached to the core composed of the F powder alone can be easily obtained.

In Aspect I, the inorganic particles are preferably spherical, more preferably approximately true spherical. The approximate true spherical shape means that when the particles are observed with a scanning electron microscope (SEM), the ratio of the short diameter to the long diameter is 0.5 or more, and the ratio of spherical particles is 95% or more. In the inorganic particles in this case, 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 "spherical shape" includes not only a true spherical shape but also a slightly deformed spherical shape. If such highly spherical inorganic particles are used, the inorganic matter, F polymer and inorganic particles, or inorganic matter, F polymer and specific resin are more uniformly distributed in the molded product, and it is easier to achieve a balance based on the physical properties of the three .

In Aspect I, the D50 of the inorganic particles is preferably in the range of 0.001 to 3 μm, more preferably 0.005 to 1 μm, and still more preferably 0.01 to 0.1 μm. When D50 is within this range, the properties and fluidity of the composite particles are easily improved, and the uniform dispersibility of the powder composition is easily improved. In addition, the particle size distribution of the inorganic particles is preferably 3 or less, more preferably 2.9 or less, using the value of D90/D10 as an index. Here, "D10" is the volume-based cumulative 10% particle size of the object measured in the same manner as D50 and D90. From the viewpoint of easy control of the fluidity of the present composite particles obtained, it is preferable that the particle size distribution is narrow.

In Aspect I, it is preferable that at least a part of the surface of the inorganic particle is surface-treated, and it is more preferable that the surface is treated with a silazane compound such as hexamethyldisilazane, a silane coupling agent, or the like. As a silane coupling agent, the above-mentioned compound is mentioned. In Aspect I, one type of inorganic particles may be used, or two or more types may be used. When two kinds of inorganic particles are used in combination, the D50 of each inorganic particle can also 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.

Also, in the case of Aspect I, a part of the inorganic particles is preferably embedded in the core of the F polymer. Thereby, the adhesion between the inorganic particles and the core of the F polymer is further improved, and the inorganic particles are less likely to fall off from the composite particles. That is, the stability of this composite particle is further improved. In the present composite 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. In the present composite particle of aspect I, the D50 of the inorganic particle is preferably 0.001 to 0.5 times, more preferably 0.001 to 0.3 times, the D50 of the core of the F polymer. Specifically, it is preferable that the D50 of the core of the F polymer exceeds 1 μm and the D50 of the inorganic particle is 0.1 μm or less.

Moreover, in the present composite particle of Aspect I, the ratio of the F polymer occupied is preferably 50 to 99 mass %, more preferably 75 to 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 to the inorganic element content on the surface of the present composite particle of aspect I measured by energy dispersive X-ray spectroscopy is preferably less than 1, more preferably 0.5 or less, and further Preferably it is 0.1 or less. The above-mentioned comparison is preferably 0 or more. In addition, the target elements in the measurement were set to four elements of carbon element, fluorine element, oxygen element and silicon element, and the ratio (unit: atomic %) of each of fluorine element and silicon element to the total was taken as each element. element content. In other words, the present composite particles in aspect I of the mass ratio are particles whose surfaces are sufficiently covered with inorganic substances, not only due to the excellent physical properties of the inorganic substances, but also the molded products formed from them tend to have a high degree of properties based on the inorganic substances, F polymers and inorganic particles. or the physical properties of inorganic substances, F polymers and specific resins.

The present composite particle of Aspect I may be further surface-treated according to the physical properties of the inorganic matter adhering to the surface. As a specific example of this surface treatment, the method of surface-treating the present composite particle of the aspect I in which the inorganic substance contains silica with siloxanes (polydimethylsiloxane etc.) or a silane coupling agent is mentioned. The surface treatment can be carried out as follows: the dispersion liquid in which the composite particles are dispersed is mixed with a siloxane or a silane coupling agent to react with the siloxane or a silane coupling agent, and the treated composite particles are recovered. As a silane coupling agent, the silane coupling agent which has the said functional group is preferable. According to this method, not only the amount of silica on the surface of the present composite particle, 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 core of the inorganic material. Thereby, the adhesion between the F polymer and the core of the inorganic substance is further improved, and the F polymer is less likely to fall off from the composite particles. That is, the stability of this composite particle is further improved. In addition, the core of the inorganic substance is preferably in the form of particles. In this case, in the present composite particle, the surface of the core of the inorganic substance is easily covered with the F polymer, whereby the present composite particle is easily prevented from agglomerating. In the production of the present composite particles of aspect II, it is preferable to set the D50 of the inorganic particles to be greater than the D50 of the F powder, and to set the amount of the inorganic particles to be greater than the amount of the F polymer particles. When the present composite particles are produced in such a relationship, the present composite particles of aspect II can be easily obtained.

In this case, the D50 of the F powder is preferably 0.001 to 0.5 times, more preferably 0.001 to 0.3 times, the D50 of the inorganic particles. Moreover, 0.1 mass part or more is preferable with respect to 100 weight part of inorganic particle|grains, and, as for the quantity of F powder, 1 mass part or more is more preferable. The upper limit thereof is preferably 50 parts by mass, more preferably 10 parts by mass. In the present composite particle of Aspect II obtained in this way, the above relationship is maintained, the D50 of the core of the inorganic substance is greater than that of the F powder, and the inorganic substance occupies more mass therein than the mass of the F polymer. In this case, the surface of the core of the inorganic substance is covered with a larger amount of F powder, so that the present composite particle of Aspect II has a core-shell structure.

In the present composite particle of aspect II, the D50 of the core of the inorganic substance is preferably 0.1 μm or more, more preferably more than 1 μm. The upper limit thereof is preferably 30 μm, more preferably 10 μm. Moreover, 50-99 mass % is preferable, and, as for the ratio which an inorganic substance occupies in the present composite 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 %.

Examples of the inorganic particles in the composition A include inorganic particles containing the same inorganic substances as the inorganic substances forming the composite particles described above. The inorganic particles in the composition A may contain the same inorganic substances as the inorganic substances forming the composite particles, or may contain different inorganic substances. The inorganic particles in the composition A preferably contain at least one selected from the group consisting of silica particles and boron nitride particles. When silicon dioxide particles are used together, the electrical properties and low linear expansion properties of the molded product can be further improved, and when boron nitride particles are used together, the electrical properties and high heat dissipation properties of the molded product can be further improved. Examples of the shape of the inorganic particles include spherical, scale-like, lamellar, leaf-like, almond-like, columnar, cockscomb, equiaxed, leaf-like, mica-like, block-like, plate-like, wedge-like, rose Flower-like, net-like, angular column-like, preferably spherical or scale-like. When the inorganic particles of this shape are used, the composite particles can be mixed more uniformly, and therefore, the distribution uniformity of each component in the obtained molded product is improved, and the function thereof can be easily improved.

Specifically, the silica particles are preferably spherical, preferably approximately true spherical. In this case, the ratio of the short diameter to the long diameter is preferably 0.5 or more, more preferably 0.8 or more. The above-mentioned comparison is preferably less than 1. If the highly spherical silica particles are used together, the inorganic matter, the F polymer and the inorganic particles are more uniformly distributed in the molded product, and the physical properties of the three are more likely to be balanced. D50 of the silica particles is preferably 0.1-20 μm, more preferably 1-10 μm. The D50 silica particles have good fluidity and excellent handleability. As a specific example of the silica particle, the same silica filler as the specific example of the inorganic substance which forms this composite particle mentioned above can be mentioned.

The boron nitride particles are preferably scaly. When scaly boron nitride particles (hexagonal boron nitride particles) are used together, the formability of the composition A is good. In addition, in the molded product, the boron nitride particles are aligned, so that the heat dissipation property of the molded product can be more easily improved. In this case, the aspect ratio of the boron nitride particles is preferably 1.0 to 3.0, more preferably 1.0 to 2.5. The D50 (equivalent to the average major diameter) is preferably 1 to 25 μm, more preferably 2 to 20 μm. The boron nitride particles preferably have a bimodal particle size distribution, and are also preferably substantially free of particles having a particle size (long axis) of 30.0 μm or more (the content is 0.1 mass % or less). Specific examples of boron nitride particles include "UHP" series (manufactured by Showa Denko Co., Ltd.), CF600 (manufactured by Momentive Co., Ltd.), FS-3 (manufactured by Mizushima Alloy Iron Co., Ltd.), "Denka Boron Nitride" series ("GP" , "HGP" grade), etc.) (manufactured by DENKA).

The present composition A may further contain other tetrafluoroethylene-based polymer particles. The tetrafluoroethylene-based polymer particles may be thermally fusible or non-thermally fusible. The tetrafluoroethylene-based polymer may be the same type of polymer as that of the above-mentioned F polymer constituting the composite particles, or may be a different type of polymer. The tetrafluoroethylene-based polymer is preferably polytetrafluoroethylene (PTFE) or F polymer, more preferably PFA or FEP, and still more preferably the above-mentioned polymer (1) or polymer (2).

When PTFE particles are used in combination, the obtained molded product tends to exhibit remarkably PTFE-based physical properties (low-dielectric loss factor and other electrical properties). PTFE is preferably PTFE (low molecular weight PTFE) having a number average molecular weight (Mn) calculated based on the following formula (1) of 200,000 or less. Mn=2.1×10 ¹⁰ ×ΔHc ^-5.16・・・ (1) In formula (1), ΔHc represents the heat of crystallization (cal/g) of PTFE measured by differential scanning calorimetry. Mn of the low molecular weight PTFE is preferably 100,000 or less, more preferably 50,000 or less. The Mn of the low molecular weight PTFE is preferably 10,000 or more. When the F polymer particles are used in combination, it is easy to obtain a molded product in which the inorganic substance and the inorganic particles are more uniformly dispersed.

The tetrafluoroethylene-based polymer particles may be composed of only the tetrafluoroethylene-based polymer, or may contain the tetrafluoroethylene-based polymer and other components (the above-mentioned resin materials, etc.). D50 of the tetrafluoroethylene-based polymer particles is preferably 50 μm or less, more preferably 20 μm or less, and still more preferably 8 μm or less. D50 of the tetrafluoroethylene-based polymer particles is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 1 μm or more. In addition, D90 of the tetrafluoroethylene-based polymer particles is preferably less than 100 μm, more preferably 90 μm or less.

