Filler for low dielectric loss resin compositions, low dielectric loss resin composition, molded body for high frequency device, and high frequency device

Abstract

Provided are: a filler for low dielectric loss resin compositions, which is an inorganic filler having a small coefficient of thermal expansion and exhibiting excellent low dielectric characteristics and moisture resistance, and which can be applied to electronic components such as circuit boards, and to information communication devices and the like; a low dielectric loss resin composition; a molded body for a high frequency device; and a high frequency device. The present invention is a filler for low dielectric loss resin compositions, is characterized by comprising an inorganic filler that has a coefficient of thermal expansion of not more than 1×10-6(1 / K), and is characterized in that the dielectric loss tangent of the inorganic filler is not more than 0.002 at a temperature of 25°C and a frequency of not less than 1 GHz, and the mass change rate of the inorganic filler is not more than 0.5 mass% after being left still for 48 hours in an environment having a temperature of 85°C and a relative humidity of 85%.

Description

Fillers for low dielectric loss resin compositions, low dielectric loss resin compositions, molded articles for high-frequency equipment and high-frequency equipment

[0001] The present invention relates to a filler for low dielectric loss resin compositions, a low dielectric loss resin composition, a molded article for high-frequency equipment, and high-frequency equipment, which can be applied to electronic components such as circuit boards and information and communication equipment.

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

[0003] In particular, in high-frequency electronic components, the attenuation of electrical signals due to transmission loss in the transmission line increases with increasing frequency, which can lead to a decrease in transmission reliability. Therefore, materials with a small loss factor are required for high-frequency equipment and its components. Here, the loss factor is the relative permittivity (ε). ｒ It is obtained by the product of the square root of () and the dielectric loss tangent (tanδ).

[0004] Furthermore, electronic components for high-frequency applications are becoming smaller and more complex as frequencies increase. Therefore, differences in thermal expansion coefficients between dissimilar materials that make up these electronic components become a significant problem. These differences can cause distortion and delamination in electronic components, leading to a decrease in structural stability and electrical properties. For this reason, it is necessary to control the thermal expansion coefficients of the main constituent materials, such as the substrate, resin film, and adhesive layer.

[0005] Generally, many solid materials exhibit thermal expansion, meaning their volume and length increase as the temperature rises. In resin materials used in high-frequency electronic components, while it is possible to lower the loss coefficient, particularly the dielectric loss tangent, through molecular design, reducing the high coefficient of thermal expansion is considered difficult.

[0006] On the other hand, there are also materials that exhibit zero thermal expansion, where the volume does not change as the temperature rises, or negative thermal expansion, where the volume contracts. Such materials are sometimes used to suppress the coefficient of thermal expansion. For example, Patent Document 1 describes a vanadium compound (Cu) that exhibits negative thermal expansion, used to suppress the thermal expansion of materials that require electrical insulation. ２－Ｘ Zn Ｘ ) V ２ O ７ A thermal expansion-suppressing filler containing (0 < x < 2) and inorganic particles is disclosed. The inorganic particles are said to have negative thermal expansion properties or a low coefficient of thermal expansion, and it is possible to control the coefficient of thermal expansion by selecting the mixing ratio of the vanadium compound and the inorganic particles, and the type of inorganic particles.

[0007] Furthermore, Patent Document 2 describes ScF having negative thermal expansion characteristics. ３ A copper-based composite material coated with copper plating is disclosed. According to this Patent Document 2, by using this copper-based composite material in microwave devices and the like, it is possible to solve the problem of reduced dimensional and structural stability of precision machinery due to thermal expansion and contraction of the material.

[0008] Furthermore, Patent Document 3 discloses a negative thermal expansion material, which is a nanoparticle having magnetic and ferroelectric properties and having a negative thermal expansion coefficient at temperatures below the magnetic transition temperature of the nanoparticle. According to Patent Document 3, by incorporating this negative thermal expansion material into other compounds, it is possible to suppress changes in the expansion coefficient of the product due to temperature changes in thin film substrates and the like, where product quality stability is required.

[0009] The technologies disclosed in Patent Documents 1 to 3 describe how the overall thermal expansion coefficient can be suppressed by using materials that exhibit negative thermal expansion. However, none of the materials disclosed in these patent documents improve low dielectric loss characteristics in the high-frequency band of 1 GHz or higher. Furthermore, the reliability (humidity resistance) required in high-temperature and high-humidity environments for electronic components used in high-frequency applications has not been considered. Therefore, there is a need to develop materials that exhibit good low dielectric loss characteristics and high humidity resistance even when used in the high-frequency band, and that also have a good reduction in thermal expansion coefficient.

