Composite compound for low-dielectric-loss resin composition, low-dielectric-loss resin composition, molded article for high-frequency device, and high-frequency device

Abstract

Provided are: a novel composite compound for a low-dielectric-loss resin composition, which suppresses the loss coefficient in a high-frequency band and has good dielectric loss; a low-dielectric-loss resin composition; a molded article for a high-frequency device; and a high-frequency device. This composite compound for a low-dielectric-loss resin composition is a composite compound for a low-dielectric-loss resin composition, and is characterized by containing a base material containing an inorganic fluoride and particles of a fluororesin held on at least a part of the surface of the base material, the dielectric loss tangent of the particles of the fluororesin is 0.002 or less at a frequency of 1 GHz or more and a temperature of 25 DEG C.

Description

Technical Field

[0001] The present invention relates to a composite compound for a low dielectric loss resin composition, a low dielectric loss resin composition, a molded article for a high-frequency device, and a high-frequency device that can be used in electronic components such as circuit boards, information communication devices, and the like. Background Art

[0002] In recent years, in electronic components such as printed wiring boards, flexible circuit boards, and high-frequency boards, and information communication equipment, the frequency of electrical signals used has been increasing in order to achieve high-speed and large-capacity data communications.

[0003] In particular, in electronic components used for high-frequency applications, as the frequency increases, the attenuation of electrical signals increases due to transmission loss in the transmission path, and transmission reliability may decrease. Therefore, materials with low loss coefficient values ​​are required in high-frequency devices and their components. Here, the loss coefficient is expressed by the relative dielectric constant (ε r ) is equal to the square root of the dielectric loss tangent (tan d ) values.

[0004] For example, Patent Document 1 discloses a thermosetting resin composition, which, in order to achieve a low relative dielectric constant and low dielectric loss tangent for a multilayer printed circuit board, contains as essential components (A) a polyimide resin having a linear hydrocarbon structure with a number-average molecular weight of 300 to 6000 and containing carboxyl or acid anhydride groups, (B) an epoxy resin, (C) an organic solvent with a boiling point of 100°C or higher, and spherical silica. Patent Document 1 enables the formation of an interlayer insulating resin layer that exhibits sufficient adhesion to a conductor, high heat resistance, flame retardancy, a low dielectric constant, a low dielectric loss tangent, and low water absorption.

[0005] Patent Document 2 also discloses an inorganic filler that has been surface-modified by sequentially introducing an alkyl group and then an amine group, which exhibits excellent compatibility and reactivity with epoxy resins. According to Patent Document 2, using this surface-modified inorganic filler, such as silica, in the production of an epoxy resin composition can impart low dielectric loss properties.

[0006] Patent Document 3 also discloses a surface-treated metal oxide particulate material comprising metal oxide particulate material such as silicon dioxide and a polyorganosiloxane compound that has been surface-treated on the metal oxide particulate material. According to Patent Document 3, by incorporating the surface-treated metal oxide particulate material into a resin material, the viscosity of the resulting resin composition can be suppressed, and the relative dielectric constant and dielectric loss tangent of the resin composition can be suppressed.

[0007] However, the resin compositions disclosed in Patent Documents 1 to 3 still have large relative dielectric constants and dielectric loss tangents in the high frequency band, and therefore further reduction in dielectric loss has been desired.

[0008] Prior art literature Patent Literature Patent Document 1: Japanese Patent No. 5564012 Patent Document 2: Japanese Patent Application Laid-Open No. 2015-67534 Patent Document 3: Japanese Patent Application Laid-Open No. 2020-66678 Summary of the Invention

[0009] Technical problem to be solved by the invention An object of the present invention is to provide a composite compound for a novel low-dielectric-loss resin composition, a low-dielectric-loss resin composition, a molded article for a high-frequency device, and a high-frequency device, which have low relative permittivity and dielectric loss tangent in a high-frequency band and are excellent in reducing dielectric loss.

[0010] Technical solutions to technical problems In order to solve the above-mentioned technical problems, the composite compound for a low dielectric loss resin composition of the present invention is a composite compound for a low dielectric loss resin composition, characterized in that it comprises a base material containing an inorganic fluoride and fluororesin particles retained on at least a portion of the surface of the base material, wherein the fluororesin particles have a dielectric loss tangent of 0.002 or less at a frequency of 1 GHz or higher and a temperature of 25°C.

[0011] In the above configuration, the fluororesin particles are preferably held on the surface of the base material containing the inorganic fluoride by thermal fusion.

[0012] Furthermore, in the above configuration, it is preferred that the fluororesin be polytetrafluoroethylene.

[0013] In addition, in the above-mentioned structure, the inorganic fluoride is preferably MFn (wherein, M is at least one selected from Li, Na, K, Mg, Al, Ca, Sc, Mn, Fe, Ga, Rb, Sr, Y, Zr, Sn, Ba, La, Ce, Yb, Hf and Bi, and n represents an integer of 1 to 4) or K2SiF6.

[0014] Furthermore, in the above-mentioned configuration, it is preferred that the inorganic fluoride is AlF 3 .

[0015] In the above configuration, it is preferred that the average particle size D50 of the matrix material containing inorganic fluoride is 0.05 m m and above and 75 m m or less.

[0016] In the above configuration, the content of the fluororesin particles is preferably 0.5% by mass or more and less than 26% by mass relative to the total mass of the base material containing the inorganic fluoride.

[0017] In order to solve the above-mentioned technical problems, the low dielectric loss resin composition of the present invention is characterized by comprising at least a polymer resin and the composite compound for the low dielectric loss resin composition.

[0018] In the above configuration, the content of the composite compound is preferably 1% by mass or more and 85% by mass or less relative to the total mass of the low dielectric loss resin composition.

[0019] Furthermore, in the above configuration, it is preferred that the polymer resin include at least one thermoplastic resin and / or at least one thermosetting resin.

[0020] Furthermore, in the above-mentioned configuration, the polymer resin is preferably at least one selected from olefin resins, styrene resins, polyvinyl resins, methacrylic resins, thermoplastic elastomer resins, thermoplastic polyurethane resins, polyacrylonitrile resins, polylactic acid resins, polyamide polyacetal resins, polycarbonate resins, polyphenylene ether resins, polyethylene terephthalate resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyetheretherketone resins, liquid crystal polymer resins, polyimide resins, fluororesins, phenolic resins, amine resins, furan resins, unsaturated polyester resins, epoxy resins, diallyl phthalate resins, guanamine resins, ketone resins, silicone resins, thermosetting elastomer resins, natural rubber, synthetic rubber, and modified products thereof.

[0021] In order to solve the above-mentioned technical problems, the molded article for high-frequency devices of the present invention is a molded article for high-frequency devices used in a frequency band of 1 GHz or higher, characterized by comprising a molded article containing the above-mentioned low dielectric loss resin composition.

[0022] In order to solve the above-mentioned technical problems, the high-frequency device of the present invention is a high-frequency device used in a frequency band of 1 GHz or higher, characterized by comprising the low dielectric loss resin composition.

[0023] Furthermore, in order to solve the above-mentioned technical problems, a high-frequency device of the present invention is a high-frequency device used in a frequency band of 1 GHz or higher, and is characterized by including the above-mentioned molded article for a high-frequency device.

[0024] Effects of the Invention According to the present invention, a composite compound containing fluororesin particles on at least a portion of the surface of an inorganic fluoride as a matrix material can be contained in a low dielectric loss resin composition to replace conventional inorganic fillers such as silicon dioxide. Thus, in the present invention, the loss factor in the high frequency band can be reduced, achieving a reduction in dielectric loss. In addition, by using the low dielectric loss resin composition containing the composite compound for a molded body or high-frequency device for high-frequency equipment, even when used in a high frequency band above 1 GHz, the attenuation of the electrical signal caused by transmission loss can be suppressed, achieving high-speed high-frequency transmission. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 (a) is to convert the α -SEM image of AlF3 and PTFE particles mixed, Figure 1 (b) is PTFE particles heat-fused to α -SEM image of the surface of the composite compound of AlF3.