As a preferred aspect of the present composition A, the combination of the present composite particles and silica particles containing the polymer (1) or the polymer (2) and silica; the polymer (1) or the polymer Combination of the present composite particles of polymer (2) and silica and boron nitride particles; the present composite particles containing polymer (1) or polymer (2) and silica, silica particles, and polymer ( 1) or a combination of particles of polymer (2); or the present composite particles containing polymer (1) or polymer (2) and silica, boron nitride particles, and polymer (1) or polymer ( 2) combination of particles.

The present composition A may further contain other resin particles. Other resins can be thermoplastic or thermoset. As the thermoplastic resin, aromatic elastomers such as aromatic polyimide, aromatic maleimide, styrene elastomer, and liquid crystal polyester can be mentioned. Specific examples of the aromatic polyimide include "Neopulim (registered trademark)" series (manufactured by Mitsubishi Gas Chemical Co., Ltd.), "SPIXAREA (registered trademark)" series (manufactured by SOMAR Corporation), "Q-PILON (registered trademark)" )” series (manufactured by PI Institute of Technology), “WINGO” series (manufactured by Wingo Technology Co., Ltd.), “TOHMIDE (registered trademark)” series (manufactured by T&K TOKA Co., Ltd.), “KPI-MX” series (manufactured by Kawamura Sangyo Co., Ltd.), "UPIA (registered trademark)-AT" series (manufactured by Ube Industries, Ltd.). As the liquid crystal polyester, polyester or polyesteramide into which an amide bond is introduced can be mentioned. Bonds derived from isocyanates, such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond, may be introduced into polyester or polyester amide. Examples of the liquid crystal polyester include polymers described in paragraphs [0010] to [0015] of JP-A No. 2000-248056. Specific examples of liquid crystal polyesters include "LAPEROS" series manufactured by Polyplastics, "Vectra" series manufactured by Celanese Corporation, "UENO LCP" series manufactured by Ueno Pharmaceutical Co., Ltd., and "SUMIKA SUPER LCP" manufactured by Sumitomo Chemical Co., Ltd. ”, “XYDAR” series manufactured by SOLVAY SPECIALTY POLYMERS, “XYDAR” series manufactured by JX Nippon Mining & Energy Co., Ltd., and “SIVERAS” series manufactured by Toray Corporation.

On the other hand, as the thermosetting resin, thermosetting polyimide, polyimide precursor (polyimide), epoxy resin, thermosetting acrylic resin, bismaleimide resin, and thermosetting polyphenylene ether resin can be exemplified .

In the present composition A, the content of the composite particles is preferably 30% by mass or more, more preferably 40% by mass or more. The upper limit of the content of the composite particles is preferably 80% by mass or less, more preferably 70% by mass or less. When the present composition A containing the present composite particles in such an amount is used, a molded product which exhibits physical properties based on the respective components in a well-balanced manner can be easily obtained. The present composition A is preferably produced by dry-blending the components. In dry blending, a mixing device such as a tumbler, a Henschel mixer, a hopper, a Banbury mixer, a drum, and a Buchner mixer can be used.

The specific resin particles in this composition B are particles of at least one resin selected from the group consisting of fluorine-based resins and aromatic-based resins. The above-mentioned particles of one resin means particles of at least one resin selected from the group consisting of particles composed of only fluorine-based resins and particles composed of only aromatic-based resins, and are distinguished from the present composite particles. When the particles of the fluorine-based resin are used in combination, the F polymer and the fluorine-based resin are uniformly mixed when the composition B is melt-kneaded, so that it is easy to obtain a molded product in which these and inorganic substances are uniformly dispersed. The molded article is excellent in physical properties (especially electrical properties and low linear expansion) based on the three. On the other hand, when the aromatic resin particles are used together, the physical properties based on the aromatic resin can be imparted to the molded article, and the molded article can exhibit excellent dimensional stability during, for example, immersion in a chemical solution or heat treatment.

The above-mentioned fluorine-based resin may be a polymer of the same type as that of the above-mentioned F polymer constituting the present composite particle, or may be a polymer of a different type. The fluorine-based resin is preferably PTFE or F polymer, more preferably PFA or FEP, and still more preferably the above-mentioned polymer (1) or polymer (2). When PTFE particles are used in combination, the obtained molded product tends to exhibit remarkably PTFE-based physical properties (low-dielectric loss factor and other electrical properties). The aspect of PTFE, specifically, the preferable range of Mn of PTFE is as described above. When F polymer particles are used in combination, it is easy to obtain a molded product in which inorganic substances are more uniformly dispersed. The fluorine-based resin particles may be composed of only the fluorine-based resin, or may contain the fluorine-based resin and other components (the above-mentioned resin materials and the like). The preferred ranges of D50 and D90 of the fluorine-based resin particles are as described above.

Further, the aromatic resin is preferably selected from the group consisting of polyimide, polyimide, polyester, polyesterimide, polyphenylene ether, polyphenylene sulfide, maleimide resin, and epoxy resin. At least one aromatic resin in the group consisting of resins. When the aromatic resin particles are used in combination, the dimensional stability and UV absorption properties (UV processability) of the obtained molded article during immersion in a chemical solution or during heat treatment are further improved. Among them, liquid crystalline aromatic polyesters are preferred. Examples of the liquid-crystalline aromatic polyester include aromatic polyester and aromatic polyester amide into which an amide bond is introduced. Bonds derived from isocyanates, such as an imide bond, a carbonate bond, a carbodiimide bond, an isocyanurate bond, etc., may further be introduced into the aromatic polyester or the aromatic polyester amide. The liquid-crystalline aromatic polyester is preferably thermoplastic, and the melting temperature is preferably in the range of 260 to 360°C, more preferably in the range of 270 to 350°C.

Among the aromatic polyesters of liquid crystallinity, polyesters containing at least a unit based on p-hydroxybenzoic acid (HBA) or a unit based on 6-hydroxy-2-naphthoic acid (HNA) are preferable, and are preferably: Polyesters comprising HBA units and HNA units; units comprising at least one aromatic hydroxycarboxylic acid in HBA or HNA, 4,4'-dihydroxybiphenyl or at least one aromatic diphenol in hydroquinone , and terephthalic acid, isophthalic acid or at least one of 2,6-naphthalene dicarboxylic acid in the unit of aromatic dicarboxylic acid polyester; containing HBA units and 2,6-dihydroxynaphthoic acid units Esters; polyesters comprising 2,6-dihydroxynaphthoic acid units, terephthalic acid units and acetaminophen units; polyesters comprising HBA units, terephthalic acid units and 4,4'-biphenol units.

These aromatic polyesters can be obtained by industrial production, and examples include "Vectra" series manufactured by Celanese Japan, "XYDAR" series by JX Energy, "LAPEROS" series by Polyplastics, and "LAPEROS" series by Ueno Pharmaceutical Co., Ltd. "UENO LCP" series, etc. The D50 of the aromatic resin particles is preferably 0.1 to 200 μm, more preferably 1 to 100 μm, and still more preferably 5 to 50 μm.

The at least one resin described above is preferably a fluorine-based resin and an aromatic-based resin. That is, the present composition B is preferably a powder composition containing the present composite particles, fluorine-based resin particles, and aromatic-based resin particles. In this case, it is easy to obtain a molded product exhibiting the above-mentioned physical properties in a well-balanced manner. As a preferable aspect of this composition B, the combination of the present composite particles containing the polymer (1) or the polymer (2) and silica and the liquid crystalline aromatic polyester particles, or the polymer containing (1) A combination of the present composite particles of polymer (2) and silica, liquid crystalline aromatic polyester particles, and particles of polymer (1) or polymer (2).

In the present composition B, the content of the composite particles is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass. On the other hand, the content of the specific resin particles is preferably 10 to 99 mass %, more preferably 20 to 90 mass %, and still more preferably 30 to 80 mass %. When the composite particles and the specific resin particles are used in combination in this quantitative relationship, it is easy to obtain a molded product that exhibits physical properties based on the respective components in a well-balanced manner. The present composition B is preferably produced by dry-blending the components. For dry blending, the above-mentioned mixing apparatus can be used.

The present composition is preferably used for melt extrusion molding, injection molding or compression molding. According to melt extrusion molding, for example, the following films can be preferably produced. On the other hand, according to injection molding or compression molding, for example, it is possible to preferably manufacture antenna parts capable of producing an antenna with excellent antenna gain. The antenna includes, for example, an antenna part formed from the composition and an antenna pattern formed of a conductor. In particular, the antenna part is preferably a holding member for holding the antenna pattern, or a matching layer for covering the antenna pattern.

When a film (hereinafter, also referred to as "this film") is formed from the present composition, the melt extrusion molding is preferably performed by a method using a T-die, more preferably by a method of The composition fed from the hopper is melt-kneaded in an extruder (single-screw or twin-screw), and extruded through a T-die provided at the front end of the extruder to form a film.

The film obtained by melt extrusion molding is preferably further subjected to extension treatment. Thereby, a more isotropic film can be obtained. The stretching process softens the film at a temperature below its melting point and unidirectional (uniaxial: MD direction) or bidirectional (biaxial: MD direction (Machine Direction, machine direction) and TD direction (Transverse Direction, perpendicular to the machine direction) )) to perform extension processing. From the viewpoint of obtaining an isotropic film, the stretching treatment is more preferably a biaxial stretching treatment. As the stretching method, an inflation method and a flattening method can be mentioned. As a flattening method, any method of simultaneous biaxial extension and successive biaxial extension may be adopted.

When a film is produced by melt extrusion molding, a lamination process, a stretching process, a cooling process, and a peeling process may be further performed on the obtained film. The lamination process is a process of laminating a release film on both sides or one side of the obtained film to form a laminate. As a lamination method, a hot pressing method and a surface treatment method are mentioned, and in this case, a hot pressing roll, a hot pressing apparatus, or a laminator can be used. For example, in the case of using a heat press roll, the obtained film and a release film can be overlapped, and the heat press can be carried out by passing the film and the like through a heat press roll. In the case of using a hot-pressing device, the obtained film and the release film can be overlapped on the bottom plate of the hot-pressing device, heat-pressed, and then cooled.

