Inorganic filler for low-dielectric-loss resin composition, slurry composition 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 inorganic filler for a low-dielectric-loss resin composition which suppresses the loss coefficient in a high-frequency band and has good low-dielectric-loss characteristics; a slurry composition for a low-dielectric-loss resin composition; a low-dielectric-loss resin composition; a molded article for a high-frequency device; this inorganic filler for a low-dielectric-loss resin composition is an inorganic filler for a low-dielectric-loss resin composition, and is characterized in that the inorganic filler is in the form of a powder and contains aluminum fluoride having an alpha phase, and the half-width of the peak of the (012) plane of the alpha phase in the X-ray diffraction pattern of the aluminum fluoride is 0.3 DEG or less.

Description

Technical Field

[0001] The present invention relates to an inorganic filler for a low-dielectric-loss resin composition comprising at least a polymer resin and an inorganic filler, which can be used in electronic components such as circuit boards, information and communication equipment, and the like; a slurry composition 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. 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, in high-frequency devices and their components, materials with low loss coefficient values, which are the main cause of transmission loss outside of the frequency range, are required. 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 amino groups that exhibit excellent compatibility and reactivity with alkyl groups and epoxy resins. According to Patent Document 2, using this surface-modified inorganic filler 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 granular material comprising metal oxide granular materials and a polyorganosiloxane compound that has been surface-treated. According to Patent Document 3, by incorporating the surface-treated metal oxide granular materials 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 also be suppressed.

[0007] However, the technology disclosed in Patent Document 1 is a technology for controlling the low dielectric loss characteristics of the resin composition itself. Furthermore, the technologies disclosed in Patent Documents 2 and 3 are technologies for controlling the low dielectric loss of the resin composition by surface-modifying the inorganic filler. In other words, the technologies disclosed in Patent Documents 1 to 3 do not use inorganic fillers with excellent low dielectric loss characteristics to enhance or improve the low dielectric loss of the resin composition.

[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 Technical problem to be solved by the invention An object of the present invention is to provide a novel inorganic filler for a low-dielectric-loss resin composition, which suppresses the loss factor in a high-frequency band and has excellent low-dielectric-loss characteristics, a slurry composition 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.

[0009] Technical solutions to technical problems In order to solve the above technical problems, the inorganic filler for the low dielectric loss resin composition of the present invention is an inorganic filler for the low dielectric loss resin composition, characterized in that the inorganic filler is in powder form, and the inorganic filler comprises α phase of aluminum fluoride, the X-ray diffraction pattern of aluminum fluoride α The half-value width of the peak of the (012) plane of the phase is 0.3° or less.

[0010] In the above configuration, the half-value width is preferably 0.12° or greater.

[0011] In the above configuration, it is preferred that the average particle size D50 of the inorganic filler is 0.05 m m and above and 75 m m or less.

[0012] Furthermore, in the above configuration, the oxygen content of the inorganic filler is preferably 2% by mass or less relative to the total mass of the inorganic filler.

[0013] In order to solve the above technical problems, the slurry composition for the low dielectric loss resin composition of the present invention is a slurry composition for the low dielectric loss resin composition in which an inorganic filler is dispersed in a solvent, characterized in that the inorganic filler comprises αphase of aluminum fluoride, the X-ray diffraction pattern of aluminum fluoride α The half-value width of the peak of the (012) plane of the phase is 0.3° or less.

[0014] In the above configuration, the half-value width is preferably 0.12° or greater.

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

[0016] Furthermore, in the above configuration, the oxygen content of the inorganic filler is preferably 2% by mass or less relative to the total mass of the inorganic filler.

[0017] Furthermore, in the above configuration, the content of the inorganic filler is preferably 1% by mass or more and 85% by mass or less relative to the total mass of the slurry composition for the low dielectric loss resin composition.

[0018] In order to solve the above technical problems, the low dielectric loss resin composition of the present invention is characterized in that it comprises at least a polymer resin and an inorganic filler, wherein the inorganic filler comprises α phase of aluminum fluoride, the X-ray diffraction pattern of aluminum fluoride α The half-value width of the peak of the (012) plane of the phase is 0.3° or less.

[0019] In the above configuration, the half-value width is preferably 0.12° or greater.

[0020] In the above configuration, it is preferred that the average particle size D50 of the inorganic filler is 0.05 m m and above and 75 m m or less.

[0021] Furthermore, in the above configuration, the oxygen content of the inorganic filler is preferably 2% by mass or less relative to the total mass of the inorganic filler.

[0022] In the above configuration, the content of the inorganic filler 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.

[0023] In the above configuration, the polymer resin preferably includes at least one thermoplastic resin and / or at least one thermosetting resin.

[0024] In the above-mentioned structure, the above-mentioned polymer resin is preferably selected from at least one of olefin resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyetheretherketone resins, liquid crystal polymer resins, polyimide resins, fluororesins, phenolic resins, epoxy resins, silicone resins and their modified products.

[0025] In order to solve the above-mentioned technical problems, the molded article for high-frequency devices of the present invention is characterized in that it is a molded article for high-frequency devices used in a frequency band of 1 GHz or higher, comprising a molded article of the low dielectric loss resin composition.

[0026] 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, and includes the low-dielectric-loss resin composition.

[0027] Furthermore, 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, and includes the above-mentioned molded article for a high-frequency device.

[0028] Effects of the Invention According to the present invention, by comprising α Phase and X-ray diffraction pattern α Using an inorganic filler containing aluminum fluoride (AlF3) having a half-width of a peak of 0.3° or less on the (012) plane of the phase, or using a slurry composition for a low-dielectric-loss resin composition in which the inorganic filler is dispersed in a solvent, can reduce the loss factor in the high-frequency band and improve low-dielectric-loss properties. As a result, even when the low-dielectric-loss resin composition containing the inorganic filler of the present invention is molded into a film or sheet-like article and used in thin-layer electronic components such as printed wiring boards, flexible circuit boards, and high-frequency boards, it is possible to prevent degradation of electrical properties due to surface irregularities.

[0029] Furthermore, according to the present invention, by using the low dielectric loss resin composition of the present invention in a molded article for a high-frequency device or a high-frequency device, even when used in a high-frequency band of 1 GHz or higher, attenuation of electrical signals due to transmission loss can be suppressed, enabling high-speed and high-frequency transmission. DETAILED DESCRIPTION

[0030] (Inorganic filler for low dielectric loss resin composition) First, an inorganic filler for a low dielectric loss resin composition according to an embodiment of the present invention (hereinafter referred to as “inorganic filler”) will be described below.