[0026] Figure 2 (a) is to convert the α -SEM image of AlF3 and PTFE particles mixed, Figure 2 (b) is PTFE particles heat-fused to α -SEM image of the surface of the composite compound of AlF3.

[0027] Figure 3 (a) is to convert the α -SEM image of AlF3 and PTFE particles mixed, Figure 3 (b) is PTFE particles heat-fused to α -SEM image of the surface of the composite compound of AlF3.

[0028] Figure 4 (a) is a SEM image of the mixture of CaF2 and PTFE particles of Example 6. Figure 4 (b) is a SEM image of a composite compound in which PTFE particles are thermally fused to the surface of CaF2.

[0029] Figure 5 (a) is to convert the α -SEM image of AlF3 and PTFE particles mixed, Figure 5 (b) is PTFE particles heat-fused to α -SEM image of the surface of the composite compound of AlF3.

[0030] Figure 6 (a) is a SEM image of a mixture of silica and PTFE particles of Comparative Example 4. Figure 6(b) is a SEM image of a composite containing silica and PTFE particles.

[0031] Figure 7 (a) is a reference photograph showing a slurry composition falling smoothly. Figure 7 (b) is a reference photograph showing a state where the slurry composition falls together. DETAILED DESCRIPTION

[0032] (Compound compound for low dielectric loss resin composition) First, the composite compound for the low dielectric loss resin composition according to the present embodiment (hereinafter referred to as “composite compound”) will be described below.

[0033] The composite compound of this embodiment includes a base material containing an inorganic fluoride (hereinafter sometimes referred to as the "base material") and fluororesin particles (hereinafter sometimes referred to as the "fluororesin particles") retained on at least a portion of the base material surface. Here, in this specification, the fluororesin particles being "retained" on at least a portion of the base material surface means that, in addition to the case where the fluororesin particles are chemically bonded to the base material surface and retained (immobilized), it also includes the case where the fluororesin particles are thermally fused to the base material surface by thermal melting, thereby being physically retained (immobilized). In this embodiment, the composite compound preferably has a method in which the fluororesin particles are retained on the base material surface by thermal melting. In addition, in this specification, "thermal melting" refers to a state in which fluororesin particles, at least the surface of which has been thermally melted by heating, come into contact with a base material containing an inorganic fluoride, and the fluororesin particles are fixed to the base material at their contact surface. It should be noted that the melting point of fluororesin is generally lower than that of inorganic fluoride.

[0034] In the present invention, by keeping fluororesin particles on the surface of a matrix containing an inorganic fluoride, the relative dielectric constant and dielectric loss tangent in the high frequency band can be reduced, thereby reducing dielectric loss, compared to the case where only inorganic fluorides are contained in the low dielectric loss resin composition. Generally, inorganic fluorides have larger relative dielectric constants and dielectric loss tangents in the high frequency band than silica. Therefore, it is also considered to use silica as a matrix and keep fluororesin on its surface. However, it is found that in this case, even if the relative dielectric constant can be reduced, the dielectric loss tangent cannot be reduced. It is also found that due to poor affinity with polymer resins, it is difficult to obtain a low dielectric loss resin composition uniformly dispersed in the polymer resin. It is further found that when such a low dielectric loss resin composition is used as a material for electronic components, for example, when it comes into contact with an alkaline solution through alkali etching, silica dissolves, and the chemical (alkali) resistance is also poor.

[0035] On the other hand, in the present invention, inorganic fluoride is adopted as matrix from a plurality of inorganic fillers, and then fluororesin is used in combination from a plurality of macromolecular resins as the macromolecular resin retained on the matrix surface. Found: thus, in the present invention, compared with the situation of using silicon dioxide alone, the situation of retaining fluororesin on the surface of the silicon dioxide, the relative dielectric constant and dielectric loss tangent in the high frequency band can be reduced. In addition, find: the affinity with macromolecular resin is also good, so the resin combination of the composite compound uniform dispersion can be obtained, and the chemical resistance is also excellent.

[0036] Relative dielectric constant ε of composite compounds r0 The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less at a frequency of 1 GHz or more and a temperature of 25°C. r0 When the coefficient of dielectric loss is 6 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0037] In addition, the dielectric loss tangent tan of the composite compound d The upper limit of 0[-] is preferably 0.01 or less, more preferably 0.005 or less, further preferably 0.002 or less, and particularly preferably 0.001 or less at a frequency of 1 GHz or more and a temperature of 25°C. d When 0 is 0.01 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0038] The upper limit of the loss factor of the composite compound is preferably less than 6, more preferably 4 or less, and particularly preferably 3 or less. When the loss factor is less than 6, the loss factor of the composite compound can be reduced, thereby reducing dielectric loss.

[0039] It should be noted that the relative dielectric constant ε used for quantifying dielectric properties and dielectric loss is r0 and dielectric loss tangent tan d Each numerical value of 0 is a numerical value based on the value obtained by measuring the composite compound. The measurement method can be selected appropriately. Specifically, for example, it can be measured by the method described in the Examples described below.

[0040] The loss factor can be calculated using the relative dielectric constant ε of the composite compound. r0 and dielectric loss tangent tan d The measured value of 0 was calculated based on the following formula.

[0041] (Loss coefficient) = (ε r0 ) 1 / 2 ×tan d 0×10 3 (where ε r0 [-] represents the relative dielectric constant of the composite compound obtained by measurement, tan d 0[-] indicates its dielectric loss tangent.) Relative dielectric constant ε r0 It is a parameter that indicates the degree of polarization of the composite compound obtained by measurement. The higher the relative dielectric constant, the greater the propagation delay of the electrical signal. Therefore, in order to increase the propagation speed of the signal, it is preferable to have a low relative dielectric constant. Dielectric loss tangent tan d 0 is a parameter that indicates the amount of signal loss due to conversion to heat within the composite compound, as measured. Therefore, the lower the dielectric loss tangent, the less signal loss and the higher the signal transmission efficiency.

[0042] <Inorganic fluorides> Next, the inorganic fluoride-containing matrix material of this embodiment will be described. The matrix material of this embodiment is preferably a powdered solid particle. Preferred inorganic fluorides include MFn (wherein M is at least one selected from Li, Na, K, Mg, Al, Ca, Sc, Mn, Fe, Ga, Rb, Sr, Y, Zr, Sn, Ba, La, Ce, Yb, Hf, and Bi, and n is an integer from 1 to 4) or K2SiF6 (potassium fluorosilicate). More specifically, examples of the inorganic fluoride include LiF (lithium fluoride), NaF (sodium fluoride), KF (potassium fluoride), MgF2 (magnesium fluoride), AlF3 (aluminum fluoride), CaF2 (calcium fluoride), ScF3 (scandium fluoride), MnF2 (manganese fluoride), FeF3 (ferric fluoride), GaF3 (gallium fluoride), RbF (rubidium fluoride), SrF2 (strontium fluoride), YF3 (yttrium fluoride), ZrF4 (zirconium fluoride), SnF2 (tin fluoride), BaF2 (barium fluoride), LaF3 (lanthanum fluoride), CeF3 (cerium fluoride), YbF2 (ytterbium difluoride), YbF3 (ytterbium trifluoride), HfF4 (hafnium fluoride), and BiF3 (bismuth fluoride).

[0043] Among the inorganic fluorides exemplified, aluminum fluoride, calcium fluoride and magnesium fluoride are preferred from the viewpoint of reducing the dielectric loss of the composite compound, and aluminum fluoride is more preferred. α Aluminum fluoride with a phase of crystalline aluminum fluoride as the main component. α Crystalline aluminum fluoride exhibits excellent low dielectric loss characteristics in high-frequency bands above 1 GHz. Therefore, by using aluminum fluoride containing this aluminum fluoride as a main component as a matrix material for a low-dielectric-loss resin composition, it is possible to achieve a significant effect of reducing the dielectric loss of the low-dielectric-loss resin composition.