In addition, a pair of hot-pressing rolls may be used, the present composition in a molten state extruded by a T-die may be supplied to the gap between two release films, and a laminate may be formed in the gap between the hot-pressing rolls. When the layered body is formed, a co-extrusion method using a multi-layer die can be used to form a multi-layered body including a film and a release film formed from the present composition as respective layers. The thickness of the release film is preferably 10 to 200 μm, more preferably 20 to 100 μm.

The stretching process is a process of softening the release film layer of the laminated body obtained by the lamination process, and simultaneously extending the above-mentioned laminated body to obtain a stretched product. This extension process can also be performed continuously. The cooling treatment is a treatment of cooling the extension obtained by the extension treatment. For cooling, natural cooling may be used, or a cooling roll or the like may be used. The peeling treatment is a treatment of peeling off the peeling film from the cooled extension. The peeling treatment can be performed by a 90° peeling method or a 180° peeling method. Through the above-mentioned series of treatments, a film whose thermal expansion coefficient is further suppressed can be obtained from the present composition.

In the forming of the film, inflation forming can also be used. In inflation molding, the melt-kneaded product of the composition extruded from a ring die (circular die, round die) extends in both directions (MD direction and TD direction), so that the isotropy of the film is easily improved. In inflation molding, the melt-kneaded product is mechanically stretched in two directions by pulling and expanding, so it is easy to form a film in which polymer molecules are aligned in two directions. In addition, in this case, a film having a structure similar to that of the above-mentioned laminate can also be formed by inflation molding. That is, the present composition and other thermoplastic polymers are melt-extruded from a ring die, and a laminate is formed by inflation molding.

Examples of laminates that can be formed at this time include a two-layer laminate (type 1) comprising one film layer formed of the present composition and one release film layer, and one layer sandwiched between two release film layers. A 3-layer laminate (type 2) of film layers formed from the present composition, a 3-layer laminate (type 3) in which a release film layer is sandwiched between two film layers formed from the present composition, preferably type 2 Layer 1 or Layer 3. In these laminates, the thickness of the film layer formed from the present composition is preferably 3 to 150 μm. Moreover, it is preferable that the thickness of a peeling film layer is more than the thickness of the said film layer and 2 times or less. A film whose thermal expansion coefficient is further suppressed can also be obtained from the present composition by the above-mentioned series of treatments.

This film is preferably a metal foil laminate by forming a metal layer on the surface thereof. Examples of the metal include various metals such as copper, nickel, aluminum, silver, gold, and tin, and alloys thereof (stainless steel, etc.). Examples of the metal foil laminate include a single-sided metal foil laminate having a metal layer and the present film in this order, and a double-sided metal foil laminate having a metal layer, the present film layer, and a metal layer in this order. Moreover, these metal foil laminates may further have other layers (prepreg layer, glass member layer, ceramic member layer, other resin film layer). As a method of forming a metal layer on the surface of the film, there may be mentioned: a method of bonding a metal foil on the surface of the film by a lamination method or a hot pressing method, and forming a metal layer on the surface of the film by a sputtering method or a vapor deposition method. method, a method of forming a metal layer on the surface of the film by a plating method (including electroless plating or electrolytic plating after electroless plating), and a printing method using a metal conductive ink (screen printing method) , inkjet method, ion plating method) to form a metal layer on the surface of the film. In addition, as a metal foil, copper foil, such as a rolled copper foil and an electrolytic copper foil, is preferable.

In order to further improve the adhesion with the metal layer, the surface of the film can also be subjected to surface treatment. The surface treatment includes plasma treatment, corona treatment, flame treatment, and ITRO treatment. The metal foil laminate can be used as a material or member of a printed circuit board, a high heat dissipation substrate, an antenna substrate, and the like. For example, when the metal layer of this metal foil laminated body is etched and a pattern circuit is formed, a printed circuit board can be obtained. In this case, after forming a pattern circuit, an interlayer insulating film may be formed on the pattern circuit, and a pattern circuit may be further formed on the interlayer insulating film. Moreover, a solder resist layer may be laminated|stacked on a pattern circuit, and a cover film may be laminated|stacked. Typically, the coverlay film includes a base film and an adhesive layer formed on the surface thereof, and the surface on the side of the adhesive layer is bonded to a printed circuit board. This film can also be used as the base film of the cover film. In addition, an interlayer insulating film (adhesion layer) using this film may be formed on a patterned circuit, and a polyimide film as a cover film may be laminated.

As described above, the present film is excellent in low linear expansion. Specifically, the linear expansion coefficient of the film is preferably 50 ppm/°C or less, more preferably 40 ppm/°C or less, and still more preferably 30 ppm/°C or less. The lower limit of the coefficient of linear expansion is 5 ppm/°C. As described above, when the present composition contains aromatic resin particles, the present film can exhibit excellent dimensional stability during immersion in a chemical solution or during heat treatment. The dimensional stability can be evaluated based on the dimensional change before and after the film is kept at 150°C for 30 minutes and then cooled to 25°C. Specifically, the dimensional change rate is preferably 2% or less, more preferably less than 1.5%. The lower limit of the dimensional change rate is 0%.

The present invention also includes composite particles (hereinafter, also referred to as "aromatic polymers") containing an F polymer having a melting temperature of 260 to 320°C and an aromatic polymer having an aromatic ring content of 45% by mass or more (hereinafter, also referred to as "aromatic polymer"). Hereinafter, also referred to as "prime particle").

This particle is a composite of F polymer and aromatic polymer, can contain any amount of aromatic polymer, and has high stability. The mechanism of action is not necessarily clear, but is considered as follows. Compared with non-thermofusible tetrafluoroethylene-based polymers, F polymer not only has excellent shape stability such as fibril resistance, but also has a high-degree-of-freedom configuration that relieves the restriction of molecular motion at the single-molecule level. The F polymer tends to form microspheroidal crystals at the level of molecular aggregates, and the surface of the F polymer tends to have a microscopic concavo-convex structure, thereby easily increasing the surface area. Therefore, it is considered that the molecular aggregate of the F polymer, typically the F polymer particle (F powder), can stably and physically adhere closely to the aromatic polymer without losing its shape, thereby forming the present particle. Moreover, it is thought that the aromatic ring content of an aromatic polymer in a specific range balances the hydrophobicity of an aromatic polymer and an F polymer, and improves the affinity of both. In particular, in the case of the F polymer having the melting temperature specified in the present invention and the aromatic polymer having the aromatic ring content specified in the present invention, these tendencies are considered to complement each other and form the particles more easily. Furthermore, it is considered that the interaction between the closely adhered aromatic polymers further promotes the adhesion of the aromatic polymers, thereby stabilizing the present particles. As a result, although the present particle can contain an arbitrary amount of the aromatic polymer, it is considered that the particle has high stability and has high physical properties of the F polymer and the physical properties of the aromatic polymer.

The melting temperature of the F polymer in this particle is 260-320°C, preferably 275-315°C, more preferably 290-310°C. Other details of the F polymer in this particle are the same as those contained in the description of this composition. In this case, the affinity with the aromatic polymer is more likely to increase. The F polymer is not only excellent in the dispersion stability of its particles, but also more easily densely and homogeneously distributed in the molded article (polymer layer, etc.) obtained from the present particles. Furthermore, it becomes easy to form microspherulites in a molded object, and it becomes easy to improve the adhesiveness with other components. As a result, it becomes easier to obtain a molded product excellent in various physical properties such as electrical properties.

The aromatic polymer constituting the particles is characterized in that the aromatic ring content is 45% by mass or more. In this specification, "aromatic ring content" is calculated|required by the following formula. In addition, the carbon atoms contained in the substituent bonded to the aromatic ring are not included in the carbon atoms forming the aromatic ring. Aromatic ring content (mass %) = 100×[mass of carbon atoms forming aromatic rings in polymer backbone (g)/total amount of polymer (g)] For example, the aromatic ring content in a typical unit contained in the liquid crystal polyester is as follows, and the aromatic ring content of each liquid crystal polyester can be calculated based on the copolymerization ratio (mol ratio) of each unit. 2-Hydroxy-6-naphthoic acid: 71% 4,4'-Dihydroxybiphenyl: 78% Terephthalic acid: 54% 2,6-Naphthalenedicarboxylic acid: 66% The aromatic ring content of the aromatic polymer is preferably 55% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more. The aromatic ring content is preferably 80% by mass or less.

The aromatic ring in the aromatic polymer may be a monocyclic ring, a condensed ring, or a heterocyclic ring, preferably a monocyclic ring or a condensed ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. An aromatic polymer may be comprised only by the unit containing an aromatic ring, and may contain the unit containing an aromatic ring, and the unit which does not contain an aromatic ring. As the aromatic polymer constituting the present particle, the former is preferred.

Specific examples of the aromatic polymers include polyimide, polyamide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polysulfite, polyetherether, aromatic polyetherketone, Liquid crystal polyester, etc. Among them, polyimide and liquid crystal polyester are preferred, and liquid polyester is more preferred. As the liquid crystal polyester, aromatic polyester or aromatic polyester amide into which an amide bond is introduced can be exemplified. An isocyanate-derived bond, such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond, etc. may be introduced into the aromatic polyester or the aromatic polyester imide. The liquid crystal polyester is preferably a thermoplastic, more preferably a liquid crystal polyester having a melting temperature in the range of 260 to 360°C, and more preferably in the range of 270 to 350°C.

Examples of liquid crystal polyesters include polymers described in paragraphs [0010] to [0015] of the above-mentioned Japanese Patent Laid-Open No. 2000-248056, and specific examples thereof include dicarboxylic acids (terephthalic acid, isophthalic acid) Formic acid, diphenyl ether-4,4'-dicarboxylic acid, acetic anhydride, etc.), dihydroxy compounds (4,4'-biphenol, etc.), aromatic hydroxycarboxylic acids (4-hydroxybenzoic acid, 6-hydroxy- 2-naphthoic acid, 2-hydroxy-6-naphthoic acid, etc.), aromatic diamines, aromatic hydroxylamines, aromatic amino acids, etc. polymers. Specific examples of liquid crystal polyesters include: a reaction product of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; a reaction product of 6-hydroxy-2-naphthoic acid, terephthalic acid and acetaminophen; 4- Reactants of hydroxybenzoic acid, terephthalic acid and 4,4'-biphenol; 2-hydroxy-6-naphthoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid and 2,6-naphthalene diphenyl Carboxylic acid reactant. As a specific example of the liquid crystal polyester which can be obtained industrially, the said commercial item is mentioned.

