TW202248354A - Low dielectric loss resin composition, method for producing same, molded body for high frequency devices, and high frequency device - Google Patents

Abstract

To provide: a novel low dielectric loss resin composition which has a low coefficient of loss in a high frequency band, while being excellent in terms of low dielectric loss characteristics; a method for producing this low dielectric loss resin composition; a molded body for high frequency devices; and a high frequency device. A low dielectric loss resin composition according to the present invention contains at least a polymer resin and an inorganic filler, and is characterized in that the inorganic filler contains at least one substance that is selected from the group consisting of BiF3, ZrF4, HfF4, CeF3 and K2SiF6. This low dielectric loss resin composition is applicable to a molded body for high frequency devices that are used in a frequency band of 1 GHz or more, and to a high frequency device that is used in a frequency band of 1 GHz or more.

Description

Low dielectric loss resin composition, manufacturing method thereof, molded body for high-frequency equipment, and high-frequency equipment

The present invention relates to a low dielectric loss resin composition containing at least a polymer resin and an inorganic filler, which can be applied to electronic parts such as circuit boards or information communication equipment, its production method, a molded body for high-frequency equipment, and a high-frequency machine.

In recent years, in electronic components such as printed wiring boards, flexible wiring boards, and high-frequency substrates, as well as information and communication equipment, in order to realize high-speed and large-capacity data communication, the high frequency of electrical signals used has been promoted.

In particular, in electronic components for high-frequency applications, the attenuation of electrical signals increases due to the transmission loss of the transmission path as the frequency increases, and the transmission reliability may decrease. For this reason, among the loss coefficients of transmission loss factors other than frequency, materials with a small value are required for high-frequency equipment or these parts. Here, the loss coefficient is obtained by multiplying the value of the square root of the relative permittivity (ε _r ) and the value of the loss tangent (tanδ).

For example, in Patent Document 1, for the purpose of achieving low relative permittivity and low loss tangent of multilayer printed circuit boards, it is disclosed that (A) has a carboxyl group or an anhydrous acid group, and has a number average molecular weight of 300~6,000. Polyimide resin with a hydrocarbon structure, (B) epoxy resin, (C) organic solvent with a boiling point of 100°C or higher, and a thermosetting resin composition with spherical silica as essential components. According to this patent document 1, it has sufficient adhesion to the conductor, and can form an interlayer insulating resin layer with high heat resistance, flame retardancy, low permittivity, low loss tangent, and low water absorption.

Also, Patent Document 2 discloses an inorganic filler in which an alkyl group and an amine group excellent in compatibility and reactivity with epoxy resins are sequentially introduced to modify the surface. According to this patent document 2, by using a surface-modified inorganic filler to produce an epoxy resin composition, the characteristic of low permittivity can be imparted.

Also, Patent Document 3 discloses a surface-treated metal oxide particle material having a metal oxide particle material and a polyorganosiloxane compound surface-treated on the metal oxide particle material. According to this patent document 3, by including the surface-treated metal oxide particle material in the resin material, the viscosity of the obtained resin composition can be suppressed, and the relative permittivity and loss tangent of the resin composition can be suppressed.

However, the techniques disclosed in Patent Documents 1 and 2 are for controlling the low dielectric loss characteristics of the resin composition itself. Also, the technique disclosed in Patent Document 3 is to control the low dielectric loss of the resin composition through surface modification with inorganic fillers. In addition, the technologies disclosed in Patent Documents 1 to 3 use the excellent low dielectric loss characteristics to enhance or improve the low dielectric loss of the inorganic filler of the resin composition. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 5564012 [Patent Document 2] Japanese Unexamined Patent Publication No. 2015-67534 [Patent Document 3] Japanese Patent Laid-Open No. 2020-66678

[Problem to be solved by the invention]

The purpose of the present invention is to provide a novel low dielectric loss resin composition with a small loss coefficient and excellent low dielectric loss characteristics in the high frequency range, a manufacturing method thereof, a molded body for high frequency equipment, and a high frequency equipment. [As a means to solve the problem]

In order to solve the aforementioned problems, the present invention has discovered an inorganic filler having excellent low dielectric loss characteristics in the high frequency band above 1 GHz, and the low dielectric loss can be improved by including the inorganic filler in a low dielectric loss resin composition Low dielectric loss characteristics of lossy resin composition.

That is, the low dielectric loss resin composition of the present invention is to solve the aforementioned problems. In the low dielectric loss resin composition containing at least a polymer resin and an inorganic filler, the aforementioned inorganic filler contains at least one selected from BiF _3. It is characterized by groups of ZrF ₄ , HfF ₄ , CeF ₃ and K ₂ SiF ₆ .

In the aforementioned constitution, the content of the aforementioned inorganic filler is preferably 0.01% by mass to 85% by mass relative to the total mass of the aforementioned low dielectric loss resin composition.

In the aforementioned configuration, it is preferable that the polymeric resin includes at least one kind of at least one kind of thermoplastic resin and/or at least one kind of thermosetting resin.

In the aforementioned constitution, the polymeric resin is selected from at least one kind of olefin-based resin, styrene-based resin, polyethylene resin, methacrylic resin, thermoplastic elastomer resin, thermoplastic polyurethane resin, polyacrylonitrile resin, poly Lactic acid resin, polyamide acetal resin, polycarbonate resin, polyphenylene ether resin, polyethylene terephthalate, polyethylene resin, polyether resin, polyphenylene sulfide, polyether ether ketone, liquid crystal Polymer resin, polyimide resin, fluororesin, phenolic resin, amine resin, furan resin, unsaturated polyester resin, epoxy resin, diallyl phthalate resin, guanamine resin, ketone resin, poly Groups of silicone resin, thermosetting resin, natural rubber, synthetic rubber, and their modified forms are preferred.

The production method of the low dielectric loss resin composition of the present invention is to solve the aforementioned problems. In the production method of the low dielectric loss resin composition containing at least a polymer resin and an inorganic filler, a metal salt and a fluorine-containing Ion and/or ammonium ion solution reaction, the project of making the slurry of metal fluoride, and the project of heating and drying the slurry of the aforementioned metal fluoride, and making the aforementioned inorganic filler containing the metal fluoride; the aforementioned metal salt is selected Grouped from at least one kind of bismuth, zirconium, hafnium or cerium, chloride, sulfate, acetate, nitrate and hydroxide, the aforementioned metal fluoride is selected from at least one kind of BiF ₃ , ZrF ₄ , HfF ₄ And CeF ₃ groups are characteristic.

In the aforementioned configuration, the solution containing the aforementioned fluoride ions and ammonium ions is preferably a solution containing fluoride and ammonium compounds.