[0044] The X-ray diffraction pattern of aluminum fluorideα The half-peak width of the peak of the (012) plane of the phase is less than 0.3°, preferably less than 0.25°, and more preferably 0.2°. Generally, as the average particle size of the inorganic compound particles decreases, the proportion of the surface layer in the entire particle increases. The energy state of the particle surface is higher than that of the interior, so the structural order is easily disordered and the crystallinity is reduced. Therefore, the physical and chemical properties from the bulk change from the original properties, and the dielectric loss tangent is likely to become larger on the particle surface. Therefore, regardless of the average particle size of the inorganic compound, high crystallinity is preferred. Here, in the case of this embodiment, the degree of crystallinity can be evaluated by the half-peak width of the X-ray diffraction peak from the (012) plane of aluminum fluoride. Generally, the smaller the half-peak width, the higher the crystallinity, the smaller the fluctuation of the crystal structure, and therefore the dielectric loss tangent also becomes smaller. Therefore, in the case of aluminum fluoride, by reducing the half-peak width of the peak of the (012) plane in the X-ray diffraction pattern, its crystallinity can also be improved. From this viewpoint, in this embodiment, by setting the upper limit of the half-value width to 0.3° or less, the crystallinity of aluminum fluoride can be suppressed from becoming too high, and the increase in the dielectric loss tangent can be suppressed, resulting in a lower dissipation factor and a lower dielectric loss.

[0045] In addition, the lower limit of the half-peak width is preferably more than 0.12 °, more preferably more than 0.15 °. By making the lower limit of the half-peak width be more than 0.12 °, when amorphous aluminum fluoride is crystallized or during crystal growth, it is possible to prevent excessive growth of crystal grains and make the particle diameter of crystal grains become too large. Thus, it is possible to prevent the average particle diameter D50 of aluminum fluoride from becoming large, and the crystallinity of aluminum fluoride is suppressed to become too high. As a result, when the composite compound of the present embodiment is applied to low dielectric loss resin composition and film-like or sheet-like molded products are made, even if the electronic components such as printed wiring substrate, flexible circuit substrate and high-frequency substrate of thin layer are used, it is also possible to reduce or suppress the concavo-convex on the surface, prevent the reduction of electrical characteristics. In addition, it is possible to manufacture the film-like or sheet-like molded products fully suppressing film thickness.

[0046] Here, in this specification, "half-maximum width" means the full width at half-maximum. In addition, "X-ray diffraction pattern" means a curve of diffraction intensity measured at each incident angle in a two-dimensional coordinate diagram with incident angle as the horizontal axis and diffraction intensity as the vertical axis when performing sample measurement based on X-ray diffraction (powder). "X-ray diffraction pattern of aluminum fluoride α The (012) plane of the phase is the orientation plane of the aluminum fluoride crystal and refers to the X-ray diffraction pattern. α It should be noted that the (012) surface of aluminum fluoride α The peak of the diffraction intensity of the (012) plane of the phase is located at 2 i It is around 25.3°.

[0047] Relative dielectric constant ε of inorganic fluoride particles r1 The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less at a frequency of 1 GHz or more and a temperature of 25°C. r1 When the coefficient of dielectric loss is 6 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0048] In addition, the dielectric loss tangent tan of inorganic fluoride particles d The upper limit of 1[-] is preferably 0.008 or less, more preferably 0.005 or less, further preferably 0.002 or less, and particularly preferably 0.001 or less at a frequency of 1 GHz or more and a temperature of 25°C. d When 1 is 0.008 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0049] The upper limit of the loss factor of the inorganic fluoride particles is preferably less than 6, more preferably 4 or less, and even more preferably 3 or less. If the loss factor is less than 6, the loss factor of the low dielectric loss resin composition can be reduced, thereby reducing dielectric loss.

[0050] It should be noted that the relative dielectric constant ε used for quantifying dielectric properties and dielectric loss is r1 and dielectric loss tangent tan d Each numerical value of 1 is a numerical value obtained by measuring the inorganic fluoride particles including the powder. The measurement method can be selected appropriately. Specifically, for example, the measurement can be performed by the method described in the Examples below.

[0051] The loss factor can be calculated using the relative dielectric constant ε of the inorganic fluoride particles comprising the powder. r1 and dielectric loss tangent tan d The measured value of 1 was calculated based on the following formula.

[0052] (Loss coefficient) = (ε r1 ) 1 / 2 ×tan d 1×10 3 (where ε r1 [-] represents the relative dielectric constant of the inorganic fluoride particles including the powder obtained by measurement, tan d 1[-] represents its dielectric loss tangent.) Relative dielectric constant ε r1It is a parameter that indicates the degree of polarization of inorganic fluoride particles obtained by measurement. The higher the relative dielectric constant, the greater the propagation delay of the electrical signal. Therefore, in order to increase the propagation speed of the signal, it is preferred to have a low relative dielectric constant. Dielectric loss tangent tan d 1 is a parameter indicating the amount of signal loss due to conversion to heat within the inorganic fluoride particles, as measured. Therefore, the lower the dielectric loss tangent, the less signal loss and the higher the signal transmission efficiency.

[0053] The average particle size D50 of the inorganic fluoride particles (the particle size at which the cumulative particle size in the volume-based cumulative particle size distribution is 50%) is not particularly limited. For example, it can be appropriately set based on the size, thickness, and other shapes of the molded article containing the low dielectric loss resin composition, the adjustment of the fluidity of the material containing the inorganic fluoride particles in the preparation of the low dielectric loss resin composition, and other reasons. Generally, the upper limit of the average particle size D50 of the inorganic fluoride particles is preferably 75 m m or less, more preferably 50 m m or less, more preferably 10 m m or less, particularly preferably 1 m On the other hand, the lower limit of the average particle size D50 of the inorganic fluoride particles is preferably 0.05 m m or more, more preferably 0.075 m m or more, more preferably 0.1 m In the embodiment of the present invention, the average particle diameter D50 of inorganic fluoride particles is too large. If the average particle diameter D50 of inorganic fluoride particles is too large, the surface of the molded product when being difficult to make to be applied to film-like or sheet-like molded product becomes flat surface. As a result, for example, when forming laminate, sometimes the electrical characteristic of laminate is damaged due to the concavo-convex on the molded product surface. On the other hand, if the average particle diameter D50 of inorganic fluoride particles is too small, when mixing composite compound in polymer resin, it is difficult to mix uniformly, and the viscosity of the mixture rises to the degree that is difficult to carry out the molding of low dielectric loss resin combination.

[0054] In addition, when the low dielectric loss resin composition of this embodiment is a film-shaped or sheet-shaped molded article, the average particle size D50 of the inorganic fluoride particles is preferably set to be less than 1 / 5 of the thickness of the molded article within the above numerical range, and more preferably set to be less than 1 / 10. For example, when the molded article of the low dielectric loss resin composition has a thickness of 20 m In the case of a film or sheet of about 10 μm, the average particle size D50 of the inorganic fluoride particles is preferably 10 m m or less, more preferably 2 m m or less, more preferably 1 mm or less.Thus, it is possible to form a film-like or sheet-like molded product under the state that the composite compound comprising inorganic fluoride particles is arranged into a monolayer.As a result, it is possible to obtain a molded product having reduced or prevented the concavo-convex surface.In addition, in the slurry composition before solidification formed by making the composite compound comprising inorganic fluoride particles dispersed in a solvent, it is possible to suppress the sedimentation of the composite compound, obtain a film-like or sheet-like molded product uniformly filled with the composite compound.

[0055] The average particle size D50 of the inorganic fluoride particles is a value measured by a laser diffraction and scattering method using, for example, Microtrac MT3300EXII (trade name: manufactured by Nikkiso Co., Ltd.).

[0056] The oxygen content of the inorganic fluoride particles is preferably 2% by mass or less, more preferably 1.5% by mass or less, and further preferably 1% by mass or less relative to the total mass of the inorganic fluoride particles. The content of oxygen-containing atom components (e.g., surface hydroxyl groups, adsorbed moisture, and oxides, fluoride oxides, etc. as impurities) contained in the inorganic fluoride particles can be reduced, and the influence on the dielectric properties can be suppressed. More specifically, by reducing the content of oxygen-containing atom components as impurities, the crystallinity of the inorganic fluoride particles can be improved. In addition, by reducing the content of fluoride oxides as oxygen-containing components, the insulation properties of the inorganic fluoride particles can also be improved. Furthermore, by reducing the hydroxyl groups and adsorbed moisture as oxygen-containing components with high polarizability, the reduction in dielectric properties can also be suppressed.