As an aspect of the present particle, an aspect in which the F polymer is used as a parent particle and an aromatic polymer is present on the surface of the parent particle is exemplified. Preferably, the F polymer is used as a core and has an aromatic polymer on the surface of the core. The aspect of the aromatic polymer (hereinafter, also referred to as "Aspect I'"); the aspect in which the aromatic polymer is used as the mother particle and the F polymer is present on the surface of the mother particle is preferably in the form of The aromatic polymer is a core and has a form of the F polymer on the surface of the core (hereinafter, also referred to as "form 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 aromatic polymer or F polymer on the core surface may be attached to only a part of the core surface, or may be attached to most or the entire surface thereof. In the former case, it can be said that the adhered matter is in a state of adhering to the surface of the nucleus as if it were dust, in other words, it is in a state in which most of the surface of the nucleus is exposed. In the latter case, it can be said that the adherents are completely dispersed on the surface of the core or the state of covering the surface of the core, and it can also be said that the particle has a core-shell structure including a core and a shell covering the core.

The present particle is preferably aspect I'. In the present particle of aspect I', the F polymer is difficult to be modified, and the fluidity and handling properties of the present particle are easily improved. Moreover, the dispersion stability of this particle|grains is easy to improve. In aspect I', it is preferable that the F polymer is particulate (F powder) and the aromatic polymer is particulate, or that the F polymer is particulate and the aromatic polymer is non-particulate state. In other words, in the aspect I', the aromatic polymer may be in the state of coating a part or the entire surface of the F powder in the form of particles, or the aromatic polymer may coat a part of the surface of the F powder in the form of non-particles or all states. More preferably, the core of the F polymer and the aromatic polymer are in the form of particles, respectively. Furthermore, in the case of aspect I', the core of the F polymer may be composed of a single particle of the F powder, or may be composed of an aggregate of the F powder. In the case of Aspect I', preferably at least a part of the aromatic polymer is bonded to the surface of the core of the F polymer. Thereby, the adhesiveness between the core of the aromatic polymer and the F polymer is further improved, and the aromatic polymer is less likely to fall off from the particles. That is, the stability of this particle is further improved. The present particle of Aspect I' is also applied to the above-mentioned preferred manufacturing method (dry method A, dry method B, wet method) of the present composite particle to obtain F powder and aromatic polymer particles. In this case, it is preferable to set the D50 of the F powder to be larger than the D50 of the aromatic polymer particles, and to set the amount of the F polymer to be larger than the amount of the aromatic polymer. If the present particle is produced in such a relationship, the present particle of aspect I' can be easily obtained.

Based on the D50 of the F powder, the D50 of the aromatic polymer particles used in the production of the present particles of the aspect I' is preferably 0.0001 to 0.1, more preferably 0.002 to 0.02. Specifically, D50 of the F powder is preferably more than 1 μm and D50 of the aromatic polymer particles is preferably 0.1 μm or less. Moreover, 0.1 mass part or more is preferable with respect to 100 mass parts of F powders, and, as for the quantity of the aromatic polymer particle used for the manufacture of the present particle of Aspect I', it is more preferable that it is 1 mass part or more. 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 the aspect I' obtained in this way, the above relationship is maintained, and the F polymer occupies therein more mass than the aromatic polymer. In addition, when the aromatic polymer in the present particle is in the form of particles, the D50 of the core of the F polymer is larger than the D50 of the aromatic polymer particle. In this case, the surface of the core of the F polymer is covered with a larger amount of aromatic polymer particles, so that the present particle of aspect I' has a core-shell structure. In addition, in this case, the aggregation of the particles of the F powder is suppressed, and the composite particles (the present particles) in which the aromatic polymer is attached to the core composed of the F powder alone can be easily obtained.

When the aromatic polymer in the particles of the aspect I' is in the form of particles, the D50 of the aromatic polymer particles is preferably in the range of 0.001 to 0.3 μm, more preferably 0.005 to 0.2 μm, and more preferably 0.01 to 0.1 μm. When D50 is within this range, the properties and fluidity of the particles are easily improved, and the dispersion stability is easily improved. In this case, a part of the aromatic polymer particles may be embedded in the core of the F polymer. 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.

In the present particle of the aspect I', the ratio of the F polymer is preferably 50 to 99 mass %, more preferably 75 to 99 mass %. The ratio of the aromatic polymer is preferably 0.1 to 50 mass %, more preferably 1 to 25 mass %. In other words, the present particle of aspect I' of the mass ratio is a particle whose surface is highly coated with an aromatic polymer, and is not only excellent in particle physical properties (dispersibility in liquid, etc.) based on the aromatic polymer, but also formed by the aromatic polymer. The molded article tends to have the properties of the aromatic polymer and the properties of the F polymer to a high degree.

From the viewpoint of adjusting the physical properties of the surface, the present particle of aspect I' may be further surface-treated. As a specific example of this surface treatment, the method of surface-treating this particle with siloxanes (polydimethylsiloxane etc.) or a silane coupling agent is 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 after reacting with the siloxane or a silane coupling agent, the particles are recovered.

In the case of aspect II', the F polymer is preferably in the form of particles. In the case of aspect II', preferably at least a part of the F polymer is bonded to the surface of the core of the aromatic polymer. Thereby, the adhesion between the F polymer and the core of the aromatic polymer is further improved, and the F polymer is less likely to fall off from the particles. That is, the stability of this particle is further improved. In addition, the core of the aromatic polymer is preferably in the form of particles. In this case, in the present particle, the surface of the core of the aromatic polymer is easily covered with the F polymer, whereby the present particle is easily prevented from agglomerating. Further, the core of the aromatic polymer may be composed of a single particle of the aromatic polymer, or may be composed of an aggregate of the aromatic polymer particles. The present particle of the aspect II' is also preferably produced by the above-mentioned dry method A, dry method B, and wet method. In this case, it is preferable to set the D50 of the aromatic polymer particles to be larger than the D50 of the F powder, and to set the amount of the aromatic polymer particles to be larger than the amount of the F powder. If the present particles are produced by the dry method A or the dry method B in such a relationship, the present particles of the aspect II' can be easily obtained.

In the case of aspect II', the D50 of the F powder used for the production of the particles is preferably 0.0001 to 0.5, more preferably 0.0002 to 0.2, based on the D50 of the aromatic polymer particles. Moreover, 0.1 mass part or more is preferable with respect to 100 mass parts of aromatic polymer particles, and, as for the quantity of F powder, 1 mass part or more is more preferable. The upper limit thereof is preferably 50 parts by mass, more preferably 10 parts by mass. In the present particle of aspect II' obtained in this way, the above-mentioned relationship is maintained, and the aromatic polymer occupies more mass therein than the F polymer. In addition, when the F polymer is in the form of particles, the D50 of the core of the aromatic polymer is larger than the D50 of the F powder. In this case, the surface of the core of the aromatic polymer is coated with a larger amount of F powder, so that the present particle of the aspect II' has a core-shell structure.

In the present particle of the aspect II', D50 of the core of the aromatic polymer is preferably 1 μm or more, more preferably more than 3 μm. The upper limit thereof is preferably 40 μm, more preferably 30 μm. In the present particle of the aspect II', when the F polymer is in the form of particles, the D50 of the F powder is preferably in the range of 0.1 to 10 μm, more preferably 1 to 5 μm. When D50 is within this range, the properties and fluidity of the particles are easily improved, and the dispersion stability is easily improved. Moreover, in the present particle of the aspect II', the ratio of the aromatic polymer is preferably 50 to 99 mass %, more preferably 60 to 90 mass %. The ratio of the F polymer is preferably from 1 to 50 mass %, more preferably from 10 to 40 mass %.

The present particles may further include inorganic particles. Examples of the inorganic particles include inorganic particles of the present composite particles described above. One type of inorganic particles may be used, or two or more types may be used in combination. When two or more types of inorganic particles are used in combination, two types of silica particles may be used in combination, or silica particles and metal oxide particles may be used in combination. The interaction between the inorganic particles and the F polymer is easily enhanced, and the dispersion stability of the dispersion liquid of the particles is easily further improved. Moreover, in the molded object (for example, the following polymer layer and film) formed from a dispersion liquid, the physical property based on an inorganic particle is easy to express remarkably. Among them, the inorganic particles preferably contain silica. The content of silica in the inorganic particles is preferably 80% by mass or more, more preferably 90% by mass or more. The upper limit of the content of silica is 100% by mass. The inorganic particles are preferably surface-treated at least a part of their surfaces. As a surface treatment agent used for this surface treatment, the said silane coupling agent is mentioned. Specific examples and shapes of the inorganic particles are also the same as those described above. The D50 of the inorganic particles is preferably 20 μm or less, more preferably 5 μm or less. D50 is preferably 0.001 μm or more, more preferably 0.01 μm or more. The ratio of the inorganic particles to the particles is preferably 0.01 to 30% by mass, more preferably 1 to 20% by mass.

D50 of this particle is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. D50 of this particle is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 3 μm or more. Moreover, D90 of this particle is preferably 80 μm or less, more preferably 30 μm or less. When the D50 and D90 of the present particle are within this range, the dispersion stability of the present particle in the dispersion liquid and the physical properties of the molded product (polymer layer, etc.) obtained from the dispersion liquid are more easily improved.

The present particles are preferably produced by a method of colliding the F powder and the aromatic polymer particles in a suspended state at a temperature equal to or higher than the melting temperature of the F polymer (corresponding to the above-mentioned "dry method A"); A method of colliding the F powder with the aromatic polymer particles in an extruded or sheared state (corresponding to the above-mentioned "dry method B"). Alternatively, it can also be produced by a method such as a method of coagulating the F powder by shearing a liquid composition containing the F powder and the aromatic polymer particles (corresponding to the above-mentioned "wet method") .