In addition, the method for producing a low dielectric loss resin composition of the present invention is to solve the above-mentioned problems. In the method for producing a low dielectric loss resin composition containing at least a polymer resin and an inorganic filler, an aqueous solution of silicon fluoride is included. The process of preparing the slurry of K ₂ SiF ₆ by reacting with potassium hydrogen fluoride, and the process of heating and drying the slurry of K ₂ SiF ₆ to produce the aforementioned inorganic filler containing the K ₂ SiF ₆ are characterized.

In order to solve the aforementioned problems, the molding system for high-frequency equipment of the present invention is characterized by a molded article of the aforementioned low dielectric loss resin composition among molded articles for high-frequency equipment used in a frequency band above 1 GHz.

In order to solve the aforementioned problems, the high-frequency equipment of the present invention is characterized in that the above-mentioned low dielectric loss resin composition is included in the high-frequency equipment used in the frequency band above 1 GHz.

In addition, the high-frequency equipment of the present invention is to solve the above-mentioned problems, and is characterized in that the molded body of the above-mentioned low dielectric loss resin composition is provided in the high-frequency equipment used in the frequency band above 1 GHz. [Invention effect]

According to the present invention, as the inorganic filler, by using at least one group selected from BiF ₃ , ZrF ₄ , HfF ₄ , CeF ₃ and K ₂ SiF ₆ , the gap between the inorganic filler and the polymer resin can be reduced. The loss coefficient of the high frequency band of the low dielectric loss resin composition improves the low dielectric loss characteristics. In addition, when the low dielectric loss resin composition of the present invention is used in molded articles for high-frequency equipment or high-frequency equipment, even if it is used in a high-frequency band above 1 GHz, it can suppress the attenuation of electrical signals caused by transmission loss , and can perform high-speed and high-frequency transmission.

(Low dielectric loss resin composition)

First, the low dielectric loss resin composition according to the embodiment of the present invention will be described below. The low dielectric loss resin composition of this embodiment contains at least a polymer resin and an inorganic filler. The low dielectric loss resin composition of this embodiment can be a paste-like composition.

<Inorganic filler> The inorganic filler is a group of solid particles selected from at least one of BiF ₃ , ZrF ₄ , HfF ₄ , CeF ₃ and K ₂ SiF ₆ .

The upper limit of the relative permittivity ε _r (-) of the inorganic filler is preferably 6 or less, more preferably 4 or less, and especially preferably 3 or less at a frequency above 1 GHz and a temperature of 25°C. When the relative permittivity ε _r of the inorganic filler is 6 or less, the reduction of the loss coefficient can be achieved, and the suppression of low dielectric loss can be achieved.

Also, the upper limit of the loss tangent tanδ(-) of the inorganic filler is preferably 0.005 or less, more preferably 0.002 or less, and especially preferably 0.001 or less at a frequency of 1 GHz or higher and a temperature of 25°C. When the loss tangent tanδ of the inorganic filler is less than 0.005, the reduction of the loss coefficient can be achieved, and the suppression of low dielectric loss can be achieved.

The upper limit of the loss coefficient of the inorganic filler is preferably less than 6, more preferably 4 or less, especially preferably 3 or less. When the loss coefficient is less than 6, the loss coefficient of the low dielectric loss resin composition can be reduced, and the low dielectric loss characteristic can be improved.

However, the values of relative permittivity ε _r and loss tangent tanδ used in the numericalization of dielectric properties and dielectric loss are based on the measurement of powders made of inorganic fillers, or dispersions of inorganic fillers dispersed in solvents, etc. The slurry (hereinafter referred to as "inorganic filler powder, etc.") is the value converted from the measured value. The measurement method refers to the shape of the object to be measured, that is, to choose appropriately for any shape of powder or slurry. Specifically, for example, they can be measured individually by the method described in the Examples described later. Also, in the form of slurry, it is preferable to use an organic solvent as a solvent for dispersing inorganic fillers, which does not damage the physical properties of relative permittivity, loss tangent, and loss coefficient, and can maintain the fluidity of the slurry. As such an organic solvent, n-hexadecane etc. are mentioned, for example.

The loss coefficient can be calculated by using the measured values of relative permittivity ε _r and loss tangent tan δ of inorganic filler powder, etc., according to the following formula. (Loss coefficient)=(ε _r ) ^1/2 ×tanδ×10 ³ (where, ε _r [-] represents the relative permittivity of the powder of the inorganic filler used in the measurement, and tanδ[-] represents The loss tangent of these.)

The relative permittivity (ε _r ) is a parameter used to measure the degree of polarization of the inorganic filler powder used. The higher the relative permittivity, the greater the propagation delay of electrical signals. Therefore, in order to increase the propagation speed of the signal, it is better to have a lower relative permittivity. Loss tangent (tanδ) is a parameter that shows the amount of signal that propagates inside the powder of the inorganic filler used in the measurement, and is converted into heat and lost. The lower the loss tangent, the less the loss of the signal, and the signal can be improved. Conveyance rate.

The average particle size D50 of the inorganic filler (the particle size at which the cumulative particle size of the volume-based cumulative particle size distribution is 50%) is not particularly limited, for example, in the shape of the size or thickness of a molded product containing a low dielectric loss resin composition , and in the production of low dielectric loss resin composition, appropriate settings can be set in response to reasons such as adjustment of fluidity of materials containing inorganic fillers. Usually, the upper limit of the average particle diameter D50 of the inorganic filler is 50 μm or less, preferably 10 μm or less, more preferably 1 μm or less. On the one hand, the lower limit of the average particle diameter D50 of the inorganic filler is 0.001 μm or more, preferably 0.01 μm or more, more preferably 0.1 μm or more. When the particle size D50 of the inorganic filler is too large, it is difficult to make the surface of the molded article flat. As a result, for example, when a laminate is formed, the electrical properties of the laminate may be impaired due to irregularities on the surface of the molded product. On the other hand, if the particle size D50 of the inorganic filler is too small, it will be difficult to mix the inorganic filler with the polymer resin evenly, and the viscosity of the mixture will increase so that it is difficult to form the low dielectric loss resin composition.

In addition, when the average particle diameter D50 of the inorganic filler is a low dielectric loss resin composition in the form of the present embodiment is a film-shaped or sheet-shaped molded product, it is set to be less than 1/5 of the thickness of the molded product. Good, more preferably set to 1/10 or less. For example, when the molded product of the low dielectric loss resin composition is in the form of a film or sheet with a thickness of about 10 μm, the average particle diameter D50 of the inorganic filler is preferably 2 μm or less, more preferably 1 μm or less.

However, the average particle diameter D50 of the inorganic filler is, for example, a value measured by the laser diffraction/scattering method using Microtrac MT3300EXII (trade name, manufactured by Nikkiso Co., Ltd.).

The shape of the inorganic filler is not particularly limited, and is appropriately selected in consideration of, for example, the fluidity of the mixture when the inorganic filler is mixed with a polymer resin. In addition, it can be appropriately selected according to the purpose of controlling the mechanical strength, thermal conductivity, and gas diffusibility of molded articles containing the low dielectric loss resin composition.