[0031] The inorganic filler of this embodiment is a powdery solid particle containingα The present invention contains crystalline aluminum fluoride (hereinafter referred to as "aluminum fluoride") of a phase as a main component. In the present invention, it has been found that aluminum fluoride exhibits excellent low dielectric loss characteristics in a high frequency band of 1 GHz or higher. Therefore, by including it as a component of a low dielectric loss resin composition (described in detail later), it exhibits a significant effect of improving the low dielectric loss characteristics of the low dielectric loss resin composition.

[0032] In the X-ray diffraction pattern of aluminum fluoride of this embodiment α 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, it is ideal that the crystallinity is high regardless of the average particle size of the inorganic compound. Here, in the case of the present invention, 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 the present invention, by setting the upper limit of the half-value width to 0.3° or less, the crystallinity of aluminum fluoride can be prevented from becoming too high, and the dielectric loss tangent can be suppressed. As a result, the loss factor can be reduced, and low dielectric loss can be suppressed.

[0033] In addition, the lower limit of half-peak width is preferably more than 0.12 °, more preferably more than 0.15 °. By making the lower limit of half-peak width be more than 0.12 °, when amorphous aluminum fluoride crystallizes or during crystal growth, it is possible to prevent grain overgrowth and make the particle diameter of crystal grain 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 inorganic filler 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 board, flexible circuit board and high-frequency substrate of thin layer are used, it is also possible to reduce or suppress the concavo-convex on surface, prevent the reduction of electrical characteristic. In addition, it is possible to manufacture the film-like or sheet-like molded products fully suppressed in thickness.

[0034] 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 graph with incident angle as the horizontal axis and diffraction intensity as the vertical axis when measuring a sample based on (powder) X-ray diffraction. "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°.

[0035] The inorganic filler of this embodiment may contain other well-known inorganic fillers within the range that does not impair the effect of the present invention, or may be composed only of α The low dielectric loss resin composition is made of aluminum fluoride. As other inorganic fillers, there are no particular restrictions, and for example, silicon dioxide, aluminum oxide, barium sulfate, talc, clay, mica powder, zirconium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, zirconium borate, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and fluorine compounds can be mentioned. In addition, as other inorganic fillers, fibrous fillers such as paper, glass nonwovens, synthetic fibers, cellulose fibers, carbon fibers and carbon nanotubes can be used without being limited to the shape of the low dielectric loss resin composition.

[0036] The content of other inorganic fillers is not particularly limited and can be appropriately set according to the application, purpose, and the like.

[0037] Relative dielectric constant ε of inorganic filler r1 The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3.5 or less at a frequency of 1 GHz or more and a temperature of 25°C. r1 When the value is 6 or less, the loss factor can be reduced, and the dielectric loss can be suppressed.

[0038] In addition, the dielectric loss tangent tan of the inorganic filler 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, and the dielectric loss can be suppressed.

[0039] The upper limit of the loss factor of the inorganic filler is preferably less than 15, more preferably 10 or less, further preferably 8 or less, and particularly preferably 5 or less. If the loss factor is less than 15, the loss factor of the low dielectric loss resin composition can be reduced, thereby improving the low dielectric loss characteristics.

[0040] 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 filler including the powder and converting the measured value. The measurement method can be selected appropriately. Specifically, for example, the method described in the Examples below can be used for each measurement.

[0041] Regarding the loss factor, the relative dielectric constant ε of the inorganic filler including the powder can be used. r1 and dielectric loss tangent tan d The loss coefficient was calculated based on the following formula using the measured value of 1.

[0042] (Loss coefficient) = (ε r1 ) 1 / 2 ×tan d 1×10 3 (where ε r1 [-] represents the relative dielectric constant of the inorganic filler including the powder used for measurement, tan d 1[-] represents its dielectric loss tangent.) Relative dielectric constant ε r1 It is a parameter that indicates the polarization degree of the inorganic filler used for 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 1 is a parameter indicating the amount of signal propagated inside the inorganic filler used for measurement and converted into heat and lost. The lower the dielectric loss tangent, the less signal loss and the higher the signal transmission efficiency.

[0043] The average particle size D50 of the inorganic filler (the particle size at which the cumulative particle size in the volume-based cumulative particle size distribution is 50%) is not particularly limited and can be appropriately set, for example, based on the shape, such as the size and thickness, of the molded article containing the low dielectric loss resin composition, and the adjustment of the fluidity of the material containing the inorganic filler in the preparation of the low dielectric loss resin composition. Generally, the upper limit of the average particle size D50 of the inorganic filler is preferably 75 m m or less, more preferably 50 m m or less, more preferably 10 m m or less, particularly preferably 1 mOn the other hand, the lower limit of the average particle size D50 of the inorganic filler is preferably 0.05 m m or more, more preferably 0.075 m m or more, more preferably 0.1 m m or more. If the average particle diameter D50 of the inorganic filler 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 a laminate, the electrical properties of the laminate are sometimes damaged due to the concavo-convexity on the molded product surface. On the other hand, if the average particle diameter D50 of the inorganic filler is too small, when mixing the inorganic filler in the macromolecular resin (details described later), uniform mixing becomes difficult, and the viscosity of the mixture rises to the degree that is difficult to carry out the molding of the low dielectric loss resin combination.

[0044] 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 filler is preferably set to be 1 / 5 or less, more preferably 1 / 10 or less of the thickness of the molded article within the above numerical range. 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 m, the average particle size D50 of the inorganic filler is preferably 10 m m or less, more preferably 2 m m or less, more preferably 1 m m or less. Thus, a film-like or sheet-like molded article can be formed by arranging the inorganic filler particles in a monolayer. As a result, a molded article with reduced or prevented surface irregularities can be obtained. Furthermore, in a pre-cured slurry composition (details of which will be described later) obtained by dispersing the inorganic filler in a solvent, the sedimentation of the inorganic filler can be suppressed, resulting in a film-like or sheet-like molded article uniformly filled with the inorganic filler.

[0045] The average particle size D50 of the inorganic filler is a value measured by a laser diffraction and scattering method using, for example, Microtrac MT3300EXII (trade name: manufactured by Nikkiso Co., Ltd.).

[0046] The oxygen content of the inorganic filler 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 filler. The content of oxygen-containing components (such as surface hydroxyl groups, adsorbed moisture, and oxides or oxyfluorides as impurities) contained in the inorganic filler can be reduced, and the influence on the dielectric properties can be suppressed. More specifically, by reducing the content of oxygen-containing components as impurities, the crystallinity of aluminum fluoride can be improved. In addition, by reducing the content of oxyfluorides as oxygen-containing components, the insulating properties of the inorganic filler can also be improved. Furthermore, as oxygen-containing components, by reducing hydroxyl groups with high polarizability and adsorbed moisture, the reduction of dielectric properties can also be suppressed.

[0047] The oxygen content of the inorganic filler can be measured, for example, using an X-ray fluorescence analyzer (X-ray Fluorescence, trade name: ZSX Primus II, manufactured by Rigaku Corporation).