The F powder and the aromatic polymer particles may be supplied together as a premixed mixture under the gas atmosphere, or may be separately supplied under the gas atmosphere. Furthermore, in the case of obtaining the present particles containing inorganic particles, the inorganic particles may also be supplied together in a premixed mixture in a gas atmosphere, or the F powder and the aromatic polymer particles may be compounded first, and then The inorganic particles are separately supplied under a gas atmosphere. In the latter case, it is preferable from the viewpoint of fluidity and handleability that at least a part of the surface, or most of the surface, or the entire surface of the present particle in which the inorganic particles are adhered can be obtained. When the F powder and the aromatic polymer particles are supplied to a high-temperature gas atmosphere, it is preferable that the particles are in a state in which they do not agglomerate with each other. As this method, a method of suspending particles in a medium (gas or liquid) can be used. Furthermore, a mixture of gas and liquid can also be used as the medium. Other details of the high-temperature turbulent gas atmosphere and the equipment that can be used in the dry method A are the same as those of the above-mentioned production of the composite particles.

The gas atmosphere in the cylindrical rotating body in the dry method B can be set to an inert gas atmosphere or a reducing gas atmosphere. The temperature of the gas atmosphere is preferably not more than the melting temperature of the aromatic polymer or the F polymer, more preferably not more than 100°C. Details such as the apparatus that can be used are the same as those in the production of the composite particles described above. Furthermore, in the case of obtaining the present particle containing inorganic particles, it may be further compounded in the coexistence of inorganic particles, or F powder and aromatic polymer particles may be compounded first, and then the obtained present particle and inorganic particles may be compounded. Particle Compounding. In the latter case, it is preferable from the viewpoint of fluidity and handleability that at least a part of the surface, or most of the surface, or the entire surface of the present particle in which the inorganic particles are adhered can be obtained.

The wet method is a method for obtaining the present particles by subjecting a liquid composition containing F powder and aromatic polymer particles to shear treatment, and combining F powder and aromatic polymer particles. In addition, in the case of obtaining the present particle containing inorganic particles, the inorganic particles may be mixed in the above-mentioned liquid composition in advance, and shearing treatment may be performed to combine them. When the inorganic particles are silica, colloidal silica is suitably used.

In the wet method, the total content of the F powder and the aromatic polymer particles in the liquid composition is preferably 20% by mass or more, more preferably 40 to 80% by mass, relative to the total mass of the liquid composition. . Moreover, regarding the mass ratio of the F powder and the aromatic polymer particles in the liquid composition, when the mass of the F powder is 1, the mass of the aromatic polymer particles is preferably 0.01 to 2.0, more specifically , in the case of obtaining the present particles of the aspect I', the liquid composition preferably contains 20-60 mass % of the F powder and 1-20 mass % of the aromatic polymer particles, and in obtaining the aspect II' In the case of this particle, the liquid composition preferably contains 1 to 20 mass % of F powder and 20 to 60 mass % of aromatic polymer particles.

The liquid composition can be prepared by mixing F powder, aromatic polymer particles, and a dispersion medium. Examples of the mixing method include: a method of adding F powder and aromatic polymer particles to a dispersion medium together and mixing; adding F powder and aromatic polymer particles to a dispersion medium in order and mixing at the same time The method of mixing the F powder with the aromatic polymer particles in advance, and then mixing the obtained mixture with the dispersion medium; respectively pre-mixing the F powder with the dispersion medium, the aromatic polymer particles and the dispersion medium. A method of mixing and then mixing the two mixtures obtained; etc. In addition, as a dispersion medium, the compound etc. which are the same as the type of the liquid dispersion medium described below are suitably used.

When F powder or aromatic polymer particles are mixed to obtain a liquid composition, stirring may be performed while mixing, or stirring may be performed after completion of mixing. As an apparatus for stirring, the stirring apparatus provided with blades (stirring blades), such as a propeller blade, a turbine blade, a paddle, and a shell-shaped blade, is mentioned, for example. In addition, the stirring speed at this time should just be the level which can disperse|distribute the F powder and the aromatic polymer particle efficiently in a liquid composition.

The method for shearing the liquid composition includes, for example, stirring by the above-mentioned stirring device, or a Henschel mixer, a pressure kneader, a Banbury mixer or a planetary mixer; Crusher, basket mill, sand mill, sand grinder, DYNO-MILL (bead mill using grinding media such as glass beads or zirconia beads), DISPERMAT, SC-MILL , Spike Mill (Spike Mill) or Agitator Mill (Agitator mill) and other disperser using medium for mixing; use micro-spray homogenizer, NANOMIZER, ULTIMAIZER and other high-pressure homogenizers, ultrasonic homogenizers, high-speed dispersing mixers (dissolver) ), disperser (disper), high-speed impeller disperser and other dispersers that do not use media for mixing.

The shear treatment is preferably a high shear condition. "High shear" has the same meaning as above. The shearing treatment may be performed while mixing the F powder and the aromatic polymer particles, or the shearing treatment may be performed after the mixing is completed.

The flow state of the liquid composition in the shearing treatment is preferably upflow. Upflow can be upflow in any state of swirling flow, up-and-down circulation flow, and radial flow. In addition, when forming an upflow, the flow pattern can be adjusted by using a baffle plate or the like, and the installation position or installation angle of the processing device (agitator, stirring tank, etc.) can be adjusted to eccentric the flow pattern. When an upward flow is formed and the liquid composition is subjected to shear treatment, the interaction between the F powder and the aromatic polymer particles during the shear treatment tends to proceed uniformly.

As a method of removing the dispersion medium after the shearing treatment and isolating the particles, heating, decompression, or filtration may be mentioned, and these may be used in combination as appropriate. Specific examples of the method for isolating the particles include: (1) distilling off the dispersion medium under atmospheric pressure or reduced pressure, then concentrating, filtering and drying if necessary; (2) facing the dispersion liquid on one side The particles are aggregated while the temperature is adjusted, or the particles are coagulated and crystallized by adding electrolytes, coagulants, coagulation aids, etc., followed by separation and drying by filtration, etc.; (3) The dispersion is sprayed to Dry in a dry gas at a temperature at which the dispersion medium can volatilize, and recover; (4) Dry the dispersion after centrifuging; and so on. Here, as a drying method, vacuum drying, high frequency drying, and hot air drying are mentioned. In each of the above-mentioned methods (1) to (4), the dispersion liquid may be diluted with a dispersion medium if necessary, and the total content of the F polymer and the aromatic polymer in the dispersion liquid may be adjusted in advance.

In the above-mentioned production of the present particles by the dry method A, the dry method B, and the wet method, from the viewpoint of further improving the adhesiveness (adhesion) with the aromatic polymer particles, it is preferable to use an aromatic Before mixing the aromatic polymer particles, or while mixing the aromatic polymer particles, the F powder is surface-treated. As a surface treatment, the above-mentioned treatment is mentioned. Moreover, according to the dry method A and the dry method B, when the F powder collides with the aromatic polymer particles, heat is easily uniformly transferred to the particles, and the present particles are easily densified and spherical. In this case, the sphericity of the present particle is preferably 0.93 to 0.99.

In the production of the particles, the D50 of the F powder is preferably 20 μm or less, more preferably 10 μm or less. D50 of the F powder is preferably 0.01 μm or more, more preferably 0.1 μm or more. In addition, D90 of the F powder is preferably 10 μm or less. In the case of D50 and D90 in this range, the fluidity and dispersibility of the F powder are good, and in the wet method, the size of the composite particles existing in the dispersion medium can be easily controlled to make it difficult to settle. The bulk density of the F powder is preferably 0.15 g/m ² or more, more preferably 0.20 g/m ² or more. The bulk density of the F powder is preferably 0.50 g/m ² or less, more preferably 0.35 g/m ² or less. In the production of the present particles, the D50 of the aromatic polymer particles is preferably 40 μm or less, more preferably 30 μm or less. D50 of the aromatic polymer particles is preferably 0.01 μm or more, more preferably 0.1 μm or more.

The present invention also relates to a dispersion liquid (hereinafter, also referred to as "the present dispersion liquid") comprising the present particles and a liquid dispersion medium, and wherein the present particles are dispersed in the liquid dispersion medium. Even if the present particles are mixed in a large amount with a liquid dispersion medium, they can be stably dispersed. In addition, in the molded article (polymer layer, film, etc.) formed from the dispersion liquid, the F polymer and the aromatic polymer are more uniformly distributed, and the physical properties based on the F polymer and the aromatic polymer are likely to be highly expressed materiality.

The liquid dispersion medium is preferably a compound that is liquid at 25°C under atmospheric pressure. The liquid dispersion medium may be polar or non-polar, preferably polar. The liquid dispersion medium is more preferably at least one selected from the group consisting of water, amides, ketones and esters. The boiling point of the liquid dispersion medium is preferably in the range of 50 to 240°C. When this liquid dispersion medium is used, it becomes easy to keep the present particle in a constant dispersed state in the present dispersion liquid. Examples of the liquid dispersion medium include water, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, -Butoxy-N,N-dimethylpropionamide, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, cyclopentanone, butyl acetate, methyl isopropyl Ketone, methyl ethyl ketone, toluene, preferably water, N-methyl-2-pyrrolidone, γ-butyrolactone, methyl ethyl ketone, cyclohexanone and cyclopentanone, more preferably N - Methyl-2-pyrrolidone, methyl ethyl ketone.

A liquid dispersion medium may be used individually by 1 type, and may use 2 or more types together. The liquid dispersion medium may also be a mixture of a fluorine-based liquid dispersion medium and a fluorine-based liquid dispersion medium. The ratio of the fluorine-based liquid dispersion medium is preferably 1 to 25% by mass relative to the total content of the fluorine-based liquid dispersion medium and the non-fluorine-based liquid dispersion medium. As the fluorine-based liquid dispersion medium, fluoroalcohols, hydrofluoroethers, and hydrofluorocarbons are preferred. In this case, the dispersion liquid tends to have excellent dispersion stability. The liquid dispersion medium may be a mixture of a liquid dispersion medium having a surface tension of 30 mN/m or less, a liquid dispersion medium having a surface tension of 20 to 50 mN/m, or water. In this case, the dispersion liquid tends to have excellent dispersion stability. The liquid dispersion medium may also be a liquid dispersion medium with a boiling point of 80 to 260°C and a liquid dispersion medium with an evaporation rate of 0.01 to 0.3 and a boiling point of 140 to 260°C when the evaporation rate of butyl acetate is set to 1. mixture. In this case, the dispersion liquid tends to have excellent dispersion stability. The content of the liquid dispersion medium in the dispersion is preferably 30 to 90% by mass, more preferably 50 to 80% by mass.