[0010] Japanese Patent Application Laid-Open No. 2021-62994, Japanese Patent Application Laid-Open No. 2022-34528, Japanese Patent Application Laid-Open No. 2010-29990

[0011] The present invention provides a filler for a low dielectric loss resin composition, a low dielectric loss resin composition, a molded body for high-frequency devices, and a high-frequency device, which is an inorganic filler having a low thermal expansion coefficient and excellent low dielectric properties and moisture resistance, and can be applied to electronic components such as circuit boards and information communication devices.

[0012] In order to solve the above problems, the filler for the low dielectric loss resin composition of the present invention is a filler for the low dielectric loss resin composition, and has a thermal expansion coefficient of 1 × 10 －６ (1 / K) or less, the dielectric tangent of the inorganic filler is 0.002 or less at a frequency of 1 GHz or more and a temperature of 25 ° C, and the mass change rate of the inorganic filler is 0.5 mass% or less after standing for 48 hours in an environment of a temperature of 85 ° C and a relative humidity of 85%.

[0013] In the above configuration, the inorganic filler is at least one kind of MXF ６ (M represents at least one selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, V, Cr, Mn, Fe, Ni, Cu, and Zn. X represents at least one selected from the group consisting of Al, Si, P, Ti, Ge, Zr, Nb, Sn, Hf, and Ta.) is preferable.

[0014] Further, in the above configuration, the MXF ６ is preferably MgZrF ６

[0015] In order to solve the above problems, the low dielectric loss resin composition of the present invention is characterized by containing at least a polymer resin and the filler for the low dielectric loss resin composition.

[0016] In the above configuration, the content of the filler for the low dielectric loss resin composition is preferably in the range of 1 mass% or more and 85 mass% or less with respect to the total mass of the low dielectric loss resin composition.

[0017] Furthermore, in the above configuration, it is preferable that the polymer resin includes at least one thermoplastic resin and / or at least one thermosetting resin.

[0018] Furthermore, in the above configuration, it is preferable that the polymer resin is at least one selected from the group consisting 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 modified versions thereof.

[0019] To solve the above-mentioned problems, the molded article for high-frequency equipment of the present invention is a molded article for high-frequency equipment used in a frequency band of 1 GHz or higher, and is characterized by comprising a molded article containing the low dielectric loss resin composition.

[0020] To solve the above-mentioned 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 is characterized by containing the low dielectric loss resin composition.

[0021] Furthermore, in order to solve the above-mentioned 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 is characterized by comprising the molded body for the high-frequency device.

[0022] According to the present invention, the coefficient of thermal expansion is 1 × 10 －６By using a filler containing an inorganic filler with a dielectric loss tangent of 0.002 or less at a frequency of 1 GHz or higher and a temperature of 25°C, in a low dielectric loss resin composition, the thermal expansion coefficient of the low dielectric loss resin composition can be reduced while maintaining good low dielectric loss characteristics in the high frequency band. As a result, for example, by using a low dielectric loss resin composition containing the filler of the present invention in molded articles for high-frequency equipment or high-frequency equipment, the thermal expansion coefficient can be reduced without impairing the low dielectric loss characteristics even when used in high frequency bands of 1 GHz or higher, and the dimensional and structural stability can be improved. Furthermore, the inorganic filler also has excellent moisture resistance, such that the mass change rate after standing for 48 hours in an environment of 85°C and 85% relative humidity is 0.5% by mass or less, so the absorption / adsorption of moisture by the inorganic filler can be suppressed, and excellent low dielectric loss characteristics can be maintained. Furthermore, when used in molded parts for high-frequency equipment or in high-frequency equipment itself, the generation of water vapor originating from the inorganic filler can be suppressed even in environments subject to thermal loads, thereby preventing interfacial delamination and cracking between the inorganic filler and dissimilar materials.

[0023] (Filler for Low Dielectric Loss Resin Composition) First, the filler for low dielectric loss resin composition according to this embodiment (hereinafter referred to as "filler") will be described below. The filler of this embodiment can be added to a low dielectric loss resin composition (details will be described later) to suppress the loss coefficient in the high-frequency band and improve or enhance the low dielectric loss characteristics. Furthermore, the filler of this embodiment can control (or reduce) the thermal expansion coefficient of the low dielectric loss resin composition and also functions as a thermal expansion inhibitor or thermal expansion reducer.