[0048] The shape of the inorganic filler is not particularly limited and can be appropriately selected, for example, considering the fluidity of the slurry composition obtained by dispersing the inorganic filler in a solvent or the mixture when the inorganic filler is mixed with a polymer resin. In addition, the shape of the inorganic filler can also be appropriately selected based on the purpose of controlling the mechanical strength, thermal conductivity and gas diffusivity of the molded article containing the low dielectric loss resin composition.

[0049] Specifically, the inorganic filler may be in any shape, such as spherical, substantially spherical, elliptical, rod-shaped, needle-shaped, spindle-shaped, or plate-shaped. Furthermore, the inorganic fillers in these shapes may be hollow with a space provided inside. Furthermore, the inorganic fillers of this embodiment may include inorganic fillers of the same shape or two or more inorganic fillers of different shapes.

[0050] In addition, in the inorganic filler of the present embodiment, for example, it is preferred to use an inorganic filler whose mass reduction after heat treatment at 400°C or above is 2% by mass or less, more preferably 1.5% by mass or less, and further preferably 1% by mass or less relative to the mass of the inorganic filler before heat treatment. By using an inorganic filler whose mass reduction after the above-mentioned heat treatment is 2% by mass or less, 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 monomer forming the polymer resin, degassing of impurities during heat treatment, and thermal decomposition of the main component of the polymer resin. In the inorganic filler, there is no particular limitation on the method for reducing the mass reduction after the above-mentioned heat treatment to 2% or less. For example, it can be mentioned that: pre-heat treatment, liquid treatment, removal or reduction of materials with high thermal decomposition temperature contained in the inorganic filler, materials that do not undergo phase change when heated, and impurities that cause mass reduction when synthesizing the inorganic filler.

[0051] Next, a method for producing aluminum fluoride contained in an inorganic filler will be described below. It should be noted that the production method described below is an example, and the present invention is not limited to this production method.

[0052] The method for producing aluminum fluoride includes at least: a step of reacting an aluminum salt with fluoride ions and / or ammonium ions to produce a slurry of aluminum fluoride; a step of performing solid-liquid separation on the slurry of aluminum fluoride and further washing it; and a step of removing water and solvent from the washed aluminum fluoride paste to produce a dry solid of aluminum fluoride.

[0053] The reaction between the aluminum salt and the fluoride ions and / or ammonium ions in the step of preparing the aluminum fluoride slurry can be carried out, for example, by adding a solid aluminum salt to a solution containing a fluoride and / or ammonium compound (hereinafter referred to as the "fluoride solution"). Alternatively, the reaction can be carried out by mixing an aluminum salt solution with a fluoride solution. It should be noted that the aluminum salt solution, fluoride solution, etc., are preferably filtered to remove foreign matter before use in these reactions.

[0054] The aluminum salt is not particularly limited, and examples thereof include aluminum chloride, aluminum sulfate, aluminum acetate, aluminum nitrate, and aluminum hydroxide. These aluminum salts may be used alone or in combination of two or more.

[0055] The solvent in the aluminum salt solution is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, and glycerol. These solvents may be used alone or in combination of two or more.

[0056] The above-mentioned aluminum salt solution is obtained by dissolving the aluminum salt in a solvent. The temperature of the solvent when dissolving the aluminum salt in the solvent can be appropriately set according to the solubility of the aluminum salt in the solvent, etc. For example, when the aluminum salt shows sufficient solubility in the solvent even at room temperature, the aluminum salt can be dissolved in the solvent at room temperature. In addition, when the solubility of the aluminum salt in the solvent is low at room temperature, the aluminum salt can be dissolved therein after the solvent is heated. Thus, the time required for the aluminum salt to dissolve in the solvent is shortened.

[0057] The fluoride and ammonium compound in the fluoride solution are not particularly limited, and examples thereof include solutions of ammonium fluoride, acidic ammonium fluoride, sodium fluoride, potassium fluoride, alkylammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, and hydrogen fluoride. These solutions may be used alone or in combination of two or more.

[0058] The solvent in the solution of the fluoride or the like is not particularly limited, and examples thereof include water, organic solvents such as alcohol, and mixed solvents thereof.

[0059] A solution of a fluoride or the like can be prepared by dissolving a fluoride and / or an ammonium compound in a solvent.

[0060] The reaction temperature of the solid aluminum salt or aluminum salt solution and the solution of the fluoride or the like is not particularly limited, but is generally 20°C or higher and 50°C or lower, preferably 25°C or higher and 45°C or lower. By setting the reaction temperature to 20°C or higher, the reaction between the solid aluminum salt or aluminum salt solution and the solution of the fluoride or the like can be suppressed from being excessively slowed down. On the other hand, by setting the reaction temperature to 50°C or lower, the volatilization of some components from the solid aluminum salt or aluminum salt solution and the solution of the fluoride or the like, which could cause changes in the concentrations of these solutions, etc., can be prevented.

[0061] The aluminum salt of solid is added in the solution such as fluoride, or when aluminum salt solution and solution such as fluoride are mixed, the reaction of aluminum salt and fluorion and / or ammonium ion is carried out rapidly, generates aluminum fluorides such as ammonium fluoroaluminate and separates out, obtains the slurry of aluminum fluoride.It should be noted that, in order to make more aluminum fluoride separate out, can concentrate the solution such as aluminum salt solution, fluoride by methods such as heating or decompression, or add poor solvent.Herein, as poor solvent, is not particularly limited, for example, can enumerate the mixed solutions of alcoholic solutions such as methanol, ethanol, propyl alcohol and alcoholic solution and water etc.

[0062] It should be noted that the aluminum fluoride slurry obtained in this process may also be dried. In this case, the drying method is not particularly limited, and examples thereof include natural drying and hot air drying. In addition, the drying conditions such as the drying temperature and the drying time are not particularly limited and may be appropriately set.

[0063] There are no particular limitations on the solid-liquid separation method for the aluminum fluoride slurry, and examples thereof include suction filtration, centrifugal dehydration, and pressure filtration. However, if the average particle size of the aluminum fluoride is small and fine, making it difficult to separate the solid from the liquid by suction filtration, centrifugal dehydration, or pressure filtration, a centrifuge may be used. Alternatively, the aluminum fluoride slurry itself may be evaporated to dryness.

[0064] Furthermore, the aluminum fluoride paste obtained by solid-liquid separation can be washed by any method, but is not particularly limited. Examples include water washing. This allows unreacted fluoride and other anions to be removed from the aluminum fluoride paste. It should be noted that the washing temperature and time are not particularly limited and can be appropriately set as needed.

[0065] An example of a method for removing water and solvent (e.g., aqueous alcohol components and ammonium components) from the washed aluminum fluoride paste is heat treatment. This produces a dry aluminum fluoride powder. While the heat treatment method is not particularly limited, an example of a method is to place the aluminum fluoride paste in a tray and dry it in a dryer.