This dispersion liquid may further contain a surfactant, and may not contain a surfactant. When the present dispersion liquid contains a surfactant, the content thereof is preferably 1 to 15% by mass, and the surfactant is preferably nonionic. As the surfactant, an acetylene-based surfactant, a silicone-based surfactant, and a fluorine-based surfactant are preferred. Furthermore, the fluorine-based surfactant is a compound having a hydrophilic part and a hydrophobic part containing a fluorine-containing organic group. However, due to the above-mentioned mechanism of action, the dispersion liquid has excellent dispersion stability and handling properties even if it does not contain a surfactant, especially a fluorine-based surfactant, and it is preferably the dispersion liquid that does not contain a fluorine-based surfactant. . In addition, the low dielectric dissipation factor and the like of the molded article formed from the dispersion liquid containing no fluorine-based surfactant can be more easily improved.

From the viewpoint of improving the electrical properties, adhesiveness, and low linear expansion properties of the molded product formed from the dispersion, the dispersion may further contain other resin materials than the particles. When the present dispersion liquid contains other resin materials, the content thereof is preferably 40% by mass or less with respect to the entire present dispersion liquid. As another resin material, F polymer and aromatic resin are mentioned. Other resin materials may be the same as the F polymer or aromatic polymer in this particle. As the F polymer among other resin materials, in addition to the above-mentioned F polymer, low molecular weight PTFE and modified PTFE can be mentioned. Furthermore, low molecular weight PTFE or modified PTFE also includes copolymers of TFE and a very small amount of comonomers (HFP, PAVE, FAE, etc.). When the F polymer in this particle is the above-mentioned polymer (1) having a polar functional group, other resin materials are preferably PFA, more preferably the above-mentioned polymer (1) having a polar functional group.

Among other resin materials, the aromatic resin is preferably aromatic polyimide, aromatic maleimide, polyphenylene ether, aromatic polyamide, or aromatic elastomer (styrene elastomer, etc.) . The aromatic polyimide may be thermoplastic or thermosetting, more preferably thermoplastic aromatic polyimide. Thermoplastic polyimide means a polyimide that completes imidization without further imidization. Examples of the aromatic polyimide include the above-mentioned polymers.

Examples of the styrene elastomer include: a copolymer of styrene and a conjugated diene or (meth)acrylate (styrene-butadiene rubber; styrene-based core-shell copolymer; styrene-butadiene) - Styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated products of styrene-butadiene-styrene block copolymers, and styrene-isoprene-benzene A styrene-based block copolymer such as a hydrogenated product of an ethylene block copolymer, etc.) is preferably a styrene elastomer having properties of both rubber and plastic, and being plasticized by heating to exhibit flexibility. In this case, not only the adhesiveness and low linear expansion properties of the molded article formed from the dispersion liquid are further improved, but also the liquid properties (viscosity, thixotropy ratio, etc.) of the dispersion liquid are balanced, and the handleability thereof is easily improved.

The present dispersion may further contain inorganic particles. As the inorganic particles, the same inorganic particles as the above-mentioned inorganic particles that can constitute the present particle can be mentioned. One type of inorganic particles may be used, or two or more types may be used. When the present dispersion liquid further contains inorganic particles, the content thereof is preferably in the range of 1 to 40% by mass, more preferably 5 to 30% by mass, with respect to the whole of the present dispersion liquid. Moreover, in the present dispersion liquid, the mass ratio (mass ratio) of the content of the inorganic particles to the content of the present particles is preferably 0.01 to 2, more preferably 0.1 to 0.6.

In addition to the above-mentioned components, the dispersion liquid 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 antifoaming agent, and a Oxidant, heat stabilizer, lubricant, antistatic agent, brightener, colorant, conductive agent, release agent, surface treatment agent, flame retardant and other ingredients.

The viscosity of the dispersion liquid is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, still more preferably 5000 mPa·s or more, particularly preferably 10000 mPa·s or more. The viscosity of the dispersion liquid is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, and still more preferably 20,000 mPa·s or less. In this case, the present dispersion liquid is easy to form a molded product (polymer layer, etc.) which is excellent in coatability and has an arbitrary thickness. In addition, with regard to the present dispersion having a viscosity in this range, especially a high viscosity range, the physical properties of each of the F polymer and the aromatic polymer are likely to be highly expressed in the molded product formed therefrom. The thixotropy ratio of the dispersion liquid is preferably 1.0 or more. The thixotropy ratio of the present dispersion is preferably 3.0 or less, more preferably 2.0 or less. In this case, the present dispersion liquid is excellent in coatability and homogeneity, and it is easy to form a denser molded product (polymer layer, etc.). The content of the present particles in the present dispersion liquid is preferably 20% by mass or more, more preferably 40 to 80% by mass, relative to the total mass of the present dispersion liquid.

When this dispersion liquid is applied to the surface of the sheet-like base material layer to form a liquid film, and the liquid film is heated to remove the dispersion medium, a dry film is formed, and the dry film is heated to further heat the F polymer. By baking, the laminated body which has the polymer layer (henceforth "F layer") containing the F polymer and the aromatic polymer on the surface of the sheet-like base material layer can be obtained.

Examples of the sheet-like base material layer include metal substrates (metal foils of copper, nickel, aluminum, titanium, alloys thereof, etc.), heat-resistant resin films (including polyimide, polyarylate, polysilicon, polyamide, etc.) A film of one or more kinds of heat-resistant resins such as arylene, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystal polyester, liquid crystal polyesteramide, etc., may be A single-layer film may also be a multilayer film), a prepreg (precursor of a fiber-reinforced resin substrate).

As a method of applying the dispersion liquid to the surface of the sheet-like base material, any method may be used to form a stable liquid film (wet film) containing the dispersion liquid on the surface of the sheet-like base material, and a coating method can be exemplified. , droplet discharge method, dipping method, preferably coating method. When the coating method is used, a liquid film can be efficiently formed on the surface of the base material by simple equipment. Examples of the coating method include spray coating, roll coating, spin coating, gravure coating, microgravure coating, gravure offset coating, blade coating, contact coating, bar coating, die coating Nozzle coating method, injection Mehler rod method, slot die nozzle coating method.

When drying the liquid film, the liquid film is heated at a temperature at which the dispersion medium volatilizes, and a dry film is formed on the surface of the sheet-like base material. The heating temperature is preferably the boiling point of the dispersion medium +50°C or lower, more preferably the boiling point of the dispersion medium or lower, and still more preferably the boiling point of the dispersion medium -50°C or lower. The temperature during drying is preferably 120°C to 200°C. Furthermore, air may be blown in the step of removing the dispersion medium. During drying, the dispersion medium does not necessarily need to be completely volatilized, and the volatilization may be sufficient to keep the shape of the layer after it is stable and can maintain a self-supporting film. When calcining the F polymer, it is preferable to heat the dry film at a temperature higher than or equal to the melting temperature of the F polymer. The heating temperature is preferably 380°C or lower, more preferably 350°C or lower. As each heating method, a method of using an oven, a method of using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays can be mentioned. Heating can also be performed in any state under normal pressure and under reduced pressure. In addition, the heating gas atmosphere may be any of an oxidizing gas atmosphere (oxygen, etc.), a reducing gas atmosphere (hydrogen, etc.), and an inert gas atmosphere (helium, neon, argon, nitrogen, etc.). The heating time is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes. When the heating is performed under the above conditions, the F layer can be preferably formed while maintaining high productivity.

The thickness of the F layer is preferably 0.1-150 μm. Specifically, when the sheet-like base material layer is a metal foil, the thickness of the F layer is preferably 1 to 30 μm. When the sheet-like base material layer is a heat-resistant resin film, the thickness of the F layer is preferably 1 to 150 μm, more preferably 10 to 50 μm. The peel strength between the F layer and the base material layer is preferably 10 N/cm or more, more preferably 15 N/cm or more. The above-mentioned peel strength is preferably 100 N/cm or less. When the present dispersion liquid is used, the present layered body can be easily formed without impairing the physical properties of the F polymer in the F layer.

The dispersion liquid may be applied to only one surface of the sheet-like base material layer, or may be applied to both sides of the sheet-like base material layer. The former can obtain a laminate having a sheet-like base material layer and an F layer on a single surface of the sheet-like base material layer, and the latter can obtain a sheet-like base material layer and an F layer on both surfaces of the sheet-like base material layer. Laminated body. The latter laminate is less likely to be warped, and therefore has excellent handling properties during processing. Specific examples of the laminate include a metal foil laminate having a metal foil and an F layer on at least one surface of the metal foil, a polyimide film and a polyimide film on both surfaces of the polyimide film. Multilayer film of layer F.

In addition, the metal foil with a carrier which consists of two or more layers of metal foils can also be used as a metal foil. The metal foil with a carrier includes a carrier copper foil (thickness: 10 to 35 μm) and an ultra-thin copper foil (thickness: 2 to 5 μm) with a carrier laminated on the carrier copper foil via a release layer. copper foil. When this copper foil with a carrier is used, a fine pattern can be formed by the MSAP (modified semi-additive) process. As said peeling layer, the metal layer which consists of nickel or chromium, or the multilayer metal layer which laminated|stacked this metal layer is preferable. As a specific example of the metal foil with a carrier, the trade name "FUTF-5DAF-2" by Futian Metal Foil Powder Industry Co., Ltd. is mentioned.

Here, the outermost surface of the sheet-like substrate (the surface on the opposite side of the F layer and the substrate layer) may be further surface-treated to further improve its low linear expansion or adhesiveness. As a method of surface treatment, annealing treatment, corona treatment, plasma treatment, ozone treatment, excimer treatment, and silane coupling treatment can be mentioned. Regarding the conditions in the annealing treatment, the temperature is preferably 120 to 180° C., the pressure is 0.005 to 0.015 MPa, and the time is preferably 30 to 120 minutes. As a gas used for plasma treatment, oxygen gas, nitrogen gas, rare gas (argon gas, etc.), hydrogen gas, ammonia gas, and vinyl acetate are mentioned. These gases may be used alone or in combination of two or more.