[0057] The oxygen content of the inorganic fluoride particles can be measured, for example, using an X-ray fluorescence analyzer (X-ray Fluorescence, trade name: ZSX Primus II, manufactured by Rigaku Corporation).

[0058] The shape of the inorganic fluoride particles is not particularly limited and can be appropriately selected, for example, considering the fluidity of the mixture when mixed with fluororesin particles when manufacturing the composite compound, or the fluidity of the mixture when the composite compound is mixed with a polymer resin. In addition, the shape can also be appropriately selected based on the purpose of controlling the mechanical strength, thermal conductivity, and gas diffusivity of the molded article comprising the low dielectric loss resin composition.

[0059] The shape of the inorganic fluoride particles can be, for example, spherical, roughly spherical, elliptical, rod-shaped, needle-shaped, spindle-shaped, plate-shaped or any other shape. In addition, the inorganic fluoride particles can also be hollow inorganic fluoride particles having any of these shapes and having a space therein. Furthermore, in the inorganic fluoride particles of the present embodiment, inorganic fluoride particles of the same shape can be included, or inorganic fluoride particles of two or more different shapes can be included.

[0060] In addition, in the inorganic fluoride particles of the present embodiment, for example, the mass reduction after heat treatment at 400°C or above is preferably 2% by mass or less relative to the mass of the inorganic fluoride particles before heat treatment, more preferably 1.5% by mass or less, and further preferably 1% by mass or less. By using inorganic fluoride particles having a reduction of 2% by mass or less after the above-mentioned heat treatment, it is possible to prevent the low dielectric loss characteristics and mechanical strength of the low dielectric loss resin composition caused by heat generation during polymerization of the monomers forming the polymer resin, degassing of impurities during heat treatment, and thermal decomposition of the main component of the polymer resin. In the inorganic fluoride particles, there is no particular limitation on the method for reducing the reduction after the above-mentioned heat treatment to less than 2% by mass. For example, the following method can be cited: pre-heat treatment, liquid treatment, removal or reduction of materials with high thermal decomposition temperatures contained in the inorganic fluoride particles, materials that do not undergo phase change when heated, and impurities that cause mass reduction when synthesizing the inorganic fluoride particles.

[0061] <Fluororesin particles> The fluororesin particles of the present embodiment are as long as they are retained at least a portion of the parent material surface. Under the situation of the mode that fluororesin particles are retained on a part of the parent material surface, become the state that Lewis acid site is exposed at the parent material surface that does not retain fluororesin particles. Usually, the compatibility of fluororesin and macromolecular resin is bad, but by making the part on the parent material surface not be coated by fluororesin particles, can well keep the affinity of composite compound relative to the macromolecular resin (details described later) in the low dielectric loss resin composition, suppress the dispersibility reduction in the macromolecular resin. On the other hand, under the situation of the mode that fluororesin particles are for example retained on the whole surface of parent material, the dielectric loss can be further reduced.

[0062] Fluororesin particles are not particularly limited, and examples thereof include particles containing polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluorovinyl ether copolymer (PFA), tetrafluoroethylene hexafluoropropylene copolymer (FEP), etc. Among these fluororesins, PTFE is preferred from the viewpoint of reducing dielectric loss.

[0063] The average particle size d50 of the fluororesin particles (the particle size at the 50th percentile of the cumulative particle size in the volume-based cumulative particle size distribution) is preferably within a range of 1 / 10 to 1 / 2 of the average particle size D50 of the inorganic fluoride particles. By setting the average particle size d50 of the fluororesin particles to 1 / 10 or greater relative to the average particle size D50 of the inorganic fluoride particles, the entire base material can be coated. On the other hand, by setting the average particle size d50 of the fluororesin particles to 1 / 2 or less relative to the average particle size D50 of the inorganic fluoride particles, self-fusion can be prevented.

[0064] The average particle size d50 of the fluororesin particles is a value measured by a laser diffraction and scattering method using, for example, Microtrac MT3300EXII (trade name: manufactured by Nikkiso Co., Ltd.).

[0065] The shape of the fluororesin particles before being held in the matrix is ​​not particularly limited. For example, fluororesin particles of any shape, such as spherical, substantially spherical, elliptical, rod-shaped, needle-shaped, spindle-shaped, or plate-shaped, can be used. Fluororesin particles of the same shape may be included, or particles of two or more different shapes may be included.

[0066] The content of fluororesin particles is preferably more than 0.5 mass % and less than in the scope of 26 mass % relative to the gross mass of parent material, more preferably more than 1 mass % and in the scope of below 25 mass %, further preferably more than 1 mass % and in the scope of below 15 mass %, particularly preferably more than 1 mass % and in the scope of below 10 mass %.Be more than 0.5 mass % by making the content of fluororesin particles, can maintain the good low dielectric loss characteristics of composite compound.On the other hand, by making the content of fluororesin particles be less than 26 mass %, can well keep the affinity of composite compound relative to macromolecular resin, can suppress the dispersive reduction in macromolecular resin.

[0067] Relative dielectric constant ε of fluororesin particles r2 The upper limit of [-] is preferably 3.5 or less, more preferably 3.0 or less, and further preferably 2.9 or less at a frequency of 1 GHz or more and a temperature of 25°C. r2 When the coefficient of dielectric constant is 3.5 or less, the loss factor of the composite compound and the low dielectric loss resin composition containing the composite compound can be reduced, thereby reducing the dielectric loss.

[0068] In addition, as fluororesin particles, dielectric loss tangent tan d 2[-] Fluorine resin particles having a dielectric loss tangent tan of 0.002 or less, preferably 0.001 or less, at a frequency of 1 GHz or more and a temperature of 25°C. dWhen 2 is 0.002 or less, the dielectric loss tangent of the composite compound and the low dielectric loss resin composition containing the composite compound can be reduced, thereby further reducing the dielectric loss.

[0069] The upper limit of the loss factor of the fluororesin particles is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. If the loss factor is 6 or less, the loss factors of the composite compound and the low dielectric loss resin composition can be reduced, further reducing the dielectric loss.

[0070] It should be noted that the relative dielectric constant ε used for quantifying dielectric properties and dielectric loss is r2 and dielectric loss tangent tan d Each numerical value of 2 is a numerical value obtained by measuring the fluororesin particles. The measurement method can be selected as appropriate. Specifically, for example, the measurement can be performed by the method described in the Examples below.

[0071] The relative dielectric constant ε of the fluororesin particles can be used to calculate the loss factor. r2 and dielectric loss tangent tan d The measured value of 2 was calculated based on the following formula.

[0072] (Loss coefficient) = (ε r2 ) 1 / 2 ×tan d 2×10 3 (where ε r2 [-] represents the relative dielectric constant of the fluororesin particles obtained by measurement, tan d 2[-] represents its dielectric loss tangent.) Relative dielectric constant ε r2 This parameter indicates the degree of polarization of the fluororesin particles obtained by measurement. The higher the relative dielectric constant, the greater the propagation delay of the electrical signal. Therefore, in order to increase the propagation speed of the signal, a low relative dielectric constant is preferred. Dielectric loss tangent tan d 2 is a parameter indicating the amount of heat loss due to the signal propagating inside the fluororesin particle, as measured. Therefore, the lower the dielectric loss tangent, the less signal loss there is, and the higher the signal transmission efficiency.

[0073] <Method for producing composite compound> Next, a method for producing the composite compound will be described below.

[0074] The method for producing the composite compound of this embodiment is not particularly limited, and known methods can be employed. For example, when producing a composite compound in which fluororesin particles are thermally fused to the surface of a base material, a method that includes at least a mixing step of mixing the fluororesin particles with an inorganic fluoride base material, a heating step of heating the mixture of the fluororesin particles and the inorganic fluoride base material, and a cooling step of cooling the heated mixture (compounding treatment) can be cited.