[0066] The heating temperature during the heat treatment is preferably in the range of 100°C to 600°C, more preferably in the range of 400°C to 600°C. By setting the heating temperature to 100°C or higher, the water and ammonium content contained in the aluminum fluoride paste can be sufficiently removed or reduced. On the other hand, by setting the heating temperature to 600°C or lower, thermal fusion and thermal decomposition of the aluminum fluoride can be prevented.

[0067] The heating time during the heat treatment is preferably in the range of 1 to 48 hours, more preferably in the range of 3 to 24 hours. A heating time of 3 hours or longer can sufficiently remove or reduce the moisture and ammonium content contained in the aluminum fluoride paste. On the other hand, a heating time of 48 hours or shorter can prevent thermal fusion and thermal decomposition of the aluminum fluoride.

[0068] In addition, the heat treatment can be carried out in the atmosphere or in an inert gas environment. The inert gas is not particularly limited, and examples thereof include nitrogen and argon. In addition, from the viewpoint of promoting the drying of the aluminum fluoride paste, the heat treatment can be carried out, for example, in a reduced pressure environment. There is no particular limitation on the degree of reduced pressure, but it is generally preferred to use a dry pump or an oil rotary pump, etc., at 10 -5 Pa~10 -2 It is carried out within the range of Pa.

[0069] Through the above, aluminum fluoride contained in the inorganic filler of this embodiment can be produced.

[0070] It should be noted that when adjusting the average particle size of the obtained aluminum fluoride, for example, the aluminum fluoride can be pulverized by a known pulverization method. The pulverization method is not particularly limited, and examples thereof include a dry method or a wet method using a pulverization device such as a bead mill or a jet mill. The pulverization method can be appropriately selected taking into account the particle size and purity of the aluminum fluoride.

[0071] In addition, in the manufacturing process of aluminum fluoride, the half-peak width, average particle size and shape can also be controlled. For example, in the process of making the slurry of aluminum fluoride, by appropriately changing the reaction temperature of the aluminum salt and the fluoride ions and / or ammonium ions, the environment and degree of aluminum fluoride crystal growth can be adjusted, and the half-peak width, average particle size and shape of aluminum fluoride can be controlled. In addition, it can also be adjusted by appropriately adjusting the concentration of the aluminum salt and the fluoride ions. By promoting crystal growth, the crystallinity can be improved and the half-peak width can be reduced. Furthermore, by performing post-treatment processes such as heat treatment after the process of making the dried solid of aluminum fluoride, the half-peak width, average particle size and shape of aluminum fluoride can also be controlled. As the heating temperature when performing heat treatment, as long as it is at least able to obtain a solid with α The range of aluminum fluoride phase is not particularly limited. More specifically, it is 510 ° C or above, preferably 640 ° C or above, more preferably 720 ° C or above. In addition, the heating time is as long as it can at least obtain the aluminum fluoride phase. α The range of aluminum fluoride phase is not particularly limited. More specifically, it is 5 hours or more, preferably 10 hours or more, more preferably 23 hours or more. For example, by setting the heating temperature to 510 ° C or more and the heating time to 23 hours or more, the β Considering the growth of particles based on heat treatment, etc., as long as at least α The heating temperature and heating time are not particularly limited and can be appropriately adjusted and set within the above numerical ranges.

[0072] (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.

[0073] The slurry composition of this embodiment contains at least the aforementioned inorganic filler and a solvent. The slurry composition is a dispersion in which the inorganic filler is dispersed (including suspended or turbid) in a solvent. As used herein, "dispersion" refers to a state in which the inorganic filler, 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.

[0074] About the content of inorganic filler, its lower limit is preferably more than 1 mass % relative to the gross mass of slurry composition, more preferably more than 10 mass %, particularly preferably more than 20 mass %.On the other hand, the upper limit of the content of inorganic filler is preferably less than 85 mass % relative to the gross mass of slurry composition, more preferably less than 82 mass %, particularly preferably less than 79 mass %.If the lower limit of the content of inorganic filler is more than 1 mass %, the loss factor of slurry composition diminishes, and the improvement of low dielectric loss characteristics can be achieved.

[0075] It should be noted that the relative dielectric constant, dielectric loss tangent, and shape of the inorganic filler are as described above, and therefore, detailed description thereof will be omitted.

[0076] 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 exists as a liquid at room temperature (e.g., 5°C to 35°C), has low polarity among linear alkanes, and is suitable for evaluating dielectric properties. 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, preventing the degradation of handling properties that would otherwise occur due to their solid state at room temperature. It should be noted that in this specification, when a range of carbon numbers is expressed, the range refers to the carbon number including all integers contained in the range. Therefore, for example, a straight-chain alkane "having 10 or more and 16 or less carbon atoms" refers to all straight-chain alkanes having 10, 11, 12, 13, 14, 15, and 16 carbon atoms.

[0077] Regarding the content of the solvent, its lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly 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 particularly preferably 80% by mass or less, relative to the total mass of the slurry composition.

[0078] Relative dielectric constant ε of the slurry composition r2 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. r2When the value is 6 or less, the loss factor can be reduced, and the dielectric loss can be suppressed.

[0079] In addition, the dielectric loss tangent tan of the slurry composition d The upper limit of 2[-] is preferably 0.005 or less, more preferably 0.004 or less, further preferably 0.003 or less, and particularly preferably 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C. d When 2 is 0.005 or less, the loss factor can be reduced, and the dielectric loss can be suppressed.

[0080] The upper limit of the loss factor of the slurry composition 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 slurry composition can be reduced, thereby improving low dielectric loss characteristics.

[0081] 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 slurry composition and converting the measured value. The measurement method can be appropriately selected. Specifically, for example, it can be measured by the method described in the Examples below.

[0082] Regarding the loss factor, the relative dielectric constant ε of the slurry composition can be used. r2 and dielectric loss tangent tan d The loss coefficient was calculated based on the following formula using the measured value of 2.

[0083] (Loss coefficient) = (ε r2 ) 1 / 2 ×tan d 2×10 3 (where ε r2 [-] represents the relative dielectric constant of the slurry composition used for measurement, tan d 2[-] represents its dielectric loss tangent.) Relative dielectric constant ε r2 It is a parameter that indicates the degree of polarization of the slurry composition used for 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 2 is a parameter indicating the amount of loss of a signal propagating inside the slurry composition used for measurement by being converted into heat. The lower the dielectric loss tangent, the less signal loss and the higher the signal transmission efficiency.

[0084] 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.

[0085] 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 an inorganic filler to a solvent and stirring the mixture for a predetermined time.

[0086] (Low dielectric loss resin composition) Next, the low dielectric loss resin composition according to the present embodiment will be described below.