Other substrates may be further laminated on the outermost surface of the laminated body. 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 base material (tow, woven cloth, etc.) of the prepreg system reinforced fiber (glass fiber, carbon fiber, etc.) is impregnated with a sheet substrate of thermosetting resin or thermoplastic resin. The heat-resistant resin film is a film containing one or more heat-resistant resins, and examples of the heat-resistant resin include the above-mentioned aromatic polymers.

As a lamination method, the method of thermocompression bonding a laminated body and another board|substrate is mentioned. The conditions for thermocompression bonding when the other substrates are prepregs are preferably 120 to 400°C for temperature, 20 kPa or less for atmospheric pressure, and 0.2 to 10 MPa for pressing pressure. The laminate has an F layer with excellent electrical properties, so it is suitable as a printed circuit board material. Specifically, it can be used as a flexible metal foil laminate or a rigid metal foil laminate for the production of a printed circuit board. In particular, it is suitable as a Flexible metal foil laminates are used in the manufacture of flexible printed circuit boards.

The metal foil in which the sheet-like base material layer is a laminate of metal foils (metal foil with F layer) can be etched to form a transmission circuit to obtain a printed circuit board. Specifically, the printed circuit board can be produced by the following methods: a method of etching a metal foil to process it into a specific transmission circuit, or by a plating method (semi-additive method (SAP method), an improved semi-additive method ( MSAP method), etc.) a method of processing metal foil into a specific transmission circuit. The printed circuit board made of the metal foil with the F layer has the transmission circuit formed of the metal foil and the F layer in this order. As a specific example of the structure of a printed circuit board, transmission circuit/F layer/prepreg layer, transmission circuit/F layer/prepreg layer/F layer/transmission circuit are mentioned. In the manufacture of the printed circuit board, an interlayer insulating film can be formed on the transmission circuit, a solder resist layer can also be laminated on the transmission circuit, and a cover film can also be laminated on the transmission circuit. These interlayer insulating films, solder resist layers, and cover films may also be formed from the present dispersion.

When this particle is used for melt extrusion molding, injection molding, and compression molding, a molded product containing the F polymer and the aromatic polymer can be obtained. For example, when the present particles are melt-extruded, a film can be obtained.

Furthermore, when the present particles and the fluoroolefin-based polymer are melt-kneaded and then extrusion-molded, a film containing the F polymer, the aromatic polymer, and the fluoroolefin-based polymer can be obtained. The fluoroolefin-based polymer melt-kneaded with the particles may be an F polymer or a polymer other than the F polymer including a fluoroolefin-based unit. 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 PTFE is preferably low molecular weight PTFE or modified PTFE. The fluoroolefin-based polymer also preferably has a polar functional group. In addition, the kind and introduction method of polar functional groups, including preferable ones, are the same as those of the above-mentioned F polymer.

The thickness of the film is preferably 5 to 150 μm, more preferably 10 to 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 direction of the elongated shape is preferably 1000 mm or more. The upper limit of the length in the short direction is usually 3000 mm.

After superimposing the obtained film and the base material layer, thermocompression bonding is performed, whereby a laminate having a polymer layer and a base material layer formed of the film can be obtained. Regarding the conditions of thermocompression bonding, it is preferable that the temperature is set to 120 to 300° C., the pressure of the gas atmosphere is set to a vacuum of 20 kPa or less, and the pressurized pressure is set to 0.2 to 10 MPa. In addition, the aspect using the printed circuit board and the multilayer printed circuit board of a base material layer, a laminated body, and a preferable aspect are also the same as the above-mentioned.

According to the present invention, the present particles (composite particles) excellent in dispersibility and dispersion stability can be obtained. The layered product of the above-mentioned F layer or the above-mentioned film and other substrates produced from the particles can be used as antenna parts, printed circuit boards, parts for aircraft, parts for automobiles, sports equipment, food industry products, paints, cosmetics and the like. Specifically, it can be used as wire covering materials (aircraft wires, etc.), electrical insulating tapes, insulating tapes for oil drilling, materials for printed circuit boards, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes) Membranes, dialysis membranes, gas separation membranes, etc.), electrode binders (for lithium secondary batteries, fuel cells, etc.), replica rolls, housings for furniture, automotive dashboards, home appliances, etc., sliding members (load bearings, sliding shafts) , valves, bearings, gears, cams, belt conveyors, conveyor belts for food handling, etc.), tools (shovels, files, cones, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, die mouths , toilet, container covering material. The particles can also be effectively used as additives and modifiers for various varnishes (resists, inks, coatings, etc.) of resins such as polyimide and liquid crystal polymers, and can impart the physical properties of F polymer.

As mentioned above, although the powder composition of this invention, this particle|grains, and this dispersion liquid were demonstrated, this invention is not limited to the structure of the said embodiment. For example, the powder composition of the present invention, the particles, and the dispersion liquid of the present invention may each have other arbitrary structures added to the structures of the above-described embodiments, or may be replaced with arbitrary structures that exhibit the same function. [Example]

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. ＜Powder composition＞ 1. Preparation of each ingredient [polymer particles] Particles of F polymer 1: Particles (D50: 2.0 μm) comprising the following polymer (melting temperature: 300° C.) containing 97.9 mol % of TFE units, 0.1 mol % of NAH units, and 2.0 mol % % of PPVE units with polar functional groups Particles of F polymer 2: particles (D50: 2.6 μm) comprising the following polymer (melting temperature: 300° C.) which contains 97.5 mol % of TFE units and 2.5 mol % of PPVE units and has no polarity functional group [Particles of Inorganic Matter (Inorganic Particles)] Particles of Silica 1: Spherical particles containing silica (D50: 0.03 μm) Particles of boron nitride 1: scaly particles containing boron nitride (D50: 7.0 μm) [Particles of specific resin] Particle 1 of Specific Resin: 60 mol % of 2-hydroxy-6-naphthoic acid, 20 mol % of 4,4'-dihydroxybiphenyl, 15.5 mol % of terephthalic acid, and 2,6-naphthalene diphenyl The ratio of 4.5 mol% of carboxylic acid to react to obtain thermoplastic polymer, powder obtained by pulverizing the polymer (D50: 16 μm)

2. Production of composite particles (Manufacturing example 1) First, a mixture of 98 parts by mass of particles of the F polymer 1 and 2 parts by mass of the silica particles 1 was prepared. Then, the mixture is put into a powder processing device (Hybridization System), which uses a stirring blade rotating at a high speed in a cylindrical container to agitate the particles while sandwiching the particles between the inner wall of the container and the stirring body. while applying stress. Then, the particles of the F polymer 1 and the silica particles 1 are suspended in a high-temperature turbulent gas atmosphere, and the particles are collided with each other, and stress is applied between the particles to perform a composite treatment. In addition, the inside of the apparatus in process was set as nitrogen atmosphere, the temperature was kept below 100 degreeC, and the process time was made into 15 minutes. The obtained treated product was a fine powder. In addition, the powder was analyzed with an optical microscope. As a result, it was a composite particle α of a core-shell structure, with the F polymer 1 as a core, and silica particles 1 adhered to the surface of the core to form a shell. In addition, the shape of the composite particle α was spherical, and the D50 thereof was 4 μm.

(Manufacturing example 2) In a tank equipped with a stirring blade, N-methyl-2-pyrrolidone and particles of F polymer 1 (98 parts by mass) were added and stirred for 10 minutes to prepare a liquid composition in which particles of F polymer 1 were dispersed . Then, silicon dioxide particles 1 (2 parts by mass) were put in, stirred at 800 rpm for 15 minutes in the tank, and sheared while forming an upflow to obtain a dispersion. Next, N-methyl-2-pyrrolidone was removed from the dispersion, and the fine powder was recovered. Further, the powder was analyzed with an optical microscope, and it was found that it was a composite particle β of a core-shell structure, with the F polymer 1 as a core, and silica particles 1 adhered to the surface of the core to form a shell. The D50 of the composite particle β was 10 μm.

(Production Example 3) Composite particles γ were obtained in the same manner as in Example 1, except that the particles of the F polymer 1 were changed to the particles of the F polymer 2 . The D50 of the composite particle γ was 6 μm.

3. Preparation of powder composition (Powder Compositions 1 to 3) 70 parts by mass of each of the composite particles α to γ and 30 parts by mass of the boron nitride particle 1 were mixed using a Henschel mixer to prepare powder compositions 1 to 3. (Powder Composition 4) Powder composition 4 was prepared by mixing 70 parts by mass of composite particles α, 15 parts by mass of particles 1 of boron nitride, and 15 parts by mass of particles of F polymer 2 using a Henschel mixer. (Powder Composition 5) Powder composition 5 was prepared by mixing 68.6 parts by mass of particles of F polymer 1, 1.4 parts by mass of silicon dioxide particles 1, and 30 parts by mass of particles 1 of boron nitride using a Henschel mixer. (Powder Compositions 6 to 8) Using a Henschel mixer, 70 parts by mass of each composite particle α to γ and 30 parts by mass of the specific resin particle 1 were mixed to prepare powder compositions 6 to 8. (Powder Composition 9) Powder composition 9 was prepared by mixing 70 parts by mass of composite particles α, 15 parts by mass of specific resin particles 1, and 15 parts by mass of particles of F polymer 2 using a Henschel mixer. (Powder Composition 10) Powder composition 10 was prepared by mixing 68.6 parts by mass of particles of F polymer 1, 1.4 parts by mass of silica particles 1, and 30 parts by mass of specific resin particles 1 using a Henschel mixer.

4. Determination of Linear Expansion Coefficient The powder compositions 1 to 5 were melt-kneaded in a twin-screw extruder (manufactured by Technovel, "KZW15TW-45MG"), and then ejected from a T-die to prepare films (thickness: 100 μm) 1 to 5 . From the obtained film, square test pieces of 180 mm square were cut out. Next, according to the measurement method prescribed|regulated by JIS C 6471:1995, the linear expansion coefficient of the test piece in the range of 25 degreeC or more and 260 degrees C or less was measured. [Evaluation benchmarks] 〇: 30 ppm/°C or less. Δ: More than 30 ppm/°C and 50 ppm/°C or less. ×: Exceeds 50 ppm/°C. As a result, the films 1, 2 and 4 were "0", the film 3 was "Δ", and the film 5 was "x".