[0075] The heating method in the heating step is not particularly limited, and known methods can be used. Furthermore, the heating temperature is not particularly limited, as long as it is above the melting point and below the boiling point of the fluororesin particles, and can be appropriately set according to the type of fluororesin. Furthermore, the heating time is not particularly limited, and can be appropriately set according to the heating temperature, the type of material of the fluororesin particles, etc. The cooling method in the cooling step is not particularly limited, and can be carried out, for example, by natural cooling or quenching.

[0076] <Other> The surface of the inorganic fluoride base material of this embodiment may be chemically modified by introducing functional groups such as hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, amino groups, perfluoroalkyl groups, ether groups, and ester groups, within a range that does not impair the effects of the present invention. Furthermore, the surface of the fluororesin particles of this embodiment may be chemically modified by introducing functional groups such as hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, amino groups, perfluoroalkyl groups, ether groups, and ester groups, within a range that does not impair the effects of the present invention.

[0077] In addition, in this embodiment, the inorganic fluoride and fluororesin particles may be any combination of the materials exemplified above, and preferably, the fluororesin particles have a lower relative dielectric constant, dielectric loss tangent, and loss coefficient than the inorganic fluoride. Thus, the dielectric loss can be further reduced compared to when only an inorganic filler containing inorganic fluoride particles is used in a low dielectric loss resin composition.

[0078] (Slurry composition for low dielectric loss resin composition) Next, the slurry composition for the low dielectric loss resin composition according to the present embodiment (hereinafter referred to as “slurry composition”) will be described below.

[0079] The slurry composition of this embodiment contains at least the aforementioned composite compound and a solvent. The slurry composition is a dispersion in which the composite compound is dispersed (including suspended or turbid) in a solvent. In this specification, "dispersion" refers to a liquid in which the composite compound, as a dispersoid, is dispersed in a solvent, serving as a dispersion medium. However, "dispersion" does not include solid colloids (organogels) in which the dispersoid is dispersed in a solid dispersion medium and has lost its fluidity.

[0080] About the content of composite compound, relative to the gross mass of slurry composition, its lower limit is preferably more than 1 mass %, more preferably more than 10 mass %, more preferably more than 20 mass %.On the other hand, the upper limit of the content of composite compound is preferably less than 85 mass %, more preferably less than 82 mass %, more preferably less than 79 mass % relative to the gross mass of slurry composition.If the lower limit of the content of composite compound is more than 1 mass %, the loss factor of slurry composition becomes smaller, and the reduction of dielectric loss can be achieved.

[0081] As solvents, linear alkanes are preferred, with linear alkanes having 10 to 16 carbon atoms being more preferred. More specific examples of linear alkanes include n-decane, n-tetradecane, and n-hexadecane. These solvents can be used alone or in mixtures of two or more. Among these linear alkanes, n-hexadecane is particularly preferred because it can exist as a liquid at room temperature (e.g., 5°C to 35°C), has low polarity, and is particularly preferred from the perspective of dielectric property evaluation. It should be noted that linear alkanes with 10 or more carbon atoms have low polarity, resulting in low dielectric constants and dielectric loss tangents, and are poorly soluble in water. Furthermore, their high boiling point can suppress concentration changes due to volatilization, as occurs with hexane, which has a lower boiling point. On the other hand, linear alkanes with 16 or fewer carbon atoms have a melting point below 20°C, thus preventing the reduction in handling performance that would otherwise occur due to their solid state at room temperature. In this specification, when a range of carbon numbers is indicated, the range includes all integers of carbon numbers included in the range. Therefore, for example, a linear alkane "having 10 or more and 16 or less carbon atoms" refers to all linear alkanes having 10, 11, 12, 13, 14, 15, and 16 carbon atoms.

[0082] Regarding the content of the solvent, its lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 15% by mass or more relative to the total mass of the slurry composition. On the other hand, the upper limit of the content of the solvent is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less relative to the total mass of the slurry composition.

[0083] Relative dielectric constant ε of the slurry composition r3 The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less at a frequency of 1 GHz or more and a temperature of 25°C. r3 When the coefficient of dielectric loss is 6 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0084] In addition, the dielectric loss tangent tan of the slurry composition d The upper limit of 3[-] is preferably 0.005 or less, more preferably 0.002 or less, and particularly preferably 0.001 or less at a frequency of 1 GHz or more and a temperature of 25°C. d When 3 is 0.005 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0085] The upper limit of the loss factor of the slurry composition is preferably less than 6, more preferably 4 or less, and further preferably 3 or less. When the loss factor is less than 6, the loss factor of the slurry composition can be reduced, thereby reducing dielectric loss.

[0086] It should be noted that the relative dielectric constant ε used for quantifying dielectric properties and dielectric loss is r3 and dielectric loss tangent tan d Each numerical value of 3 is a numerical value based on the value obtained by measuring the slurry composition. The measurement method can be appropriately selected. Specifically, for example, it can be measured by the method described in the Examples below.

[0087] The loss factor can be calculated using the relative dielectric constant ε of the slurry composition. r3 and dielectric loss tangent tan d The measured value of 3 was calculated based on the following formula.

[0088] (Loss coefficient) = (ε r3 ) 1 / 2 ×tan d 3×10 3 (where ε r3 [-] represents the relative dielectric constant of the slurry composition obtained by measurement, tan d 3[-] represents its dielectric loss tangent.) Relative dielectric constant ε r3 It is a parameter that indicates the degree of polarization of the slurry composition obtained by measurement. The higher the relative dielectric constant, the greater the propagation delay of the electrical signal. Therefore, in order to increase the propagation speed of the signal, it is preferred to have a low relative dielectric constant. Dielectric loss tangent tan d 3 is a parameter indicating the amount of loss of a signal propagating inside the slurry composition due to conversion into heat, as measured. Therefore, the lower the dielectric loss tangent, the less signal loss and the higher the signal transmission efficiency.

[0089] In addition, the slurry composition of this embodiment may contain other additives within the scope that does not violate the purpose of the present invention. Other additives are not particularly limited, and examples thereof include ultraviolet light inhibitors, colorants, flame retardants, stabilizers, and dispersants. In addition, the content of other additives is not particularly limited and can be appropriately set according to the application, purpose, etc.

[0090] The method for producing the slurry composition of the present embodiment is not particularly limited, and the slurry composition of the present embodiment can be produced by adding a predetermined amount of the composite compound to a solvent and stirring the mixture for a predetermined time.

[0091] (Low dielectric loss resin composition) Next, the low dielectric loss resin composition according to the present embodiment will be described below.

[0092] The low dielectric loss resin composition of the present embodiment contains at least the above-mentioned composite compound and a polymer resin.

[0093] About the content of composite compound, its lower limit is preferably more than 1 mass % relative to the gross mass of low dielectric loss resin composition, more preferably more than 10 mass %, more preferably more than 20 mass %.On the other hand, the upper limit of the content of composite compound is preferably less than 85 mass % relative to the gross mass of low dielectric loss resin composition, more preferably less than 82 mass %, more preferably less than 79 mass %.If the lower limit of the content of composite compound is more than 1 mass %, the loss factor of low dielectric loss resin composition decreases, and the reduction of dielectric loss can be achieved.On the other hand, if the upper limit of the content of composite compound is less than 85 mass %, the deterioration of physical strength such as brittleness can be prevented, and the increase in hardness, the reduction in thermal expansion coefficient and the increase in weather resistance can be achieved.

[0094] The polymer resin preferably contains at least one thermoplastic resin and / or at least one thermosetting resin.