Specific examples of the shape of the inorganic filler include arbitrary shapes such as a spherical shape, a substantially spherical shape, an elliptical shape, a rod shape, a needle shape, a spindle shape, and a plate shape. Moreover, the inorganic filler of these shapes may be hollow in the internal installation space. Furthermore, the low dielectric loss resin composition of this embodiment may contain inorganic fillers of the same shape, or two or more inorganic fillers of different shapes.

Inorganic fillers improve the wettability of polymer resins, improve the dispersibility of polymer resins, improve the processability of molded products containing low dielectric loss resin compositions during and after molding, and combine with polymer resins. Adhesion of resin, improvement of mechanical strength of low dielectric loss resin composition, inhibition or prevention of moisture absorption or oxidation by inorganic filler, prevention of electrification during treatment of inorganic filler, aggregation of inorganic filler Surface treatment (surface modification) may be performed for the purpose of preventing, or for the purpose of coloring or adjusting the refractive index according to the application.

As surface modifiers that can be used for surface modification of inorganic fillers, specifically, fatty acids such as stearic acid, oleic acid, and linoleic acid; anionic, cationic, and nonionic, depending on the purpose Surfactants such as surfactants; coupling agents of phosphoric acid, silane and carboxylic acid systems; polymer surface modifiers such as maleic acid-modified polypropylene, etc. Among these surface modifiers, phosphoric acid-based, silane-based, and carboxylic acid-based coupling agents are used from the viewpoint of improving the wettability of polymer resins and the dispersibility of inorganic fillers in polymer resins. better.

Regarding the content of the inorganic filler, the lower limit is preferably at least 1% by mass, more preferably at least 10% by mass, especially preferably at least 20% by mass, with respect to the total mass of the low dielectric loss resin composition . On the other hand, the upper limit of the content of the inorganic filler is preferably not more than 85% by mass, more preferably not more than 82% by mass, especially not more than 79% by mass, with respect to the total mass of the low dielectric loss resin composition better. When the lower limit of the content of the inorganic filler is more than 1% by mass, the loss coefficient of the low dielectric loss resin composition is small, and the improvement of the low dielectric loss property can be achieved. On the other hand, when the upper limit of the content of the inorganic filler is 85% by mass or less, the physical strength such as brittleness can be prevented, the hardness can be improved, the coefficient of thermal expansion (CTE: Coefficient of Thermal Expansion) can be reduced, and weather resistance can be achieved. Enhancement of sex.

In addition, in the inorganic filler of this embodiment, for example, the mass reduction after heat treatment at 400° C. or higher can be used in an amount of 2 mass % or less, preferably 1.5 mass %, with respect to the mass of the inorganic filler before heat treatment. mass % or less, more preferably 1 mass % or less. Through the use of inorganic fillers whose mass reduction after heat treatment is 2% by mass or less, heat generation during polymerization of monomers forming polymer resins, degassing of impurities during heat treatment, and degassing of main components of polymer resins Thermal decomposition, etc., can prevent the low dielectric loss properties and mechanical strength of the low dielectric loss resin composition from decreasing. Among the inorganic fillers, there are no particular limitations on the method of reducing the mass loss after the heat treatment to 2% by mass or less. For example, materials with high thermal decomposition temperature or heating Materials that do not undergo a phase change from time to time, and impurities that cause mass loss during the synthesis of inorganic fillers, which are removed or reduced by heat treatment or chemical solution treatment in advance. However, the above-mentioned content of the inorganic filler shows the value before the heat treatment at 400° C. or higher.

<The manufacturing method of the inorganic filler> Next, the manufacturing method of the inorganic filler is demonstrated as follows. First, the production method when the inorganic filler is BiF ₃ , ZrF ₄ , HfF ₄ , or CeF ₃ will be described.

When the inorganic filler is _BiF3 , etc., the production method includes the process of making a metal fluoride slurry by reacting a metal salt with a solution containing fluoride ions and/or ammonium ions, and the process of separating the metal fluoride from solid and liquid. The slurry is further cleaned, and the water and solvent are removed from the cleaned metal fluoride paste, and an inorganic compound selected from at least one kind of BiF ₃ , ZrF ₄ , HfF ₄ , and CeF ₃ is produced. The dry solid engineering of fillers. The solid-liquid separation of the metal fluoride slurry and the further cleaning process can be omitted as appropriate.

The reaction system between metal salts and fluoride ions and/or ammonium ions for making metal fluoride slurries can be, for example, adding solid metal salts to solutions containing fluoride and/or ammonium compounds (hereinafter referred to as "fluoride Wait for the solution".) to proceed. Also, it may be carried out by mixing a metal salt solution and a solution such as a fluoride compound. However, it is preferable to pass through a solution such as a metal salt solution or a fluoride compound before being used in these reactions to remove foreign substances.

The metal salt is not particularly limited, and examples include bismuth chloride, bismuth sulfate, bismuth acetate, bismuth nitrate, bismuth hydroxide, zirconium chloride, zirconium sulfate, zirconium acetate, zirconium nitrate, zirconium hydroxide, hafnium chloride, sulfuric acid Hafnium, hafnium acetate, hafnium nitrate, hafnium hydroxide, cerium chloride, cerium sulfate, cerium acetate, cerium nitrate, cerium hydroxide, etc. These metal salts may be used alone or in combination of two or more.

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

The aforementioned metal salt solution is obtained by dissolving metal salt in a solvent. The temperature of the medium at the time of dissolving the metal salt in the solvent is appropriately set in accordance with the solubility of the metal salt in the solvent and the like. For example, when the metal salt exhibits sufficient solubility in the solvent at room temperature, the metal salt may be dissolved in the solvent at room temperature. Also, when the solubility of the solvent of the metal salt is small at room temperature, the metal salt may be added after heating the solvent. Thereby, shortening of the time required for the metal salt to dissolve in the solvent can be achieved.

Fluoride and ammonium compounds in solutions such as fluoride are not particularly limited, for example, ammonium fluoride, acidic ammonium fluoride, sodium fluoride, potassium fluoride, alkyl ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate , And hydrogen fluoride etc. These fluorides and ammonium compounds may be used alone or in combination of two or more.

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

Solutions such as fluoride can be prepared by dissolving fluoride and/or ammonium compounds in a solvent.

Although the reaction temperature of solid metal salt or metal salt solution, and fluoride and other solutions is not particularly limited, usually, the lower limit is above 20°C, and the upper limit is below 60°C, preferably the lower limit is 20°C Above, the upper limit is 50°C or less. By setting the reaction temperature at 20° C. or higher, it is possible to suppress an excessive decline in the reaction between a solid metal salt or a metal salt solution, and a solution such as a fluoride. On the other hand, by keeping the reaction temperature below 60°C, it is possible to prevent the volatilization of some components from the solid metal salt or metal salt solution, and fluoride and other solutions, and change the concentration of these solutions.