5. Evaluation of dimensional stability Each powder composition 6-10 was melt-kneaded in a twin-screw extruder (manufactured by Technovel, "KZW15TW-45MG"), and then ejected from a T-die to prepare films (thickness: 100 μm) 6-10 . The dimensional change rate of the obtained film before and after retention was measured as follows, and evaluated according to the following criteria. Furthermore, the evaluation of the dimensional stability of the film is based on JIS C 6481:1996. From the obtained film, a 30 cm square sample was cut out. A line segment with a length of 25 cm was drawn on the surface of the sample to form punching holes centered on both ends of the line segment.

The sample was heated at 150°C for 30 minutes and then cooled to 25°C. The distance between the centers of the two punching holes before and after the heat treatment was measured, and the absolute value of the stretch ratio of the film during the heat treatment was used as the dimensional change rate. [Evaluation benchmarks] 〇: The dimensional change rate is less than 1.5% △: Dimensional change rate of 1.5 or more and 2% or less ×: The dimensional change rate exceeds 2% As a result, the films 6, 7 and 9 were "0", the film 8 was "Δ", and the film 10 was "x".

<Composite particle containing F polymer and aromatic polymer> [F powder] F powder 1: particle (average particle diameter 2 μm, bulk density 0.18 g/m ² ) containing the following polymer (melting temperature 300° C.) , the polymer contains 97.9 mol % of TFE units, 0.1 mol % of NAH units and 2.0 mol % of PPVE units and has an acid anhydride group F powder Particle size 2 μm, bulk density 0.19 g/m ² ), the polymer contains 97.5 mol % of TFE units and 2.5 mol % of NAH units and has no functional group F Powder 3: Particles containing non-thermal fusible PTFE (average particle size: 0.3 μm, bulk density: 0.2 g/m ² ) [Aromatic polymer] Aromatic powder 1: 60 mol% of 2-hydroxy-6-naphthoic acid, 4,4'-dihydroxy 20 mol % of benzene, 15.5 mol % of terephthalic acid, and 4.5 mol % of 2,6-naphthalenedicarboxylic acid were reacted to obtain an aromatic polymer 1 (aromatic ring content: 69 mass %) ), the powder obtained by pulverizing the aromatic polymer 1 (D50: 20 μm). Aromatic powder 2: Powder (D50: 18 μm) of aromatic polymer 2 (aromatic ring content: 40% by mass) [Inorganic particles] Inorganic particles 1: Contains silica surface-treated with a silane coupling agent spherical particles (D50: 0.03 μm) [Dispersion medium] NMP: N-methyl-2-pyrrolidone

[Example 1-1] 1. Manufacture of composite particles A mixture of 99 parts by mass of F powder 1 and 1 part by mass of aromatic powder 1 was prepared. Next, the mixture is put into a powder processing apparatus (mechanical fusion apparatus) equipped with a cylindrical rotating body having a receiving surface on its inner peripheral surface, and internals arranged at a slight distance from the receiving surface. Then, the cylindrical rotating body is rotated at a high speed around the central axis. With 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 part, so that the particles collide in a sheared state for processing. The obtained treated product was a fine powder. In addition, when this powder was analyzed with an optical microscope, it was found that the F powder 1 was used as a parent particle and the composite particle 1 of the aromatic powder 1 adhered to the surface of the parent particle. The D50 of the composite particle 1 was 25 μm.

2. Manufacturing and evaluation of dispersions In a tank equipped with a stirring blade, 150 parts by mass of NMP was added, and the inside of the tank was sufficiently stirred. Next, 100 parts by mass of the obtained composite particles 1 were added to the tank, and the mixture was stirred for 10 minutes to obtain a dispersion liquid 1 in which the composite particles 1 were dispersed. The viscosity of the obtained dispersion liquid 1 was 12000 mPa·s. The state immediately after the preparation of the dispersion liquid 1 and the state after storage at 25° C. in a container for 3 hours were visually confirmed, and the dispersion stability was evaluated according to the following criteria. <Evaluation Criteria for Dispersion Stability> 〇: There is little foaming immediately after preparation and storage, no aggregates are seen, and uniform dispersion is observed △: Some aggregates were observed immediately after preparation and after storage ×: A lot of aggregates are seen, and the dispersion is not uniform

3. Fabrication and evaluation of laminates On the surface of the long copper foil (thickness 18 micrometers), the dispersion liquid 1 was apply|coated using the bar coater, and the wet film was formed. Next, the metal foil on which the wet film was formed was passed through a drying furnace at 110° C. for 5 minutes, and dried by heating to obtain a dry film. The dry film was then heated at 380°C for 3 minutes in a nitrogen oven. Thereby, the laminated body 1 which has a metal foil and the polymer layer (thickness 20 micrometers) on the surface which consists of the melt-fired product of the F powder 1 and the molded object of the aromatic polymer 1 was produced. Cut out a square test piece of 180 mm square from the laminated body 1, and measure the linear expansion coefficient of the test piece in the range of 25°C to 260°C according to the measurement method specified in JIS C 6471:1995. The following benchmarks are evaluated. <Evaluation Criteria for Coefficient of Linear Expansion> 〇: Linear expansion coefficient is 50 ppm/°C or less △: Linear expansion coefficient exceeds 50 ppm/°C and is 75 ppm/°C or less ×: Linear expansion coefficient exceeds 75 ppm/°C

[Example 1-2 to Example 1-6] Except having changed the kind and amount of each component as shown in Table 1 below, composite particles 2 to 6 and dispersion liquids 2 to 6 were obtained in the same manner as in Example 1-1, and laminated bodies 2 to 6 were produced. Table 1 shows the evaluation results of the obtained dispersion liquid and layered body.

[Table 1] example 1-1 1-2 1-3 1-4 1-5 1-6 Dispersion No. 1 2 3 4 5 6 Composition of the dispersion Composite particles (F powder) F powder 1 (parts by mass) 99 98 1 99 F powder 2 (parts by mass) 99 F powder 3 (parts by mass) 99 Composite particles (aromatic polymers) Aromatic powder 1 (mass part) 1 1 1 99 1 Aromatic powder 2 (parts by mass) 1 Composite particles (inorganic particles) Inorganic particles 1 (parts by mass) 1 dispersion medium NMP (parts by mass) 150 150 150 150 150 150 Dispersion Evaluation Dispersion stability 〇 〇 △ 〇 × × Viscosity (25℃) (mPa s) 14000 12000 16000 14000 80000 85000 Laminate Evaluation Linear expansion coefficient 〇 〇 △ 〇 × × [Industrial Availability]

The powder composition of the present invention can be used to produce a molded product having physical properties based on the following components: F polymer, inorganic substances and inorganic particles, and at least one resin selected from the group consisting of fluorine-based resins and aromatic-based resins. particle. The powder molded product of the present invention can be used as films, antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, paints, cosmetics, etc. Aircraft wires, etc.), electrical insulating tapes, insulating tapes for oil drilling, 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, automotive instrument panels, home appliances, etc., sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belts) Conveyors, conveyor belts for food conveying, etc.), tools (shovels, files, cones, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, mold nozzles, toilets, container covering materials. In addition, the composite particles of the present invention comprising the specific tetrafluoroethylene-based polymer and the specific aromatic polymer have excellent dispersion stability, and can be easily processed into films, fiber-reinforced films, prepregs, Metal laminate (metal foil with resin). The obtained processed articles can be used as materials for antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry supplies, sliding bearings, and the like. In addition, the composite particles can be effectively used as additives and modifiers for various varnishes (resist, ink, paint, etc.).

Claims (15)

A powder composition comprising: composite particles containing a heat-fusible tetrafluoroethylene-based polymer and an inorganic substance; and at least one of resin particles and inorganic particles, wherein the resin system of the resin particles is selected from fluorine-based resins and aromatics At least one of the group consisting of family resins. The powder composition according to claim 1, wherein the tetrafluoroethylene-based polymer is selected from the group consisting of a tetrafluoroethylene-based polymer containing a perfluoro(alkyl vinyl ether)-based unit and having a polar functional group, and a All units contain 2.0 to 5.0 mol % of perfluoro(alkyl vinyl ether)-based units and at least one of the group consisting of tetrafluoroethylene-based polymers having no polar functional group. The powder composition according to any one of claim 1 or 2, wherein the inorganic substance is silicon dioxide. The powder composition according to any one of claims 1 to 3, wherein at least a part of the surface of the inorganic substance is surface-treated with a silane coupling agent. The powder composition according to any one of claims 1 to 4, wherein the composite particles are composite particles having the tetrafluoroethylene-based polymer as a core and the inorganic substance on the surface of the core. The powder composition according to any one of claims 1 to 5, wherein the average particle size of the composite particles is 1-30 μm. The powder composition according to any one of claims 1 to 6, wherein in the composite particles, the inorganic substance is in the form of particles and spherical or scaly. The powder composition according to any one of claims 1 to 7, wherein in the composite particles, the tetrafluoroethylene-based polymer and the inorganic substance are each in the form of particles. The powder composition according to any one of claims 1 to 8, comprising the inorganic particles, and the inorganic particles contain at least one selected from the group consisting of silicon dioxide particles and boron nitride particles. The powder composition according to any one of claims 1 to 9, comprising particles of the at least one resin, and the at least one resin is selected from the group consisting of polyimide, polyimide, polyester, polyester At least one aromatic resin in the group consisting of amide, polyphenylene ether, polyphenylene sulfide, maleimide resin and epoxy resin. The powder composition according to any one of claims 1 to 10, comprising particles of the at least one resin, and the at least one resin is polytetrafluoroethylene or a hot-melt tetrafluoroethylene-based polymer. A composite particle comprising a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an aromatic polymer having an aromatic ring content of 45% by mass or more. The composite particle according to claim 12, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a unit based on perfluoro(alkyl vinyl ether) and having a polar functional group, or contains 2.0 per unit of the tetrafluoroethylene-based polymer. -5.0 mol % of a tetrafluoroethylene-based polymer based on perfluoro(alkyl vinyl ether) units and having no polar functional groups. The composite particle according to claim 12, wherein the aromatic polymer is a liquid crystal polyester. The composite particle according to any one of claims 12 to 14, wherein the above-mentioned tetrafluoroethylene-based polymer is used as a parent particle, and the surface of the above-mentioned parent particle has the above-mentioned aromatic polymer.