[0095] More specifically, examples of the polymer resin include: olefin resins such as polyethylene resin and polypropylene resin; styrene resins such as polystyrene resin and acrylonitrile butadiene styrene resin (ABS resin); polyvinyl acetate resin; polyethylene resins such as polyvinyl chloride resin, polyvinyl alcohol resin and polyvinylidene chloride resin; methacrylic resin; thermoplastic elastomer resin; thermoplastic polyurethane resin; polyacrylonitrile resin; polylactic acid resin; polyamide polyacetal resin; polycarbonate resin; polyphenylene ether resin; polyethylene terephthalate resin; polysulfone resin; polyethersulfone resin; polyphenylene sulfide resin; polyetheretherketone resin; liquid crystal polymer resin; polyimide resin Fluororesins such as polytetrafluoroethylene resin (PTFE), copolymers of polytetrafluoroethylene and perfluoroalkoxyethylene (PFA), polychlorotrifluoroethylene resin (PCTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (ETFE); phenolic resins; amine resins such as urea resin and melamine resin; furan resins; unsaturated polyester resins; epoxy resins; diallyl phthalate resins; guanamine resins; ketone resins; silicone resins; thermosetting elastomer resins; natural rubber; synthetic rubbers such as chloroprene rubber, styrene butadiene rubber, isoprene rubber, butyl rubber, and polyurethane rubber; and modified products thereof. These polymer resins can be used alone or in combination of two or more, depending on the processability and application of the low dielectric loss resin composition. For example, when a polymer resin in which an epoxy resin is mixed with a polyphenylene ether resin is used, the processability can be improved by increasing the fluidity. It should be noted that the degree of polymerization of the polymer resin is not particularly limited and can be appropriately selected according to the application of the low dielectric loss resin composition.

[0096] The content of polymer resin is preferably more than 15 mass % and below 99 mass % relative to the gross mass of low dielectric loss resin combination, more preferably more than 18 mass % and below 90 mass %, further preferably more than 21 mass % and below 80 mass %.By making the content of polymer resin be more than 15 mass %, it is possible to fully show the characteristics of the polymer resins such as adhesiveness, water resistance.On the other hand, by making the content of polymer resin be below 99 mass %, it is possible to maintain the characteristic of polymer resin, and it is possible to reduce the dielectric loss of resin combination by adding composite compound.

[0097] Relative dielectric constant ε of low dielectric loss resin composition r4 The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less at a frequency of 1 GHz or more and a temperature of 25°C. r4 When the coefficient of dielectric loss is 6 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0098] In addition, the dielectric loss tangent tan of the low dielectric loss resin composition d The upper limit of 4[-] is preferably 0.02 or less, more preferably 0.005 or less, further preferably 0.002 or less, and particularly preferably 0.001 or less at a frequency of 1 GHz or more and a temperature of 25°C. d When 4 is 0.02 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0099] The upper limit of the loss factor of the low dielectric loss resin composition is preferably less than 6, more preferably 4 or less, and particularly preferably 3 or less. If the loss factor is less than 6, the loss factor of the low dielectric loss resin composition can be reduced, thereby reducing dielectric loss.

[0100] It should be noted that the relative dielectric constant ε used for quantifying dielectric properties and dielectric loss is r4 and dielectric loss tangent tan d Each numerical value of 4 is a numerical value based on the value obtained by measuring the low dielectric loss resin composition. The measurement method can be selected appropriately. Specifically, for example, it can be measured by the method described in the Examples below.

[0101] The loss factor can be calculated using the relative dielectric constant ε of the low dielectric loss resin composition. r4 and dielectric loss tangent tan d The measured value of 4 was calculated based on the following formula.

[0102] (Loss coefficient) = (ε r4 ) 1 / 2 ×tan d 4×10 3 (where ε r4 [-] represents the relative dielectric constant of the low dielectric loss resin composition obtained by measurement, tan d 4[-] represents its dielectric loss tangent.) Relative dielectric constant ε r4 It is a parameter that indicates the degree of polarization of the low dielectric loss resin composition obtained by measurement. The higher the relative dielectric constant, the greater the propagation delay of the electrical signal. Therefore, in order to increase the propagation speed of the signal, it is preferable to have a low relative dielectric constant. Dielectric loss tangent tan d 4 is a parameter indicating the amount of heat loss due to the signal propagating through the low dielectric loss resin composition. Therefore, the lower the dielectric loss tangent, the less signal loss there is, and the higher the signal transmission efficiency.

[0103] Next, a method for producing the low dielectric loss resin composition according to this embodiment will be described below.

[0104] The low dielectric loss resin composition of this embodiment can be produced by adding the composite compound and any other additives to a polymer resin and uniformly mixing or kneading the mixture. Alternatively, the composition can be produced by adding the composite compound and any other additives to a solution (e.g., a varnish or dispersion) obtained by dissolving or dispersing the polymer resin or monomers forming the polymer resin in an organic solvent and dissolving the polymer resin in the solution (e.g., a varnish or dispersion).

[0105] The low dielectric loss resin composition of this embodiment may contain impurities within a range that does not violate the purpose of the present invention. Examples of such impurities include metal impurities containing elements other than those constituting inorganic fluorides, and metal oxides. The content of impurities is preferably 100 ppm or less, more preferably 10 ppm or less, relative to the total mass of the low dielectric loss resin composition.

[0106] In addition, in the low dielectric loss resin composition of the present embodiment, other additives may be contained within the scope not violating the purpose of the present invention. As other additives, there are no particular limitations, and for example, curing agents, lubricants, crystal nucleating agents, UV inhibitors, colorants, flame retardants, stabilizers, plasticizers, reinforcing agents and dispersants can be cited. The content of other additives is not particularly limited and can be appropriately set according to use, purpose, etc.

[0107] The low dielectric loss resin composition of this embodiment can be used as a resin composition for insulating films (solder resists), a semiconductor encapsulating resin composition, an adhesive, a coating material, a covering material for wiring for power supplies and communications, and the like.

[0108] (Molded article for high-frequency devices and method for producing the same) The molded article for high-frequency devices (hereinafter referred to as “molded article”) according to the present embodiment includes a molded article containing a low-dielectric-loss resin composition.

[0109] Molded body can for example be manufactured by using known mixing mill and extruder.As mixing mill, for example, closed pressure kneading machine, open roller can be used.After using these mixing mills to manufacture the low dielectric loss resin composition material of sheet, this low dielectric loss resin composition material can be used to manufacture molded body.In addition, after utilizing extruder to manufacture granular low dielectric loss resin composition material, injection molding machine can be used to manufacture molded body.When using forming machines such as extruder to carry out mixing of macromolecular resin and composite compound and other additives etc., the number of steps can be reduced, and production efficiency can be improved.In addition, before mixing with macromolecular resin, composite compound can be suitably carried out drying process etc.

[0110] Furthermore, when producing a sheet-like molded article, it can be produced by known methods. For example, the composite compound and any other additives are added to a varnish tank filled with a solution containing a polymer resin (resin varnish) and uniformly dispersed. The dispersion is then heated under predetermined temperature conditions. The resulting cured product is then stretched into a sheet, thereby producing a sheet-like molded article.

[0111] In addition, the sheet-like substrates such as glass cloth and bonding sheet are passed through the liquid tank of the dispersion liquid comprising macromolecular resin, composite compound and other additives arbitrarily in the state of impregnation, so that the dispersion liquid is impregnated in the sheet-like substrate. Then, the sheet material impregnated with the dispersion liquid can be subjected to drying treatment to manufacture the impregnation sheet material impregnated with the low dielectric loss resin composition. It should be noted that the number of times that the sheet-like substrate can be passed through the liquid tank of the dispersion liquid is multiple, thus manufacturing the laminated product stacked with multiple low dielectric loss resin composition layers.

[0112] (High-frequency equipment) The high-frequency device according to the present embodiment includes a low-dielectric-loss resin composition or a molded article including the low-dielectric-loss resin composition.

[0113] The high-frequency device of this embodiment is used for information processing and communication by electronically exchanging signals. In particular, the high-frequency device of this embodiment is used in high-frequency bands where the radio waves and signals used for communication have a frequency band of 1 GHz or higher, more preferably 10 GHz or higher. Furthermore, the high-frequency device of this embodiment also includes high-frequency electronic components used in such high-frequency bands.