When a solid metal salt is added to a solution such as fluoride, or a solution of a mixed metal salt and fluoride ions, the reaction between the metal salt and fluoride ions and/or ammonium ions proceeds rapidly, resulting in the precipitation of ammonium fluoride zirconate and other metals Fluoride, resulting in a slurry of metal fluoride. However. In order to precipitate more metal fluorides, it can be concentrated by heating or reducing the pressure of metal salt solution or fluoride solution, or adding a weak solvent. Here, the weak solvent is not particularly limited, and examples thereof include alcohol solutions such as methanol, ethanol, propanol, and propanol, and mixed solutions of alcohol solutions and water.

However, for the slurry of metal fluoride obtained in this project, it is also possible to apply drying treatment. In this case, although it does not specifically limit as a drying method, For example, natural drying, hot-air drying, etc. are mentioned. Moreover, drying conditions, such as a drying temperature and drying hours, are not specifically limited, either, and can be set suitably.

The method for solid-liquid separation of the metal fluoride slurry is not particularly limited, and examples thereof include centrifugal dehydration and pressure filtration. However, the particle size of the metal fluoride is small and fine, and when the solid-liquid separation is difficult for suction filtration, centrifugal dehydration, and pressure filtration, a centrifuge can be used. Also, the slurry itself of the metal fluoride may be dried up by evaporation.

Furthermore, the method of cleaning the metal fluoride paste obtained by solid-liquid separation is not particularly limited, and examples thereof include washing with water. Thereby, unreacted fluoride and other anions can be removed from the metal fluoride paste. However, the washing temperature and washing time are not particularly limited, and can be appropriately set as needed.

As a method of removing moisture and a solvent (such as a water-containing alcohol component or an ammonium component) from the washed metal fluoride paste, for example, heating treatment is mentioned. Thus, a dry powder of the metal fluoride can be obtained. The heat treatment method is not particularly limited, and examples include a method in which a metal fluoride paste is placed in a drying table and dried in a dryer.

The heating temperature during 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, moisture and ammonium components contained in the metal fluoride paste can be sufficiently removed or reduced. On the other hand, by setting the heating temperature at 600° C. or lower, thermal fusion or thermal decomposition of metal fluorides can be prevented.

The heating time during the heat treatment is preferably in the range of 1 hour to 48 hours, more preferably in the range of 3 hours to 8 hours. By setting the heating time to 1 hour or more, the moisture and ammonium components contained in the metal fluoride paste can be sufficiently removed or reduced. On the other hand, by setting the heating time to 48 hours or less, thermal fusion or thermal decomposition of metal fluorides can be prevented.

In addition, the heat treatment may be performed in the atmosphere or in an inert gas atmosphere. It does not specifically limit as an inert gas, For example, nitrogen gas, argon gas, etc. are mentioned. Also, from the viewpoint of accelerating the drying of the metal fluoride paste, for example, heat treatment may be performed under a reduced pressure environment. Although the degree of decompression is not particularly limited, it is better to use an oil-free dry vacuum pump or an oil rotary vacuum pump in the range of 10 ^-5 Pa to 10 ^-2 Pa.

Next, the production method when the inorganic filler is K ₂ SiF ₆ will be described. In the production method when the inorganic filler is K ₂ SiF ₆ , the metal salt in the slurry process for making the aforementioned metal fluoride is replaced by silicon fluoride. In more detail, it includes the process of making a slurry of K ₂ SiF ₆ by reacting silicon fluoride and potassium hydrogen fluoride, and the process of separating the slurry of K ₂ SiF ₆ from solid and liquid for further cleaning, and from cleaning After the K ₂ SiF ₆ paste, the water and solvent are removed, and the dry solid of the inorganic filler made of K ₂ SiF ₆ is made.

The reaction of silicon fluoride and potassium hydrogen fluoride in the process of making K ₂ SiF ₆ slurry can be carried out by adding solid potassium hydrogen fluoride to an aqueous solution of silicon fluoride, for example. Also, it may be performed by mixing a solution of silicon fluoride and a solution in which potassium hydrogen fluoride is dissolved. However, it is better to filter the aqueous solution of silicon fluoride or the solution of dissolving potassium bifluoride before using in these reactions to remove foreign matter.

The silicon fluoride system is not particularly limited, and examples thereof include hydrogen silicon fluoride (H ₂ SiF ₆ ), ammonium silicon fluoride ((NH ₄ ) ₂ SiF ₆ ), and hexafluorosilicic acid (H ₂ SiF ₆ ).

The process of solid-liquid separation of K ₂ SiF ₆ slurry and cleaning, and the process of removing water and solvent from the washed K ₂ SiF ₆ paste to make K ₂ SiF ₆ dry solid and the above-mentioned The same applies to inorganic fillers such as BiF ₃ . Therefore, this detailed description is omitted.

Through the above, the inorganic filler of the aspect of this embodiment can be manufactured. In the above description, the case where an inorganic filler such as BiF ₃ or K ₂ SiF ₆ is produced by a wet method has been described as an example. However, the inorganic filler of the present invention can be produced by a dry method. That is, for example, when producing ZrF ₄ as an inorganic filler, (NH ₄ ) ₂ ZrF ₆ as a raw material is heat-treated in an inert gas atmosphere. Thus, (NH ₄ ) ₂ ZrF ₆ can be thermally decomposed to generate ZrF ₄ . In this dry method, compared with the wet method, it is possible to produce inorganic fillers with reduced impurities. It does not specifically limit as an inert gas, For example, nitrogen gas, argon gas, etc. are mentioned.

The heating temperature during heat treatment is preferably in the range of 400°C to 500°C. By setting the heating temperature at 400°C or higher, (NH ₄ ) ₂ ZrF ₆ can be sufficiently thermally decomposed. On the other hand, by setting the heating temperature at 500° C. or lower, thermal fusion or thermal decomposition of ZrF ₄ can be prevented.

The heating time during heat treatment is preferably in the range of 2 hours to 6 hours. By setting the heating time to 2 hours or more, (NH ₄ ) ₂ ZrF ₆ can be sufficiently thermally decomposed. On the other hand, by setting the heating time to 6 hours or less, thermal fusion or thermal decomposition of ZrF ₄ can be prevented.

However, when adjusting the average particle diameter of the obtained inorganic filler, it can grind|pulverize an inorganic filler by a well-known pulverization method etc., for example. 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 is to consider the degree of particle size or purity of the inorganic filler, and it can be selected appropriately.