[0087] The low dielectric loss resin composition of the present embodiment contains at least the above-mentioned inorganic filler and a polymer resin.

[0088] Inorganic fillers may be subjected to surface treatment (surface modification) for purposes such as improving wettability with respect to polymer resins, improving dispersibility with respect to polymer resins, improving processability of molded articles containing the low dielectric loss resin composition during and after molding, improving adhesion with the polymer resin, improving the mechanical strength of the low dielectric loss resin composition, suppressing or preventing moisture absorption and oxidation by the inorganic filler, preventing static charging during handling of the inorganic filler, preventing aggregation of the inorganic filler, coloring according to the intended use, and adjusting the refractive index.

[0089] Surface modifiers that can be used to modify the surface of inorganic fillers include, specifically, fatty acids such as stearic acid, oleic acid, and linoleic acid; anionic, cationic, and nonionic surfactants; coupling agents such as phosphoric acid, silane, and carboxylic acid; maleic acid-modified polypropylene; and polymeric surface modifiers such as titanate coupling agents, depending on the intended purpose. Among these surface modifiers, phosphoric acid, silane, and carboxylic acid coupling agents are preferred from the perspective of improving the wettability and dispersibility of the inorganic filler in the polymer resin.

[0090] About the content of inorganic filler, 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 %, particularly preferably more than 20 mass %.On the other hand, the upper limit of the content of inorganic filler is preferably less than 85 mass % relative to the gross mass of low dielectric loss resin composition, more preferably less than 82 mass %, particularly preferably less than 79 mass %.If the lower limit of the content of inorganic filler is more than 1 mass %, then the loss factor of low dielectric loss resin composition diminishes, and the raising of low dielectric loss characteristics can be achieved.On the other hand, if the upper limit of the content of inorganic filler is less than 85 mass %, then the deterioration of the physical strengths such as brittleness can be prevented, and the raising of the raising of hardness, the reduction of thermal expansion coefficient and weather resistance can be achieved.

[0091] The polymer resin preferably includes at least one thermoplastic resin and / or at least one thermosetting resin.

[0092] More specifically, examples of polymer resins include olefin resins such as polyethylene resins and polypropylene resins; polycarbonate resins; polyphenylene ether resins; polysulfone resins; polyethersulfone resins; polyphenylene sulfide resins; polyetheretherketone resins; liquid crystal polymer resins; polyimide resins; fluororesins such as polytetrafluoroethylene resin (PTFE), copolymers of polytetrafluoroethylene and perfluoroalkoxyethylene (PFA), polychlorotrifluoroethylene resin (PCTFE), tetrafluoroethylene-hexafluoropropylene copolymers (FEP), and tetrafluoroethylene-ethylene copolymers (ETFE); phenolic resins; epoxy resins; silicone resins; 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 is used in which an epoxy resin is mixed with a polyphenylene ether resin, 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.

[0093] 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 %, particularly preferably more than 21 mass % and below 80 mass %.Be more than 15 mass % by making the content of polymer resin, it is possible to fully show the characteristic of the polymer resins such as adhesiveness, water resistance.On the other hand, be below 99 mass % by making the content of polymer resin, it is possible to maintain the characteristic of polymer resin, and it is possible to reduce the dielectric loss of resin combination by adding inorganic filler.

[0094] Relative dielectric constant ε of low dielectric loss resin composition r3The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3.5 or less at a frequency of 1 GHz or more and a temperature of 25°C. r3 When the value is 6 or less, the loss factor can be reduced, and the dielectric loss can be suppressed.

[0095] In addition, the dielectric loss tangent tan of the low dielectric loss resin composition d The upper limit of 3[-] is preferably 0.03 or less, more preferably 0.025 or less, and particularly preferably 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C. d When 3 is 0.03 or less, the loss factor can be reduced, and the dielectric loss can be suppressed.

[0096] The upper limit of the loss factor of the low dielectric loss resin composition is preferably less than 40, more preferably 38 or less, and particularly preferably 35 or less. If the loss factor is less than 40, the loss factor of the low dielectric loss resin composition can be reduced, thereby improving the low dielectric loss characteristics.

[0097] 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 obtained by measuring the low dielectric loss resin composition and converting the measured value. The measurement method can be selected appropriately. Specifically, for example, it can be measured by a method based on the method described in the examples below.

[0098] Regarding the loss factor, the relative dielectric constant ε of the low dielectric loss resin composition can be used. r3 and dielectric loss tangent tan d The loss coefficient was calculated based on the following formula using the measured value of 3.

[0099] (Loss coefficient) = (ε r3 ) 1 / 2 ×tan d 3×10 3 (where ε r3 [-] represents the relative dielectric constant of the low dielectric loss resin composition used for measurement, tan d 3[-] represents its dielectric loss tangent.) Relative dielectric constant ε r3It is a parameter that indicates the degree of polarization of the low dielectric loss resin composition used for 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 3 is a parameter indicating the amount of loss of a signal propagating inside the low dielectric loss resin composition used for measurement by being converted into heat. The lower the dielectric loss tangent, the less signal loss and the higher the signal transmission efficiency.

[0100] Next, a method for producing the low dielectric loss resin composition according to this embodiment will be described below.

[0101] The low dielectric loss resin composition of this embodiment can be produced by adding an inorganic filler and any other additives to a polymer resin and uniformly mixing or kneading the mixture. Alternatively, the composition can be produced by adding an inorganic filler and any other additives to a solution (e.g., a varnish or dispersion) obtained by dissolving or dispersing a polymer resin or a monomer forming the polymer resin in an organic solvent and dissolving the inorganic filler and any other additives in the solution.

[0102] 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 Al and F, metal oxides, and metal fluorides. The impurity content is preferably 100 ppm or less, more preferably 10 ppm or less, relative to the total mass of the low dielectric loss resin composition.

[0103] In addition, the low dielectric loss resin composition of this embodiment may contain other additives within the scope not contradicting the purpose of the present invention. Such other additives are not particularly limited, and examples thereof include curing agents, lubricants, crystal nucleating agents, UV inhibitors, colorants, flame retardants, stabilizers, plasticizers, reinforcing agents, and dispersants.

[0104] The content of other additives is not particularly limited and can be appropriately set according to the application, purpose, and the like.

[0105] The low dielectric loss resin composition of this embodiment can be used as a resin composition for insulating films (solder resist), a semiconductor sealing resin composition, an adhesive, a coating material, a covering material for wiring for power supplies and communications, and the like.

[0106] (Molded article for high-frequency devices and method for producing the same) The molded article for high-frequency devices (hereinafter referred to as a "molded article") of this embodiment includes a molded article containing a low-dielectric loss resin composition. The molded article may be composed solely of the low-dielectric loss resin composition.