[0024] The filler of this embodiment includes at least an inorganic filler having a low coefficient of thermal expansion and excellent moisture resistance. In addition to the embodiment in which the filler consists only of an inorganic filler, the filler of this embodiment may also include other fillers or additives intended to impart functionality.

[0025] <Inorganic Fillers> Inorganic fillers consist of powdered solid particles and, as mentioned above, have a well-suppressed thermal expansion coefficient and excellent moisture resistance. Therefore, when inorganic fillers are included in a low dielectric loss resin composition, the thermal expansion of the low dielectric loss resin composition can be suppressed. Here, "thermal expansion" means that in response to a rise in temperature, the area or volume of a substance or object increases, or its shape expands, without a phase transition. The thermal expansion coefficient of inorganic fillers is 1 × 10⁻⁶. －６ (1 / K) or less, preferably 0.9 × 10 －６ (1 / K) or less, more preferably 0.5 × 10 －６ (1 / K) or less, more preferably 0.1 × 10 －６ (1 / K) or less, particularly preferably -0.5 × 10 －６ The thermal expansion coefficient is less than or equal to (1 / K). －６ If the thermal expansion coefficient is 1 × 10⁻¹⁰ or less, for example, if an inorganic filler is included in a low dielectric loss resin composition, the thermal expansion coefficient of the low dielectric loss resin composition itself can be reduced. Conventional low dielectric loss resin compositions have been mixed with many different types of fillers in order to reduce their thermal expansion coefficient. However, with this method, the proportion of polymer resin in the low dielectric loss resin composition decreases, which leads to the problem that the inherent properties of the polymer resin, such as adhesion, are impaired. However, as in this embodiment, the thermal expansion coefficient is 1 × 10⁻¹⁰. －６ By using an inorganic filler with a thermal expansion coefficient of (1 / K) or less, the amount of inorganic filler can be reduced compared to conventional low dielectric loss resin compositions when adjusting the thermal expansion coefficient of a low dielectric loss resin composition to an arbitrary value. As a result, the decrease in the content of polymer resin in the low dielectric loss resin composition can be suppressed, and the loss of properties of the polymer resin can be prevented. However, if the thermal expansion coefficient of the inorganic filler is too small, for example, when it is included in a low dielectric loss resin composition, the discrepancy with the thermal expansion coefficient of the polymer resin may become large. In such cases, the difference in thermal shrinkage between the two may reduce the dimensional and structural stability of molded articles for high-frequency equipment and high-frequency equipment using the low dielectric loss resin composition. Therefore, from the viewpoint of preventing this, the lower limit of the thermal expansion coefficient of the inorganic filler should be -50 × 10 －６ It is preferable that it be (1 / K) or higher, -30 × 10－６ It is more preferable that it be (1 / K) or higher, -20 × 10 －６ It is even more preferable that the coefficient of thermal expansion is 1 / K or higher. Furthermore, the "coefficient of thermal expansion" can be measured by the method described in the examples below.

[0026] Relative permittivity ε of inorganic fillers ｒ１ The upper limit of [-] is preferably 6 or less, more preferably 5 or less, and particularly preferably 4 or less at frequencies of 1 GHz or higher and temperatures of 25°C. Relative permittivity ε ｒ１ If the value is 6 or less, the loss coefficient can be reduced, thereby reducing dielectric loss.

[0027] Furthermore, the dielectric loss tangent tanδ of the inorganic filler １ The upper limit of [-] is 0.002 or less, preferably 0.0015 or less, and more preferably 0.0010 or less, at frequencies of 1 GHz or higher and temperatures of 25°C. Dielectric loss tangent tanδ １ If the value is 0.002 or less, the loss coefficient can be reduced, and dielectric loss can be reduced.

[0028] Furthermore, the upper limit of the loss coefficient of the inorganic filler is preferably less than 5, more preferably 4 or less, and particularly preferably 3 or less. When the loss coefficient is less than 5, the loss coefficient can be reduced, and dielectric loss can be reduced.

[0029] Furthermore, the relative permittivity ε used to quantify dielectric properties and dielectric loss is... ｒ１ and dielectric loss tangent tanδ １ Each of these values ​​is based on measurements of the inorganic filler and conversions derived from those measurements. The measurement method can be selected as appropriate. Specifically, for example, each can be measured by the method described in the examples below.