In addition, in the production process of the inorganic filler, the particle size and shape can be controlled. For example, when producing zirconium fluoride (ZrF ₄ ), in the process of making zirconium fluoride slurry, the environment for the growth of inorganic fillers can be adjusted by appropriately changing the reaction temperature of zirconium salt, fluoride ion and/or ammonium ion And to this extent, the particle size and shape of the inorganic filler are controlled. In addition, after the process of producing the dry solid of zirconium fluoride, the particle size and shape of the inorganic filler can also be controlled by performing post-processing processes such as heat treatment. The heating temperature and heating time during the heat treatment are not particularly limited, and can be appropriately set. However, the particle size and shape of BiF ₃ , HfF ₄ , CeF ₃ , and K ₂ SiF ₆ can be controlled in the same manner as ZrF ₄ .

＜Polymer resin＞ The polymer resin preferably contains at least one kind of thermoplastic resin and/or at least one kind of thermosetting resin.

More specifically, polymer resins include olefin-based resins such as polyethylene resins and polypropylene resins; styrene-based resins such as polystyrene resins and acrylonitrile butadiene styrene resins (ABS resins); Polyethylene resins such as vinyl acetate resin, polyvinyl chloride resin, polyvinyl alcohol resin and polyvinylidene chloride resin; methacrylic resin; thermoplastic elastomer resin; thermoplastic polyurethane resin; polyacrylonitrile resin; polylactic acid Resin; polyamide acetal resin; polycarbonate resin; polyphenylene ether resin; polyethylene terephthalate resin; polyethylene resin; polyether resin; polyphenylene sulfide resin; polyether ether ketone resin ; liquid crystal polymer resin; polyimide resin; polytetrafluoroethylene (PTFE), polytetrafluoroethylene and perfluoroalkoxy vinyl copolymer (PFA), polychlorotrifluoroethylene resin (PCTFE), four Fluorine resins such as fluoroethylene-hexafluoropropylene copolymer (FEP) and tetrafluoroethylene-ethylene copolymer (ETFE); phenolic resins; amine resins such as urea resins and melamine resins; furan resins; unsaturated polyester resins; Oxygen resin; diallyl phthalate resin; guanamine resin; ketone resin; silicone resin; thermosetting elastomer resin; natural rubber; chloroprene rubber, styrene butadiene rubber, isoprene Synthetic rubbers such as diene rubber, butyl rubber and urethane rubber; and their modified products, etc. 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 using a polymer resin mixed with polyphenylene ether resin and epoxy resin, the processability can be improved by increasing the fluidity. However, the degree of polymerization of the polymer resin is not particularly limited, and may be appropriately selected according to the application of the low dielectric loss resin composition.

The content of the polymer resin is not particularly limited, and can be appropriately set as needed.

＜Other matters＞ In the low dielectric loss resin composition of this embodiment, impurities may be contained within the range that does not violate the object of the present invention. Examples of impurities include metal impurities having elements other than Bi, Zr, Hf, Ce, Si, and F, metal oxides, and metal fluorides. The content of impurities is preferably 100 ppm or less, more preferably 10 ppm or less, with respect to the total mass of the low dielectric loss resin composition.

In addition, the low dielectric loss resin composition of this embodiment may contain other additives within the range that does not violate the object of the present invention. The other additives are not particularly limited, and examples thereof include hardeners, lubricants, crystal nucleating agents, UV protection agents, colorants, flame retardants, stabilizers, plasticizers, and strengthening agents.

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

In addition, the low dielectric loss resin composition of this embodiment may contain other inorganic fillers than the aforementioned inorganic fillers. Other inorganic fillers are not particularly limited, and examples include silica, alumina, barium sulfate, talc, clay, mica powder, zirconium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, nitrogen Boron oxide, zirconium borate, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and fluorine compounds. As other inorganic fillers, fibrous fillers such as paper, glass non-woven fabrics, synthetic fibers, cellulose insulation materials, carbon fibers, and carbon nanotubes are not limited to the shape of low dielectric loss resin compositions Wait for it to be used.

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

However, the low dielectric loss resin composition of this embodiment includes not only the case where other additives or other inorganic fillers are included, but also the case where only the inorganic filler and polymer resin are included.

The low dielectric loss resin composition of this embodiment can be a resin composition for an insulating film (solder resist), a semiconductor sealing resin composition, an adhesive, a paint, a coating material for wiring such as power supply and communication, etc. use.

<Manufacturing method of low dielectric loss resin composition> Next, the method of manufacturing the low dielectric loss resin composition according to this embodiment will be described below. 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 through uniform mixing or kneading. In addition, it is also possible to dissolve or disperse polymer resins or monomers forming polymer resins in organic solvents (such as varnishes or dispersions, etc.), by adding inorganic fillers and any other additives. Distributed and manufactured.

(Molded body for high-frequency equipment and its manufacturing method) The molded article for high-frequency equipment (hereinafter referred to as "the molded article") according to this embodiment is made of a molded article containing a low dielectric loss resin composition.

The molding system can be produced, for example, through known kneading machines and extruders. As the kneading machine, for example, a closed pressurized kneader or an open kneader can be used. After using these kneading machines to produce a sheet-like low dielectric loss resin composition material, a molded body can be produced using the low dielectric loss resin composition material. In addition, after the pelletized low dielectric loss resin composition material is produced by an extruder, a molded body can be produced by using an injection molding machine. When using molding machines such as extruders to mix polymer resins with inorganic fillers and other additives, the number of processes can be reduced and production efficiency can be improved. In addition, since the inorganic filler is easy to absorb moisture, it can be properly dried before being mixed with the polymer resin.

Moreover, when manufacturing a sheet-shaped molded body, it can manufacture by a well-known method. For example, in a varnish tank filled with a polymer resin-containing solution (resin varnish), add an inorganic filler and any other additives to uniformly disperse them, and heat the dispersion at a specific temperature. The cured product produced by heating is stretched into a thin sheet to produce a thin sheet-shaped molded body.

Also, pass through a liquid tank containing a dispersion liquid of a polymer resin, an inorganic filler, and any other additives, etc., while impregnating a sheet-shaped base material such as glass valves, bonding sheets, etc., on the sheet-shaped base material, impregnated with dispersion liquid. Afterwards, the sheet impregnated with the dispersion liquid can be dried to produce an impregnated sheet impregnated with the low dielectric loss resin composition. However, a laminate in which a plurality of low dielectric loss resin composition layers are laminated can be produced by passing the sheet-like base material through the liquid tank of the dispersion liquid multiple times.

(high frequency machine) The high-frequency equipment related to the form of this embodiment includes a low dielectric loss resin composition, or a molded body having a low dielectric loss resin composition.

The high-frequency equipment in this embodiment is used for information processing and information communication by processing electronic signals. In particular, the high-frequency device of this embodiment is used in a frequency band of radio signals used for communication of 1 GHz or higher, more preferably 10 GHz or higher. In addition, the high-frequency equipment of this embodiment also includes high-frequency electronic components used in the high-frequency band.