[0114] Examples of high-frequency devices include housings, circuit boards, printed wiring boards, transmission lines, high-frequency electronic components such as capacitors and inductors for information processing and information communication equipment, and ceiling and wall materials for rooms in which high-frequency devices are installed. Furthermore, the high-frequency devices of this embodiment also include those having an insulating film formed from a low-dielectric loss resin composition, a semiconductor encapsulating resin, and wiring coated with a low-dielectric loss resin composition as a coating material.

[0115] Example Hereinafter, preferred embodiments of the present invention will be described in detail. However, the materials, blending amounts, etc. described in these embodiments are not intended to limit the scope of the present invention to these unless otherwise specified.

[0116] (Example 1) <Inorganic fluorides> First, prepare α -AlF3 (manufactured by Stella Chemifa Co., Ltd.) as an inorganic fluoride, for the powder α-AlF3, and the half-value width of the peak of the (012) plane in the X-ray diffraction pattern was measured. An X-ray diffractometer (trade name: RINT-ULTIMA, manufactured by Rigaku Co., Ltd.) was used for the measurement. The measurement conditions were as follows.

[0117] X-ray tube: Cu Tube voltage: 40kV Tube current: 40mA Step length (width): 0.02° ·Measurement range (scanning range of diffraction angle): 2 i =10°~70° According to 2 i =25.3° and α -Calculate the half-peak width of the diffraction intensity peak corresponding to the (012) plane of AlF3. α The half-value width of -AlF3 is 0.17°.

[0118] Next, measure α - Average particle size D50 of AlF3. First, 0.1 to 0.3 g of powdered AlF3 was added to 200 mL of circulating solvent (water) flowing in a particle size distribution measuring device (trade name: Microtrac MT3300EXII, manufactured by Nikkiso Co., Ltd.). α -AlF3. Thus, α The concentration of AlF3 in the aqueous dispersion was 0.05 to 0.15 mass % relative to the total mass, and the aqueous dispersion was measured by laser diffraction and scattering. In the obtained particle size distribution, the average particle size at 50% cumulative volume was calculated as D50. α -The average particle size D50 of AlF3 is 2 m m.

[0119] Next, α -AlF3 powder was filled in a quartz tube, and the relative dielectric constant and dielectric loss tangent were measured by the cavity resonator method in the 10 GHz frequency range in an atmosphere of 25°C and 40% relative humidity. A vector network analyzer (manufactured by Anritsu Co., Ltd., trade name: MS46122B) was used for the measurement. α -Measurement of relative dielectric constant and dielectric loss tangent of AlF3 quartz tube using α - Bulk density and true density of AlF3, and relative to the filling volume α -AlF3 filling amount is used to correct the voids and calculate α -Relative dielectric constant ε of AlF3 r1[-] and dielectric loss tangent tan d 1[-]. As a result, the relative dielectric constant ε r1 is 3.2[-], dielectric loss tangent tan d 1 is 0.0027[-].

[0120] <Fluororesin particles> As the fluororesin particles, particles having an average particle size d50 of 200 nm to 500 nm and a relative dielectric constant ε r2 3.0[-] or less, dielectric loss tangent tan d 2 is PTFE particles with a particle size of 0.002 [-] or less.

[0121] <Production of Composite Compounds> 99 parts by mass of α -AlF3 is mixed with 1 part by mass of PTFE particles, and then the PTFE particles are heat-fused to the substrate at a temperature above the melting point of the PTFE particles. α -AlF3 was heated and then cooled to room temperature to produce the composite compound of this example.

[0122] (Example 2) In this embodiment, α The composite compound according to this example was prepared in the same manner as in Example 1 except that the content of -AlF3 was changed to 90 parts by mass and the content of PTFE particles was changed to 10 parts by mass.

[0123] (Comparative Example 1) In this comparative example, the α -100 parts by mass of an inorganic filler of AlF3 was used instead of the composite compound.

[0124] (Example 3) In this embodiment, the average particle size D50 is 2 m m's α -AlF3 is changed to an average particle size D50 of 10 m m's α -AlF3. Except for this, the composite compound according to this example was prepared in the same manner as in Example 1.

[0125] (Example 4) In this embodiment, the average particle size D50 is 2 m m's α -AlF3 is changed to an average particle size D50 of 10 m m's α -AlF3. Except for this, the composite compound according to this example was prepared in the same manner as in Example 2.

[0126] (Example 5) In this embodiment, α The composite compound according to this example was prepared in the same manner as in Example 3 except that the content of -AlF3 was changed to 80 parts by mass and the content of PTFE particles was changed to 20 parts by mass.

[0127] (Example 6) In this embodiment, the average particle size D50 is 40 m 95 parts by mass of CaF2 (produced by Stella Chemifa Co., Ltd.) α -AlF3. In addition, the content of PTFE particles was changed to 5 parts by mass. Except for this, the composite compound according to this example was prepared in the same manner as in Example 1.

[0128] (Example 7) In this embodiment, the average particle size D50 is 3 m 95 parts by mass of K2SiF6 (produced by Stella Chemifa Co., Ltd.) α -AlF3. In addition, the content of PTFE particles was changed to 5 parts by mass. Except for this, the composite compound according to this example was prepared in the same manner as in Example 1.

[0129] (Comparative Example 2) In this comparative example, a particle having an average particle size D50 of 10 m m's α -100 parts by mass of an inorganic filler of AlF3 was used instead of the composite compound.

[0130] (Comparative Example 3) In this comparative example, the average particle size D50 of the m 100 parts by mass of an inorganic filler of silica of m was used instead of the composite compound.

[0131] (Comparative Example 4) In this comparative example, the average particle size D50 was 1 m 95 parts by mass of silicon dioxide is replaced by α -AlF3. In addition, the content of PTFE particles was changed to 5 parts by mass. Except for this, the composite material according to this comparative example was prepared in the same manner as in Example 1.

[0132] (Comparative Example 5) In this comparative example, the average particle size D50 of 40 m 100 parts by mass of an inorganic filler of CaF2 of m is used instead of the composite compound.

[0133] (Comparative Example 6) In this comparative example, the average particle size D50 of the m 100 parts by mass of an inorganic filler of K2SiF6 was used instead of the composite compound.

[0134] (Example 8) In this embodiment, α The composite compound according to this example was prepared in the same manner as in Example 1 except that the content of -AlF3 was changed to 95 parts by mass and the content of PTFE particles was changed to 5 parts by mass.

[0135] (SEM image) SEM images of the composite compounds according to Examples 1, 2, 5, 6, and 8 and the composite according to Comparative Example 4 were taken using an electron microscope (trade name: SU1510, manufactured by Hitachi High-Technologies Corporation). Figure 1~Figure 6 Respective SEM images are shown in .

[0136] Depend on Figure 1~Figure 3 and Figure 5 It can be seen that in Examples 1, 2, 5 and 8, it was confirmed that α -AlF3 and PTFE particles were composited to obtain PTFE particles that were thermally bonded to α -AlF3 surface part of the complex compound. Figure 4 It is known that in Example 6, by compounding the mixture of CaF2 and PTFE particles, a composite compound in which PTFE particles are thermally fused to a portion of the surface of CaF2 is obtained. Figure 6 It was found that even if the mixture of silica and PTFE particles was subjected to a composite treatment, a composite compound such as that in Example 1 could not be obtained.

[0137] (Determination of relative dielectric constant and dielectric loss tangent) For each sample of the composite compound involved in Examples 1 to 7, the inorganic filler involved in Comparative Examples 1 to 3, 5 and 6, and the composite involved in Comparative Example 4, the relative dielectric constant and dielectric loss tangent of each were measured. That is, for each sample, it was filled in a quartz tube, and the relative dielectric constant and dielectric loss tangent were measured by the cavity resonator method in the 10 GHz frequency region under an ambient atmosphere of a temperature of 25°C and a relative humidity of 40%. A vector network analyzer (manufactured by Anritsu Co., Ltd., trade name: MS46122B) was used in the measurement. Furthermore, for the measured values ​​of the relative dielectric constant and dielectric loss tangent of the quartz tube filled with each sample, the volume density and true density of each sample, as well as the filling amount of each sample relative to the filling volume, were used to correct the void portion and calculate the relative dielectric constant ε of each sample. r0 [-] and dielectric loss tangent tan d 0[-]. The results are shown in Table 1.