[0030] The loss factor is the relative permittivity ε of the inorganic filler. ｒ１ and dielectric loss tangent tanδ １ Using the measured values, it can be calculated based on the following formula: (Loss factor) = (ε ｒ１ ) １／２ ×tanδ １ ×10 ３ (In the formula, εｒ１ [-] represents the relative permittivity of the inorganic filler, tanδ １ [-] represents the dielectric loss tangent.

[0031] Relative permittivity ε ｒ１ δ is a parameter that indicates the degree of polarization of the inorganic filler; the higher the relative permittivity, the greater the delay in electrical signal propagation. Therefore, a lower relative permittivity is preferable to increase the signal propagation speed. Dielectric loss tangent tanδ １ This parameter indicates the amount of signal loss that occurs when signals propagating through the inorganic filler are converted into heat. Therefore, a lower dielectric loss tangent results in less signal loss and improved signal transmission efficiency.

[0032] As described above, inorganic fillers have excellent moisture resistance and can effectively suppress the absorption and / or adsorption of moisture. The moisture resistance of inorganic fillers can be quantitatively evaluated by measuring the rate of mass change (or moisture absorption) with respect to moisture. In this embodiment, the rate of mass change of the inorganic filler is 0.5% by mass or less, preferably 0.45% by mass or less, more preferably 0.4% by mass or less, and even more preferably 0.35% by mass or less, after being left standing for 48 hours in an environment with a temperature of 85°C and a relative humidity of 85%. When the rate of mass change is 0.5% by mass or less, even when electronic components such as circuit boards using inorganic fillers are used in environments subject to thermal load, the generation of water vapor originating from the inorganic filler can be suppressed or prevented. Furthermore, by suppressing the generation of water vapor, the occurrence of cracks, interfacial delamination, etc., between inorganic fillers and dissimilar materials can be reduced or suppressed.

[0033] In this specification, the "rate of mass change" (or "moisture absorption") of an inorganic filler is defined by the following formula: Rate of mass change (mass%) = [(M １ -M ０ ) / M ０ ] x 100 (M ０ This represents the initial mass of the inorganic filler under conditions of 25°C and 50% relative humidity. １ This represents the mass of the inorganic filler after standing for 48 hours in an environment with a temperature of 85°C and a relative humidity of 85%.

[0034] As an inorganic filler, at least one type of MXF ６ (M represents at least one selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, V, Cr, Mn, Fe, Ni, Cu, and Zn. X represents at least one selected from the group consisting of Al, Si, P, Ti, Ge, Zr, Nb, Sn, Hf, and Ta.) Preferably represented as MgZrF ６ MgZrF is more preferable. ６ In this embodiment, a portion of Mg may be substituted with at least one metal ion selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, V, Cr, Mn, Fe, Ni, Cu, and Zn, and a portion of Zr may be substituted with at least one element selected from the group consisting of Ti, Hf, Nb, Ta, Si, Ge, P, Sn, and Al. Furthermore, in the inorganic filler of this embodiment, MgZrF ６ And, MgZrF ６ At least one other type of MXF ６ Products containing MXF may also be used. ６ It can exhibit excellent low dielectric loss characteristics in the high frequency band above 1 GHz. Therefore, MXF ６ By including it as a component of the low dielectric loss resin composition, not only can the low dielectric loss characteristics of the low dielectric loss resin composition be improved, but the coefficient of thermal expansion can also be reduced. ６ It also exhibits excellent moisture resistance. In particular, MgZrF ６ These effects can be significantly achieved. Furthermore, two or more different inorganic fillers may be used in combination.

[0035] MXF ６ It can be manufactured, for example, by the following method: namely, MXF ６ , MF ２ and XF ４ It can be manufactured by a manufacturing method that includes at least a mixing step to prepare a mixed powder containing and a heating step to heat the mixed powder.

[0036] In the mixing process, MF ２ and XF４ The method of mixing is not particularly limited and includes, for example, a mortar and pestle, a shaker, a dry bead mill, and a mixer. The average particle size and bulk density of the resulting mixed powder can be set as appropriate.

[0037] Furthermore, in the mixing process, the raw material MF ２ and XF ４ Preferably, the process includes a step to reduce (or remove) the oxygen atom-containing components contained therein. Examples of oxygen atom-containing components include MF ２ and XF ４ Examples include hydroxyl groups present on the surface of the powder, adsorbed moisture present on the surface, and oxides and oxyfluorides as impurities. By performing a process to reduce (or remove) oxygen atom-containing components, MXF ６ During the production of this product, the inclusion of impurities such as oxyfluorides can be reduced or prevented. The method for reducing (or removing) oxygen atom-containing components is not particularly limited and includes, for example, heat treatment and vacuum treatment. When heat treatment is performed, the heating temperature is preferably in the range of 80°C to 400°C, more preferably in the range of 100°C to 350°C, and even more preferably in the range of 120°C to 300°C. The heating time is preferably in the range of 1 hour to 48 hours, more preferably in the range of 6 hours to 36 hours, and even more preferably in the range of 12 hours to 24 hours.