Examples of high-frequency equipment include housings, circuit boards, printed wiring boards, transmission lines, capacitors, and inductors for information processing and information communication equipment, and roofing materials for rooms where high-frequency equipment is installed. Wall materials, etc. In addition, high-frequency equipment equipped with an insulating film or semiconductor sealing resin formed with a low dielectric loss resin composition, a covering material, wiring coated with a low dielectric loss resin composition, etc., are also included in the form of this embodiment. The high frequency machine. [Example]

Hereinafter, suitable embodiments of this invention will be described in detail by way of example. Materials However, the scope of the present invention is not limited to the materials and compounding amounts described in the following examples unless there is any particular limitation.

(Manufacturing example of BiF ₃ ) Measured separately, 50 g of Bi(OH) ₃ (manufactured by High Purity Chemical Research Institute Co., Ltd.), 72 g of pure water, and 66 g of HNO ₃ aqueous solution (concentration: 69 % by mass, manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd.), was placed in a reaction container made of PFA, and the temperature of the liquid was raised to 60° C. in a water bath to generate bismuth nitrate. Next, the liquid temperature was kept at 60° C. and stirred, and 41 g of HF aqueous solution (concentration: 50% by mass, manufactured by STELLA CHEMIFA Co., Ltd.) was continuously added in small amounts over about 30 minutes to obtain a reaction liquid. Afterwards, the temperature of the reaction solution was kept below 60° C., and the reaction solution was matured for 1 hour.

Next, the reaction container was taken out from the water bath, and was left still for 30 minutes to precipitate a product. After discarding the supernatant, methanol (200 g, manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd.) was added, followed by stirring for 5 minutes. Next, the stirred reaction solution was suction-filtered with a filter membrane (pore size: 5 μm: manufactured by Millipore), and left as a filter to obtain rough BiF ₃ particles (51.1 g). The obtained white powder was filled in an alumina crucible, and the white powder was heat-treated in an _N2 gas environment using an electric furnace. The heat treatment temperature was 600° C., and the heat treatment time was 2 hours. After the heat treatment, return to room temperature under N ₂ gas atmosphere, and take out 49.0 g of white powder from the alumina crucible. As a result of analyzing the white powder by XRD (X-ray Diffraction, trade name: RINT-Ultima III, manufactured by Rigaku Corporation), the white powder is BiF ₃ . Also, the yield of BiF ₃ was 95%.

(Production example of ZrF ₄ ) An alumina crucible was filled with 1250 g of (NH ₄ ) ₂ ZrF ₆ (manufactured by STELLA CHEMIFA Co., Ltd.), and heat-treated in an N ₂ gas atmosphere using an electric furnace. The heat treatment temperature was 400° C., and the heat treatment time was 2 hours. After the heat treatment, return to room temperature under N ₂ gas atmosphere, and take out 860 g of white powder from the alumina crucible. As a result of analyzing the white powder by XRD (X-ray Diffraction, trade name: RINT-Ultima III, manufactured by Rigaku Corporation), the white powder is ZrF ₄ . Also, the yield of ZrF ₄ was 99%.

(Manufacturing example of HfF ₄ ) Measured separately, 10g of HfO ₂ (manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd.) and 40g of pure water were placed in a reaction vessel made of PFA, and the temperature of the liquid was adjusted to After 20°C, keep the liquid temperature at 20°C and stir, and add 5.1 g of HF aqueous solution (concentration: 75% by mass, manufactured by STELLA CHEMIFA Co., Ltd.) continuously for about 30 minutes in small amounts to obtain a reaction liquid . Thereafter, the temperature of the reaction solution was kept below 30° C., and the reaction solution was matured for 2 hours.

Next, the reaction container was taken out from the water bath and placed on a stand for 2 hours. When the reaction solution reached room temperature, isopropanol (150 g, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) was added and stirred well. Next, the stirred reaction solution was suction-filtered with a filter membrane (pore size: 5 μm: manufactured by Millipore), and left as a filter to obtain coarse HfF ₄ particles (11 g). The obtained white powder was filled in an alumina crucible, and the white powder was heat-treated in an _N2 gas environment using an electric furnace. The heat treatment temperature was 400° C., and the heat treatment time was 2 hours. After the heat treatment, return to room temperature under N ₂ gas atmosphere, and take out 11 g of white powder from the alumina crucible. As a result of analyzing the white powder by XRD (X-ray Diffraction, trade name: RINT-Ultima III, manufactured by Rigaku Corporation), the white powder was HfF ₄ . Also, the yield of HfF ₄ was 91%.

(Manufacturing example of CeF ₃ ) Measured separately, 10g of CeCl ₃・7H ₂ O (High Purity Chemical Laboratory), 115g of pure water, and 7.4g of HNO ₃ aqueous solution (concentration: 69% by mass, Fuji Wako Pure Pharmaceutical Co., Ltd.) was placed in a reaction vessel made of PFA, and the temperature of the liquid was brought to 60° C. in a water bath to generate cerium nitrate. Furthermore, while stirring while keeping the liquid temperature at 60° C., 3.3 g of HF aqueous solution (concentration: 50% by mass, manufactured by STELLA CHEMIFA Co., Ltd.) was continuously added in small amounts over about 30 minutes to obtain a reaction liquid. Afterwards, the temperature of the reaction solution was kept below 60° C., and the reaction solution was matured for 1 hour.

Next, the reaction container was taken out from the water bath, and was left still for 30 minutes to precipitate a product. After discarding the supernatant, methanol (100 g, manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd.) was added, followed by stirring for 5 minutes. Next, the stirred reaction solution was suction-filtered with a filter membrane (pore size: 5 μm: manufactured by Millipore) and left on the filter to obtain coarse CeF ₃ particles (4.9 g). The obtained white powder was filled in an alumina crucible, and the white powder was heat-treated in an _N2 gas environment using an electric furnace. The heat treatment temperature was 600° C., and the heat treatment time was 2 hours. After the heat treatment, return to room temperature under N ₂ gas atmosphere, and take out 4.8 g of white powder from the alumina crucible. As a result of analyzing the white powder by XRD (X-ray Diffraction, trade name: RINT-Ultima III, manufactured by Rigaku Corporation), the white powder is CeF ₃ . Also, the yield of CeF ₃ was 91%.

(Production example of K ₂ SiF ₆ ) Each was measured, and 400 g of H ₂ SiF ₆ aqueous solution (concentration: 40% by mass) was placed in a reaction container made of PFA, and the liquid temperature was adjusted to 40° C. in a water bath. Stirring was maintained at 40°C, and 208 g of KF・HF (manufactured by STELLA CHEMIFA Co., Ltd.) was continuously added in small amounts over about 30 minutes to obtain a reaction liquid. Thereafter, the temperature of the reaction solution was kept below 40° C., and the reaction solution was matured for 2 hours.