[0138] As can be seen from Table 1, the α -AlF3 inorganic filler, the dielectric loss tangent value of the composite compounds of Examples 1 and 2 was lowered, and the dielectric loss was reduced. In addition, it was confirmed that the composite compounds of Examples 3 to 5 were better than those of Comparative Example 2. α Compared with the inorganic filler containing -AlF3, the value of the dielectric loss tangent decreases, and the dielectric loss decreases. In addition, it was confirmed that in the composite compound involved in Example 6, the value of the dielectric loss tangent decreases compared with the inorganic filler containing CaF2 involved in Comparative Example 5; in the composite compound involved in Example 7, the value of the dielectric loss tangent decreases compared with the inorganic filler containing K2SiF6 involved in Comparative Example 6, and the dielectric loss is reduced. It is believed that this is because the PTFE particles are thermally fused to the surface of the base material containing each inorganic fluoride and composited, so that the dielectric loss of the PTFE particles shows a synergistic effect.

[0139] In addition, when the inorganic filler comprising silicon dioxide that comparative example 3 relates to, relative dielectric constant is 2.8, and dielectric loss tangent is 0.0016.In addition, in the comparative example 4 to which the mixture of silicon dioxide and PTFE particle has been subjected to composite treatment, when comparing with the silicon dioxide related to comparative example 3, although the value of relative dielectric constant reduces, the value of dielectric loss tangent increases (deterioration), does not confirm the synergistic effect brought by and using PTFE particle. It should be noted that, in the composite treatment with PTFE particle, the value of relative dielectric constant reduces, and it is inferred that air layer etc. are formed in silicon dioxide.

[0140] (Evaluation of dispersion and fluidity) Next, the dispersibility of each sample of the composite compound according to Examples 1 to 7, the inorganic filler according to Comparative Examples 1 to 3, 5, and 6, and the composite according to Comparative Example 4 in a polymer resin was evaluated. Specifically, each sample and an epoxy resin (trade names: jER (registered trademark) 828, jER (registered trademark) CURE, manufactured by Mitsubishi Chemical Corporation) were placed in a container cup and kneaded using a deaerator to prepare a composition such that the concentration of each sample was 50% by mass relative to the total mass of the resulting composition.

[0141] The dispersibility and fluidity of each of the obtained compositions were evaluated based on the following criteria. The results are shown in Table 1.

[0142] ○: Such as Figure 7 As shown in (a), the slurry composition falls smoothly.

[0143] Δ: The slurry composition fell but lacked smoothness.

[0144] ×: No slurry composition can be obtained, or Figure 7 As shown in (b), the slurry composition falls together.

[0145] As can be seen from Table 1, Examples 1 to 7 all produced slurry compositions in which the composite compound was well dispersed (suspended) in the epoxy resin. In particular, the composite compounds involved in Examples 1 to 4, 6, and 7 had excellent dispersibility in the epoxy resin, and all produced slurry compositions with good fluidity. It is generally believed that PTFE has poor compatibility with polymer resins, but in the composite compounds of Examples 1 to 4, 6, and 7, the surface of the base material containing the respective inorganic fluorides was not completely covered with PTFE particles, and the Lewis acid sites on the surface of the base material were exposed. Therefore, it is believed that the affinity of these composite compounds with the epoxy resin was maintained, resulting in uniform dispersion in the epoxy resin. On the other hand, it is believed that in the composite compound of Example 5, the content of PTFE particles was high, so compared with the composite compounds of Examples 1 to 4, 6, and 7, more PTFE particles were thermally fused to the surface of the base material, resulting in reduced affinity with the epoxy resin and slightly reduced fluidity.

[0146] In Comparative Examples 3 and 4, silica did not originally have a good affinity for the epoxy resin, and thus phase separation occurred with the epoxy resin, and no slurry composition was obtained.

[0147] [Table 1]

[0148] (Evaluation of chemical resistance) Each of the composite compound of Example 8, the silica of Comparative Example 3, and the composite of Comparative Example 4 was added to a 1N aqueous NaOH solution to a concentration of 10% by mass. The mixture was then stored at 80°C for 3 days. After storage, the amount of Al or Si elution was measured using an ICP-AES analyzer (trade name: ULTIMA2, manufactured by Horiba, Ltd.) (Al detection wavelengths: 396 nm and 152 nm, Si detection wavelengths: 611 nm and 251 nm). The results are shown in Table 2.

[0149] [Table 2]

[0150] As shown in Table 2, the composite compound of Example 8 was able to suppress aluminum elution to 100 ppm or less even after immersion in an aqueous sodium hydroxide solution at 80°C for 3 days, confirming excellent chemical resistance. On the other hand, the silica of Comparative Example 3 and the composite of Comparative Example 4 both exhibited silicon elution of 3% by mass or more relative to their respective total masses, confirming poor chemical resistance.

Claims

1. A composite compound for a low dielectric loss resin composition, characterized in that: Include: Base materials containing inorganic fluorides, and Fluorine resin particles held on at least a portion of the surface of the base material, The dielectric loss tangent of the fluororesin particles is 0.002 or less at a frequency of 1 GHz or higher and a temperature of 25°C.

2. The composite compound for a low dielectric loss resin composition according to claim 1, wherein The fluororesin particles are held on the surface of the base material containing the inorganic fluoride by thermal fusion.

3. The composite compound for a low dielectric loss resin composition according to claim 1, wherein The fluororesin is polytetrafluoroethylene.

4. The composite compound for a low dielectric loss resin composition according to claim 1, wherein The inorganic fluoride is MFn or K2SiF6, In the formula MFn, M is at least one selected from Li, Na, K, Mg, Al, Ca, Sc, Mn, Fe, Ga, Rb, Sr, Y, Zr, Sn, Ba, La, Ce, Yb, Hf and Bi, and n represents an integer of 1 to 4.

5. The composite compound for a low dielectric loss resin composition according to claim 4, wherein The inorganic fluoride is AlF3.

6. The composite compound for a low dielectric loss resin composition according to claim 1, wherein The average particle size D50 of the matrix containing inorganic fluoride is 0.05 μ m and above and 75 μ m or less.

7. The composite compound for a low dielectric loss resin composition according to claim 1, wherein The content of the fluororesin particles is 0.5% by mass or more and less than 26% by mass relative to the total mass of the base material containing the inorganic fluoride.

8. A low dielectric loss resin composition, characterized in that A composite compound comprising at least a polymer resin and the low dielectric loss resin composition according to any one of claims 1 to 7.

9. The low dielectric loss resin composition according to claim 8, wherein The content of the composite compound is 1% by mass or more and 85% by mass or less relative to the total mass of the low dielectric loss resin composition.

10. The low dielectric loss resin composition according to claim 8, wherein The polymer resin includes at least one thermoplastic resin and / or at least one thermosetting resin.

11. The low dielectric loss resin composition according to claim 10, wherein The polymer resin is at least one selected from olefin resins, styrene resins, polyethylene resins, methacrylic resins, thermoplastic elastomer resins, thermoplastic polyurethane resins, polyacrylonitrile resins, polylactic acid resins, polyamide polyacetal resins, polycarbonate resins, polyphenylene ether resins, polyethylene terephthalate resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyetheretherketone resins, liquid crystal polymer resins, polyimide resins, fluororesins, phenolic resins, amine resins, furan resins, unsaturated polyester resins, epoxy resins, diallyl phthalate resins, guanamine resins, ketone resins, silicone resins, thermosetting elastomer resins, natural rubber, synthetic rubber and their modifications.

12. A molded body for high-frequency devices, characterized in that: Used in frequency bands above 1GHz, The molded article for high-frequency devices includes a molded article containing the low dielectric loss resin composition according to claim 8 .

13. A high-frequency device, characterized in that: Used in frequency bands above 1GHz, The high-frequency device comprises the low dielectric loss resin composition according to claim 8.

14. A high-frequency device, characterized in that: Used in frequency bands above 1GHz, The high-frequency device includes the molded article for a high-frequency device according to claim 12 .

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