[0038] The heating method in the heating process is not particularly limited, and known methods can be used. Furthermore, the heating temperature is preferably in the range of 400°C to 800°C, more preferably in the range of 500°C to 800°C, and even more preferably in the range of 600°C to 800°C. By heating to 400°C or higher, residual moisture and organic matter and other impurities can be removed or reduced. On the other hand, by heating to 800°C or lower, the generated MXF... ６This prevents thermal fusion and thermal decomposition between the materials. Furthermore, the heating time is preferably within the range of 1 hour to 24 hours, and more preferably within the range of 3 hours to 8 hours. By heating for 3 hours or more, residual moisture and organic matter and other impurities can be removed or reduced. On the other hand, by heating for 24 hours or less, the resulting MXF can be reduced. ６ This prevents thermal fusion and thermal decomposition between the materials.

[0039] The shape of the inorganic filler is not particularly limited and can be appropriately selected considering, for example, the fluidity when different solid particles are mixed, or the fluidity and viscosity of the mixture when mixed with a polymer resin (details will be described later). It can also be appropriately selected depending on the purpose, such as controlling the mechanical strength, thermal conductivity, and gas diffusivity of molded articles containing a low dielectric loss resin composition.

[0040] The shape of the inorganic filler can be any shape, such as spherical, nearly spherical, elliptical, rod-shaped, needle-shaped, spindle-shaped, or plate-shaped. It may also be hollow, having one of these shapes and having a space inside. Furthermore, in this embodiment, in addition to using inorganic fillers of the same shape, two or more inorganic fillers of different shapes can be used in combination.

[0041] The average particle size D50 of the inorganic filler (the particle size representing 50% of the cumulative particle size distribution in the volume-based cumulative particle size distribution) is not particularly limited and can be appropriately set depending on the shape of the molded product containing the low dielectric loss resin composition, such as its size and thickness, and for reasons such as adjusting the fluidity of the material containing the inorganic filler during the production of the low dielectric loss resin composition. Generally, the upper limit of the average particle size D50 of the inorganic filler is preferably 75 μm or less, more preferably 50 μm or less, even more preferably 10 μm or less, and particularly preferably 1 μm or less. On the other hand, the lower limit of the average particle size D50 of the inorganic filler is preferably 0.05 μm or more, more preferably 0.075 μm or more, and even more preferably 0.1 μm or more. If the average particle size D50 of the inorganic filler is too large, it becomes difficult to make the surface of the molded product flat when applied to a film-like or sheet-like molded product. As a result, for example, when forming a laminate, 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 average particle size D50 of the inorganic filler is too small, uniform mixing becomes difficult when mixing it with the polymer resin, and the viscosity of the mixture may increase to such an extent that it becomes difficult to mold the low dielectric loss resin composition.

[0042] Furthermore, when the low dielectric loss resin composition of this embodiment is a film or sheet-shaped molded product, the average particle size D50 of the inorganic filler is preferably set to 1 / 5 or less of the thickness of the molded product within the aforementioned numerical range, and more preferably to 1 / 10 or less. For example, when the molded product of the low dielectric loss resin composition is a film or sheet-shaped product with a thickness of about 20 μm, the average particle size D50 of the inorganic filler is preferably 10 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. This makes it possible to mold a film or sheet-shaped molded product with the inorganic filler aligned in a single layer. As a result, a molded product with reduced or prevented surface irregularities can be obtained. In addition, in a slurry composition before curing in which the inorganic filler is dispersed in a solvent, the settling of the inorganic filler can be suppressed, and a film or sheet-shaped molded product with uniformly filled inorganic filler can be obtained.

[0043] Furthermore, the average particle size D50 of the inorganic filler is a value obtained by measuring it using the laser diffraction / scattering method with, for example, a Microtrac MT3300EXII (product name: manufactured by Nikkiso Co., Ltd.).