[0107] Relative dielectric constant ε of the molded body r4The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3.5 or less at a frequency of 1 GHz or higher and a temperature of 25°C. If the relative dielectric constant ε4 of the molded article is 6 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0108] In addition, the dielectric loss tangent tan d The upper limit of 4[-] is preferably 0.03 or less, more preferably 0.025 or less, and further preferably 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C. d When 4 is 0.03 or less, the loss factor can be reduced, thereby achieving a reduction in dielectric loss.

[0109] The upper limit of the loss factor of the molded article is preferably less than 40, more preferably not more than 38, and particularly preferably not more than 35. When the loss factor is less than 40, the loss factor of the molded article can be reduced, thereby reducing dielectric loss.

[0110] 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 obtained by measuring the molded article and converting the measured value. The measurement method can be selected appropriately. Specifically, for example, the method described in the Examples below can be used for each measurement.

[0111] Regarding the loss factor, the relative dielectric constant ε of the molded body can be used. r4 and dielectric loss tangent tan d The measured value of 4 was calculated based on the following formula.

[0112] (Loss coefficient) = (ε r4 ) 1 / 2 ×tan d 4×10 3 (where ε r4 [-] represents the relative dielectric constant of the molded body, tan d 4[-] represents its dielectric loss tangent.) 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, it is also possible to use injection molding machine to manufacture molded body after utilizing extruder to manufacture granular low dielectric loss resin composition material. When using forming machines such as extruder to carry out mixing of macromolecular resin and inorganic filler and other additives etc., it is possible to reduce the number of steps, it is possible to improve production efficiency. In addition, because inorganic filler easily absorbs moisture, it is possible to suitably carry out drying process etc. before mixing with macromolecular resin.

[0113] Furthermore, when producing sheet-shaped molded articles, known methods can be used. For example, inorganic fillers 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-shaped molded article.

[0114] 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, inorganic filler and other additives arbitrarily in the state of impregnation, so that the dispersion liquid is impregnated in the sheet-like substrate. Then, drying is implemented to the sheet material impregnated with the dispersion liquid, and the impregnation sheet material impregnated with the low dielectric loss resin composition can be manufactured. It should be noted that, by making the sheet-like substrate pass through the liquid tank of the dispersion liquid for many times, the laminated product stacked with a plurality of low dielectric loss resin composition layers can also be manufactured.

[0115] (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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] ( α -AlF3(A) As α -AlF3 (A), manufactured by Stella Chemifa Co., Ltd. α -AlF3(A), 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.

[0120] 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 the peak of -AlF3 (A) is 0.162°.

[0121] Next, determine α - Average particle size D50 of AlF3 (A). First, 0.1 to 0.3 g of powdered AlF3 (A) 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 (A). Thus, αAn aqueous dispersion containing AlF3(A) in a concentration range of 0.05 to 0.15 mass % relative to the total mass was measured using laser diffraction and scattering. The particle size distribution obtained was calculated as the average particle size at 50% cumulative volume, D50. The results confirmed that: α -The average particle size D50 of AlF3 (A) is 9.3 m m, for example, also suitable for a thickness of 20 m A film-shaped or sheet-shaped molded article of a low dielectric loss resin composition having a thickness of about m.

[0122] Furthermore, the oxygen content of the inorganic filler was measured using a fluorescent X-ray analyzer (X-ray Fluorescence, trade name: ZSX Primus II, manufactured by Rigaku Co., Ltd.). α -The oxygen content of AlF3(A) relative to α -The total mass of AlF3(A) is 0.2 mass%.

[0123] ( α -AlF3(B) As α -AlF3(B) manufactured by Stella Chemifa Co., Ltd. α -AlF3(B), with α -AlF3 (A) was measured in the same manner as the half-peak width of the (012) plane peak in the X-ray diffraction pattern, the average particle size D50 and α -The oxygen content of AlF3 (B). The results of the measurement, α The half-peak width of -AlF3 (B) is 0.165°. In addition, it was confirmed that: α -The average particle size D50 of AlF3 (B) is 4.6 m m, for example, also suitable for a thickness of 20 m m or so low dielectric loss resin composition film or sheet molded products. α The total mass of -AlF3(B) is 0.4 mass%.

[0124] ( α -AlF3(C) As α -AlF3(C), manufactured by Stella Chemifa Co., Ltd. α -AlF3(C), with α -AlF3 (A) was measured in the same manner as the half-peak width of the (012) plane peak in the X-ray diffraction pattern, the average particle size D50 and α-The oxygen content of AlF3 (C). The results of the measurement, α The half-peak width of -AlF3(C) is 0.169°. In addition, it was confirmed that: α -The average particle size D50 of AlF3 (C) is 2.7 m m, for example, also suitable for a thickness of 20 m m or so low dielectric loss resin composition film or sheet molded products. α The total mass of -AlF3(C) is 0.4 mass%.

[0125] ( α -AlF3(D) For powder α -AlF3(D), with α -AlF3 (A) was measured in the same manner as the half-peak width of the (012) plane peak in the X-ray diffraction pattern, the average particle size D50 and α -The oxygen content of AlF3 (D). The results of the measurement, α The half-peak width of -AlF3 (D) is 0.176°. α -The average particle size D50 of AlF3 (D) is 72 m m. Furthermore, the oxygen content is relative to α The total mass of -AlF3(D) is 0.9 mass%.

[0126] ( α -AlF3(E) As α -AlF3(E), manufactured by Stella Chemifa Co., Ltd. α -AlF3(E), with α -AlF3 (A) was measured in the same manner as the half-peak width of the (012) plane peak in the X-ray diffraction pattern, the average particle size D50 and α -The oxygen content of AlF3 (E). The results of the measurement, α The half-peak width of -AlF3(E) is 0.187°. In addition, it was confirmed that: α -The average particle size D50 of AlF3(E) is 2.3 m m, for example, also suitable for a thickness of 20 m m or so low dielectric loss resin composition film or sheet molded products. α The total mass of -AlF3(E) is 1.0 mass%.

[0127] ( α -AlF3(F) As α-AlF3(F), manufactured by Stella Chemifa Co., Ltd. α -AlF3(F), with α -AlF3 (A) was measured in the same manner as the half-peak width of the (012) plane peak in the X-ray diffraction pattern, the average particle size D50 and α -The oxygen content of AlF3 (F). The results of the measurement, α The half-peak width of -AlF3 (F) is 0.290°. α -The average particle size D50 of AlF3 (F) is 70 m m. Furthermore, the oxygen content is relative to α -The total mass of AlF3(F) is 1.3 mass%.

[0128] ( α -AlF3(G) For powder α -AlF3(G), with α -AlF3 (A) was measured in the same manner as the half-peak width of the (012) plane peak in the X-ray diffraction pattern, the average particle size D50 and α -The oxygen content of AlF3 (G). The results of the measurement, α The half-peak width of -AlF3 (G) is 0.304°. α -The average particle size D50 of AlF3 (G) is 82 m m. Furthermore, the oxygen content is relative to α The total mass of -AlF3(G) is 2.1 mass%.