Next, the reaction container was taken out from the water bath and left to stand for 2 hours. When the reaction liquid reached room temperature, isopropanol (600 g, manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd.) was added and stirred well. Next, the stirred reaction solution was suction-filtered with a filter membrane (pore size: 5 μm: manufactured by Millipore), and left as a filter to obtain coarse K ₂ SiF ₆ particles (238 g). The obtained white powder (K ₂ SiF ₆ crystal) was filled in an alumina crucible, and the white powder was heat-treated in an electric furnace under N ₂ gas atmosphere. The heat treatment temperature was 400° C., and the heat treatment time was 4 hours. However, the mass reduction of K ₂ SiF ₆ after heat treatment is ((mass of K ₂ SiF ₆ before heat treatment)-(mass of K ₂ SiF ₆ after heat treatment))/(mass of K ₂ SiF ₆ before heat treatment) ×100 (mass %)) is 0.1 mass % or less.

After the heat treatment, return to room temperature under N ₂ gas atmosphere, and take out 237 g of white powder from the alumina crucible. As a result of analyzing the white powder by XRD (X-ray Diffraction, trade name: RINT-Ultima III, manufactured by Rigaku Corporation), the white powder is K ₂ SiF ₆ . Also, the yield of K ₂ SiF ₆ was 97%.

(Example 1) In a tube made of fluororesin, the powder of the aforementioned inorganic filler ZrF ₄ (D50: 5.0 μm) was filled in advance, and passed through a frequency of 10 GHz at a temperature of 19°C and an ambient atmosphere of a relative humidity of 50%. The cavity resonator method in the field measures the relative permittivity and loss tangent respectively. In the measurement, a circuit network analyzer (manufactured by Keysight Technologies Co., Ltd., trade name: E8361A) was used. After that, for the relative permittivity and loss tangent measurements of the fluororesin tubes filled with inorganic fillers, the bulk density and true density of the inorganic fillers, and the filling amount of the inorganic fillers that lead to the filled volume, were used for porosity measurement. For partial correction, calculate the relative permittivity and loss tangent of the inorganic filler. Furthermore, the measured values of relative permittivity and loss tangent of the inorganic filler are corrected, and the dielectric loss of the inorganic filler is calculated according to the following formula using the corrected value. The results are shown in Table 1. However, the values of the relative permittivity and loss tangent of the inorganic filler in Table 1 represent corrected measured values. (Loss coefficient)=(ε _r1 ) ^1/2 ×tanδ ₁ ×10 ³ (where, ε _r1 [-] represents the relative permittivity of inorganic filler powder, etc., and tanδ ₁ [-] represents the inorganic filler agent loss tangent.)

(Example 2) In Example 2, as shown in Table 1, the inorganic filler was changed to the previously prepared K ₂ SiF ₆ (D50: 1.9 μm). Other than that, it measured similarly to Example 1.

(Comparative Example 1) In Comparative Example 1, as shown in Table 1, the inorganic filler was changed to SiO ₂ (D50: 2.0 μm). Other than that, it measured similarly to Example 1.

(result 1) As shown in Table 1, the inorganic fillers used in Examples 1 and 2 have smaller loss coefficients measured at the same frequency than the inorganic fillers used in Comparative Example 1, and it was confirmed that they have excellent low dielectric loss characteristics.

(Example 3) 80.0 g of the aforementioned inorganic filler BiF ₃ (D50: 8.5 μm) and 120 g of n-hexadecane (manufactured by Fujifilm Wako Pure Chemical Co., Ltd., premium grade for reagents) were placed in The container cup is stirred with a tissue homogenizer to make a slurry.

Next, inject the prepared inorganic filler slurry into a PFA heat-shrinkable tube (length 8cm, outer diameter 2.2mm, inner diameter 1.8mm) through a syringe, etc., to prevent the slurry from leaking, and use a PFA rod (diameter 2mm) to Closed and heated with a hot air hairdryer. Thereby, the test piece of the slurry containing the inorganic filler of this Example was produced.

Then, for the slurry of the inorganic filler in the obtained test piece, the relative permittivity and loss tangent of the 1GHz and 10GHz frequency ranges were respectively measured by the cavity resonator method in an ambient atmosphere with a temperature of 19°C and a relative humidity of 50%. . In the measurement, a circuit network analyzer (manufactured by Keysight Technologies Co., Ltd., trade name: E8361A) was used. The loss coefficient of the slurry of the inorganic filler was calculated using the measured values of the relative permittivity and loss tangent of the slurry of the inorganic filler according to the following formula. The results are shown in Table 2. (Loss coefficient)=(ε _r2 ) ^1/2 ×tanδ ₂ ×10 ³ (where, ε _r2 [-] represents the relative permittivity of the slurry of the inorganic filler, and tanδ ₂ [-] represents the inorganic filler The loss tangent of the slurry.)

(Examples 4~9) In Examples 4~9, as shown in Table 2, the inorganic fillers were changed to ZrF ₄ (D50: 5.0 μm), HfF ₄ (D50: 5.9 μm), CeF ₃ (D50: 2.0 μm), or K ₂ SiF ₆ (D50: 1.9 μm). In addition, the mass percent concentration and the volume percent concentration of the inorganic filler were changed to the values shown in Table 2, respectively. Other than that, it carried out similarly to Example 3, and produced the test piece about each of Examples 4-9. Furthermore, the relative permittivity and loss tangent were measured similarly to Example 1 about each inorganic filler of Examples 4-9, and the loss coefficient was calculated, respectively. The results are shown in Table 2.

(Comparative Examples 2 to 7) In Comparative Examples 2 to 7, as shown in Table 2, the inorganic filler was changed to MgF ₂ (D50: 20 μm), CaF ₂ (D50: 9.0 μm), or SiO ₂ ( D50: 2.0 μm). In addition, the mass percent concentration and the volume percent concentration of the inorganic filler were changed to the values shown in Table 2, respectively. Except for this, it carried out similarly to Example 3, and produced the test piece about each of Comparative Examples 2-7. Furthermore, the relative permittivity and loss tangent were measured similarly to Example 1 about each inorganic filler of Comparative Examples 2-7, and the loss coefficient was calculated, respectively. The results are shown in Table 2.

(result 2) As shown in Table 2, compared with the inorganic fillers used in Comparative Examples 2 to 7, the inorganic fillers used in Examples 3 to 9 have smaller loss coefficients measured at the same frequency and volume concentration, confirming that Excellent low dielectric loss characteristics.