[0129] ( β -AlF3(H) 50 g of (NH4)3AlF6 (manufactured by Stella Chemifa Co., Ltd.) was placed in an alumina crucible and heated in an electric furnace under atmospheric conditions. The heat treatment temperature was 400°C and the heat treatment time was 6 hours. After the heat treatment, the crucible was cooled to room temperature, and 22 g of white powder was taken out of the alumina crucible. The white powder was analyzed using XRD (X-ray Diffraction, trade name: RINT-Ultima III, manufactured by Rigaku Co., Ltd.). The results showed that the white powder was β -AlF3.

[0130] For the obtained β -AlF3(H), with α -AlF3 (A) in the same manner, the average particle size D50 and β -The oxygen content of AlF3 (H). The results of the measurement, β-The average particle size D50 of AlF3(H) is 21 m m. In addition, the oxygen content is relative to β The total mass of -AlF3(H) is 3.5 mass%.

[0131] ( α -AlF3(I) For powder α -AlF3(I), with α -AlF3 (A) was measured in the same manner as above. The half-value width of the peak of the (012) plane in the X-ray diffraction pattern and the average particle size D50 were measured. α The half-peak width of -AlF3(I) is 0.190°. α -The average particle size D50 of AlF3(I) is 54 m m.

[0132] ( α -AlF3(J) For powder α -AlF3(J), with α -AlF3 (A) was measured in the same manner as above. The half-value width of the peak of the (012) plane in the X-ray diffraction pattern and the average particle size D50 were measured. α The half-peak width of -AlF3 (J) is 0.260°. α -The average particle size D50 of AlF3 (J) is 74 m m.

[0133] ( α -AlF3(K) For powder α -AlF3(K), with α -AlF3 (A) was measured in the same manner as the half-peak width of the (012) plane peak in the X-ray diffraction pattern, the average particle size D50 and α -The oxygen content of AlF3 (K). The results of the measurement, α The half-peak width of -AlF3 (K) is 0.127°. α -The average particle size D50 of AlF3 (K) is 45 m m. Furthermore, the oxygen content is relative to α The total mass of -AlF3(K) is 0.7 mass%.

[0134] (Example 1) The quartz tube is filled with a half-peak width of 0.127° αUsing AlF3(K) powder as an inorganic filler, the relative dielectric constant and dielectric loss tangent were measured using the cavity resonator method in the 10 GHz frequency range in an ambient atmosphere at a temperature of 19°C and a relative humidity of 50%. A vector network analyzer (Anritsu Corporation, trade name: MS46122B) was used for the measurement. The measured values ​​of the relative dielectric constant and dielectric loss tangent of the quartz tube filled with the inorganic filler were then corrected for voids using the bulk density and true density of the inorganic filler, as well as the amount of inorganic filler filled relative to the filled volume, to calculate the relative dielectric constant and dielectric loss tangent of the inorganic filler. Furthermore, using the values ​​obtained by correcting the measured values ​​of the relative dielectric constant and dielectric loss tangent of the inorganic filler, the dielectric loss of the inorganic filler was calculated based on the following formula. The results are shown in Table 1. In addition, the values ​​of the relative dielectric constant and dielectric loss tangent of the inorganic filler in Table 1 are values ​​obtained by correcting the measured values.

[0135] (Loss coefficient) = (ε r1 ) 1 / 2 ×tan d 1×10 3 (where ε r1 Indicates the relative dielectric constant of the inorganic filler, tan d 1 represents the dielectric loss tangent of the inorganic filler.) (Examples 2 to 7) In Examples 2 to 7, the inorganic fillers were respectively changed to those shown in Table 1. Measurement was performed in the same manner as in Example 1 except for these differences.

[0136] (Comparative Examples 1 and 2) In Comparative Examples 1 and 2, the inorganic fillers were changed to those shown in Table 1. Measurement was performed in the same manner as in Example 1 except for these differences.

[0137] [Table 1] (Result 1) As shown in Table 1, it was confirmed that the inorganic fillers of Examples 1 to 7 had lower loss factors measured at the same frequency than the inorganic fillers used in Comparative Examples 1 and 2, and were excellent in low dielectric loss characteristics. α In the AlF3 phase, from the viewpoint of crystallinity and average particle size, the low dielectric loss characteristics are excellent in the range of the half-peak width of the (012) plane being 0.12° or more and 0.3° or less. In addition, it was confirmed that the oxygen content of the inorganic fillers of Examples 1 to 7 is smaller than that of the inorganic fillers used in Comparative Examples 1 and 2, and the dielectric loss tangent tan is d The values ​​of are reduced.

[0138] (Example 8) 80.0 g of α AlF 3 (B) and 120 g of n-hexadecane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) were placed in a container cup and stirred with a homogenizer to prepare a slurry composition.

[0139] Next, the prepared slurry composition was injected into a PFA heat-shrinkable tube (8 cm long, 2.2 mm outer diameter, 1.8 mm inner diameter) using a syringe or other device. The tube was sealed with a PFA rod (2 mm diameter) to prevent leakage of the slurry composition. The tube was then heated in a hot air dryer. This produced a test piece containing the slurry composition of this example.

[0140] Next, the relative dielectric constant and dielectric loss tangent of the slurry composition in the resulting test piece were measured using the cavity resonator method in the 10 GHz frequency range at a temperature of 19°C and a relative humidity of 50%. This measurement was performed using a network analyzer (Keysight Technologies, trade name: E8361A). The measured relative dielectric constant and dielectric loss tangent of the slurry containing the inorganic filler were used to calculate the loss factor of the slurry composition using the following formula. The results are shown in Table 2.

[0141] (Loss coefficient) = (ε r2 ) 1 / 2 ×tan d 2×10 3 (where ε r2 represents the relative dielectric constant of the slurry composition, tan d 2 represents the dielectric loss tangent of the slurry composition. (Example 9) In Example 9, as shown in Table 2, the inorganic filler was changed to a filler having a half-peak width of 0.190. α -AlF3(I). A test piece according to Example 9 was prepared in the same manner as in Example 8 except for the above. Furthermore, the relative dielectric constant and dielectric loss tangent of the test piece according to Example 9 were measured in the same manner as in Example 8, and the loss factor was calculated. The results are shown in Table 2.

[0142] (Comparative Examples 3 and 4) In Comparative Examples 3 and 4, as shown in Table 2, the inorganic filler was changed to a half-peak width of 0.304. α -AlF3(G) and has β similar β-AlF3(H). Test pieces for Comparative Examples 3 and 4 were prepared in the same manner as in Example 8. Furthermore, the relative permittivity and dielectric loss tangent of the test pieces for Comparative Examples 3 and 4 were measured in the same manner as in Example 8, and the loss coefficient was calculated. The results are shown in Table 2.

[0143] [Table 2] (Result 2) As shown in Table 2, it was confirmed that the slurry compositions of Examples 8 and 9 had smaller dissipation factors measured at the same frequency than the slurry compositions of Comparative Examples 3 and 4, and were excellent in low dielectric loss characteristics.

[0144] (Example 10 (Preparation of Test Specimen Using Epoxy Resin)) 10 g of epoxy resin (trade name: jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation), 5 g of epoxy resin curing agent (trade name: jERCURE (registered trademark), manufactured by Mitsubishi Chemical Corporation) and α -15 g of AlF3 (A) was placed in a container cup and kneaded with a deaerator to prepare a paste.

[0145] The prepared paste was placed in a mold, cured at room temperature for 1 day, and then heat-cured at 80°C for 3 hours. The paste was then removed from the mold to produce a molded article (inorganic-organic composite material test piece) of the low dielectric loss resin composition according to Example 10.

[0146] Next, the resulting molded article was measured for relative permittivity and dielectric loss tangent using the cavity resonator method in the 10 GHz frequency range at a temperature of 19°C and a relative humidity of 50%. This measurement was performed using a network analyzer (trade name: E8361A, manufactured by Keysight Technologies, Inc.). Furthermore, the loss factor of the molded article was calculated using the following formula. The results are shown in Table 3.

[0147] (Loss coefficient) = (ε r4 ) 1 / 2 ×tan d 4×10 3 (where ε r4 Relative dielectric constant of the molded body, tan d 4 represents the dielectric loss tangent of the molded body.) (Examples 11 to 15 (Preparation of Test Specimens Using Epoxy Resin)) In Examples 11 to 15, the inorganic fillers shown in Table 3 were used instead. Molded articles of the low dielectric loss resin compositions of Examples 11 to 15 were prepared in the same manner as in Example 10. Furthermore, the relative dielectric constant and dielectric loss tangent of the molded articles of Examples 11 to 15 were measured in the same manner as in Example 10, and the loss coefficient was calculated. The results are shown in Table 3.

[0148] (Comparative Examples 5 to 7 (Preparation of Test Specimens Using Epoxy Resin)) In Comparative Examples 5 and 6, the inorganic fillers shown in Table 3 were used instead. In Comparative Example 7, no inorganic filler was used. Otherwise, molded articles of the low dielectric loss resin compositions of Comparative Examples 5 to 7 were prepared in the same manner as in Example 10. Furthermore, the relative dielectric constant and dielectric loss tangent of the molded articles of Comparative Examples 5 to 7 were measured in the same manner as in Example 10, and the loss coefficient was calculated. The results are shown in Table 3.

[0149] [Table 3] (Result 3) As shown in Table 3, it was confirmed that the molded articles comprising the low dielectric loss resin compositions of Examples 10 to 15 had lower loss coefficients measured at the same frequency than the molded articles of Comparative Examples 5 to 7, and were superior in low dielectric loss characteristics. α In the AlF 3 phase, from the viewpoint of crystallinity and average particle size, the low dielectric loss characteristics are excellent when the half-value width of the (012) plane is within the range of 0.12° to 0.3°.

Claims

1. An inorganic filler for a low dielectric loss resin composition, characterized in that The inorganic filler is in powder form and contains α phase of aluminum fluoride, The X-ray diffraction pattern of aluminum fluoride α The half-value width of the peak of the (012) plane of the phase is 0.3° or less.

2. The inorganic filler for the low dielectric loss resin composition according to claim 1, wherein The half-value width is greater than 0.12°.

3. The inorganic filler for the low dielectric loss resin composition according to claim 1, wherein The average particle size D50 of the inorganic filler is 0.05 μ m and above and 75 μ m or less.

4. The inorganic filler for the low dielectric loss resin composition according to claim 1, wherein The oxygen content of the inorganic filler is 2% by mass or less relative to the total mass of the inorganic filler.

5. A slurry composition for a low dielectric loss resin composition, characterized in that: Inorganic fillers are dispersed in the solvent. The inorganic filler comprises α phase of aluminum fluoride, The X-ray diffraction pattern of aluminum fluoride α The half-value width of the peak of the (012) plane of the phase is 0.3° or less.

6. The slurry composition for a low dielectric loss resin composition according to claim 5, wherein The half-value width is greater than 0.12°.

7. The slurry composition for a low dielectric loss resin composition according to claim 5, wherein The average particle size D50 of the inorganic filler is 0.05 μ m and above and 75 μ m or less.

8. The slurry composition for a low dielectric loss resin composition according to claim 5, wherein The oxygen content of the inorganic filler is 2% by mass or less relative to the total mass of the inorganic filler.

9. The slurry composition for a low dielectric loss resin composition according to claim 5, wherein The content of the inorganic filler is 1% by mass or more and 85% by mass or less relative to the total mass of the slurry composition for the low dielectric loss resin composition.

10. A low dielectric loss resin composition, characterized in that Contains at least polymer resin and inorganic filler, The inorganic filler comprises α phase of aluminum fluoride, The X-ray diffraction pattern of aluminum fluoride α The half-value width of the peak of the (012) plane of the phase is 0.3° or less.

11. The low dielectric loss resin composition according to claim 10, wherein The half-value width is greater than 0.12°.

12. The low dielectric loss resin composition according to claim 10, wherein The average particle size D50 of the inorganic filler is 0.05 μ m and above and 75 μ m or less.

13. The low dielectric loss resin composition according to claim 10, wherein The oxygen content of the inorganic filler is 2% by mass or less relative to the total mass of the inorganic filler.

14. The low dielectric loss resin composition according to claim 10, wherein The content of the inorganic filler is 1% by mass or more and 85% by mass or less relative to the total mass of the low dielectric loss resin composition.

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

16. The low dielectric loss resin composition according to claim 15, wherein The polymer resin is at least one selected from olefin resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyetheretherketone resins, liquid crystal polymer resins, polyimide resins, fluororesins, phenolic resins, epoxy resins, silicone resins and modified products thereof.

17. A molded body for high-frequency devices, characterized in that: The molded article for high-frequency devices is used in a frequency band of 1 GHz or higher, and comprises a molded article containing the low dielectric loss resin composition according to any one of claims 10 to 15.

18. A high-frequency device, characterized in that: The high-frequency device is used in a frequency band of 1 GHz or higher, and comprises the low dielectric loss resin composition according to any one of claims 10 to 15.

19. A high-frequency device, characterized in that: The high-frequency device is used in a frequency band of 1 GHz or higher, and includes the molded article for a high-frequency device according to claim 17 .

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