(Example 10 (production of test piece using epoxy resin)) 10 g of epoxy resin (trade name: jER (registered trademark) 820, manufactured by Mitsubishi Chemical Co., Ltd.), epoxy resin hardener (trade name : jERCURE (registered trademark), Mitsubishi Chemical Co., Ltd.) 5g, and inorganic filler (ZrF ₄ (D50: 5.0μm)) 15g, put in a container cup, mix in a defoaming mixer, and make a paste low dielectric loss resin composition.

The prepared paste-like low dielectric loss resin composition was put into a metal mold, and cured at room temperature for 1 day, and then heated and cured at 80° C. for 3 hours. After that, it was taken out from the metal mold, and a molded body (inorganic-organic composite material test piece) of the low dielectric loss resin composition of Example 10 was produced.

Next, the relative permittivity and loss tangent in the frequency range of 10 GHz were measured for the obtained molded body by the cavity resonator method in an ambient atmosphere at a temperature of 19°C and a relative humidity of 50%. For the measurement, a circuit network analyzer (trade name: E8361A, manufactured by Keysight Technologies Co., Ltd.) was used. Furthermore, the loss coefficient of the molded body was calculated according to the following formula. The results are shown in Table 3. (Loss coefficient)=(ε _r3 ) ^1/2 ×tanδ ₃ ×10 ³ (In the formula, ε _r3 [-] means the relative permittivity of the molded body, and tanδ ₃ [-] means the loss tangent of the molded body.)

(Examples 11 to 17 (production of test pieces using epoxy resin)) In Examples 11 to 17, as shown in Table 3, the inorganic filler was changed to HfF ₄ (D50: 5.9 μm), Or K ₂ SiF ₆ (D50: 1.9 μm). Moreover, the mass percentage concentration of the inorganic filler was changed to the value shown in Table 3, respectively. Other than that, in the same manner as in Example 10, molded articles of the low dielectric loss resin compositions of Examples 11 to 17 were produced. Furthermore, the relative permittivity and loss tangent were measured in the same manner as in Example 10 for the molded articles of Examples 11 to 17, and the loss coefficients were calculated respectively. The results are shown in Table 3.

(Comparative Examples 8~11 (production of test pieces using epoxy resin)) In Comparative Examples 8~10, as shown in Table 3, the inorganic fillers were changed to CaF ₂ (D50: 9.0μm), SiO ₂ (D50: 2.0 μm) or Al ₂ O ₃ (D50: 4.7 μm). In addition, in Comparative Example 11, no inorganic filler was used. Other than that, in the same manner as in Example 10, molded articles of the low dielectric loss resin compositions of Comparative Examples 8 to 11 were produced. Furthermore, the relative permittivity and loss tangent were measured in the same manner as in Example 10 for the molded articles of Comparative Examples 8 to 11, and the loss coefficients were calculated respectively. The results are shown in Table 3.

(Comparative example 12 (production of test piece using epoxy resin)) In addition, in Comparative Example 12, as shown in Table 3, no inorganic filler was used. Other than that, similarly to Example 17, a molded body of the low dielectric loss resin composition of Comparative Example 12 was produced. Furthermore, with respect to the molded article of Comparative Example 12, the relative permittivity and loss tangent were measured in the same manner as in Example 17, and the loss coefficients were calculated respectively. The results are shown in Table 3.

(result 3) As shown in Table 3, compared with the molded products of Comparative Examples 8-12, the low dielectric loss resin composition of Examples 10-17 can reduce the content of inorganic filler at the same mass percentage concentration. loss factor. In addition, the molding system formed by the low dielectric loss resin composition of Examples 10-17 can also reduce the loss coefficient when the content of the inorganic filler is a low volume percentage concentration compared with the moldings of Comparative Examples 8-12 . Therefore, it can be confirmed that the molded systems formed by the low dielectric loss resin compositions of Examples 10-17 are superior in low dielectric loss characteristics compared with the molded bodies of Comparative Examples 8-12.

Claims (10)

A low dielectric loss resin composition, which is a low dielectric loss resin composition containing at least a polymer resin and an inorganic filler, characterized in that the aforementioned inorganic filler is selected from BiF ₃ , ZrF ₄ , HfF ₄ , and CeF ₃ and at least one group of K ₂ SiF ₆ . The low dielectric loss resin composition according to Claim 1, wherein the content of the inorganic filler is 0.01% by mass to 85% by mass relative to the total mass of the low dielectric loss resin composition. The low dielectric loss resin composition according to claim 1, wherein the polymer resin includes at least one kind of thermoplastic resin and/or at least one kind of thermosetting resin. The low dielectric loss resin composition as described in Claim 1, wherein the polymer resin is selected from olefin resins, styrene resins, polyethylene resins, methacrylic resins, thermoplastic elastomer resins, thermoplastic Polyurethane resin, polyacrylonitrile resin, polylactic acid resin, polyamide acetal resin, polycarbonate resin, polyphenylene ether resin, polyethylene terephthalate, polyethylene resin, polyether resin, polyphenylene Sulfide, polyether ether ketone, liquid crystal polymer resin, polyimide resin, fluororesin, phenolic resin, amine resin, furan resin, unsaturated polyester resin, epoxy resin, diallyl phthalate resin , guanamine resin, ketone resin, polysiloxane resin, thermosetting resin, natural rubber, synthetic rubber, and at least one of these modified groups. A method for manufacturing a low dielectric loss resin composition, which is a method for manufacturing a low dielectric loss resin composition containing at least a polymer resin and an inorganic filler. The solution reaction of ions, the process of making the slurry of metal fluoride, and the process of heating and drying the slurry of the aforementioned metal fluoride to produce the aforementioned inorganic filler containing the metal fluoride; the aforementioned metal salt is selected from bismuth, zirconium, At least one of the group consisting of hafnium or cerium, chloride, sulfate, acetate, nitrate and hydroxide, the aforementioned metal fluoride is selected from the group consisting of BiF ₃ , ZrF ₄ , HfF ₄ and CeF ₃ At least 1 species. The method for producing a low dielectric loss resin composition according to claim 5, wherein the solution containing the aforementioned fluoride ions and/or ammonium ions is a solution containing fluoride and/or ammonium compounds. A method for producing a low dielectric loss resin composition, which is a method for producing a low dielectric loss resin composition containing at least a polymer resin and an inorganic filler. ₂ Process of SiF ₆ slurry, and process of heating and drying the aforementioned K ₂ SiF ₆ slurry to produce the aforementioned inorganic filler containing K ₂ SiF ₆ . A molded body for high-frequency machines, which is a molded body for high-frequency machines used in a frequency band above 1 GHz, characterized by It is made of a molded body containing the low dielectric loss resin composition described in any one of Claims 1 to 4. A high-frequency machine for use in a frequency band above 1 GHz, characterized by Including the low dielectric loss resin composition described in any one of Claims 1-4. A high-frequency machine for use in a frequency band above 1 GHz, characterized by A molded body comprising the low dielectric loss resin composition described in Claim 8.