[0044] The oxygen content of the inorganic filler is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, relative to the total mass of the inorganic filler. This reduces the content of oxygen atom-containing components (e.g., surface hydroxyl groups, adsorbed water, and oxides and oxyfluorides as impurities) in the inorganic filler, thereby suppressing their effect on dielectric properties. More specifically, reducing the content of oxygen atom-containing components as impurities improves the crystallinity of the inorganic filler. Furthermore, reducing the content of oxyfluorides as oxygen atom-containing components improves the insulating properties of the inorganic filler. In addition, reducing hydroxyl groups and adsorbed water, which have high polarizability, as oxygen atom-containing components also suppresses the deterioration of dielectric properties.

[0045] Furthermore, the oxygen content of inorganic fillers can be measured, for example, using an X-ray fluorescence analyzer (product name: ZSX Primus II, manufactured by Rigaku Corporation).

[0046] Furthermore, in the inorganic filler of this embodiment, it is preferable that the mass loss after heat treatment in the range of 25°C to 300°C for 10 to 60 minutes is 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, relative to the mass of the inorganic filler before heat treatment. By using an inorganic filler with a mass loss of 3% by mass or less after heat treatment, it is possible to prevent a decrease in the low dielectric loss properties and mechanical strength of the low dielectric loss resin composition due to heat generation during polymerization of monomers forming the polymer resin, degassing of impurities during heat treatment, and thermal decomposition of the main components of the polymer resin. There are no particular limitations on the method for reducing the mass loss after heat treatment to 3% by mass or less in the inorganic filler. For example, one method is to remove or reduce impurities that cause mass loss from the inorganic filler by pre-treating them with heat or chemical solutions. The mass loss of the inorganic filler can be measured by differential thermal-thermogravimetric analysis (TG-DTA), etc.

[0047] The surface of the inorganic filler in this embodiment may be chemically modified by introducing functional groups such as hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, amino groups, perfluoroalkane groups, ether groups, and ester groups, to the extent that it does not impede the effects of the present invention.

[0048] Furthermore, inorganic fluorides or fluororesin particles may be retained on at least a portion of the surface of the inorganic filler. Here, it is preferable to use inorganic fluorides and fluororesin particles that have a smaller relative permittivity, dielectric loss tangent, and moisture absorption value compared to the inorganic filler. This makes it possible to further reduce dielectric loss and / or moisture absorption compared to when an inorganic filler that does not retain inorganic fluorides and fluororesin particles is used in a low dielectric loss resin composition. The manner in which the inorganic fluorides or fluororesin particles are retained on the surface of the inorganic filler is not particularly limited. For example, the inorganic fluorides or fluororesin particles may be chemically bonded on the surface of the inorganic filler, or they may be fixed by thermal fusion utilizing the difference in melting points.

[0049] The inorganic fluoride is not particularly limited, but is preferably represented by MFn (wherein M is at least one selected from the group consisting of Li, Na, K, Mg, Al, Ca, Sc, Mn, Fe, Ga, Rb, Sr, Y, Zr, Sn, Ba, La, Ce, Yb, Hf, and Bi, and n is an integer from 1 to 4). More specifically, the inorganic fluoride may be NaF (sodium fluoride), KF (potassium fluoride), MgF ２ (Magnesium fluoride), AlF ３ (Aluminum fluoride), CaF ２ (Calcium fluoride), ScF ３ (Scandium fluoride), MnF ２ (Manganese fluoride), FeF ３ (Iron fluoride), GaF ３ (Gallium fluoride), RbF (Rubidium fluoride), SrF ２ (Strontium fluoride), YF ３ (Yttrium fluoride), ZrF ４ (Zirconium fluoride), SnF ２ (Tin fluoride), BaF ２ (Barium fluoride), LaF ３ (Lanthan fluoride), CeF ３ (Cerium fluoride), YbF ２ (Ytterbium difluoride), YbF ３ (Ytterbium trifluoride), HfF ４ (Hafnium fluoride) and BiF ３ Examples include bismuth fluoride. Of the inorganic fluorides exemplified, aluminum fluoride, cerium fluoride, magnesium fluoride, and bismuth fluoride are preferred from the viewpoint of reducing dielectric loss and / or moisture absorption of the inorganic filler, with aluminum fluoride and bismuth fluoride being more preferred.

[0050] Furthermore, the fluororesin particles are not particularly limited and include, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluorovinyl ether copolymer (PFA), and tetrafluoroethylene hexafluoropropylene copolymer (FEP). Of these fluororesins, PTFE is preferred from the viewpoint of reducing dielectric loss and moisture absorption of the inorganic filler.

[0051] The method for retaining inorganic fluoride or fluororesin particles on at least a portion of the surface of the inorganic filler is not particularly limited, and known methods can be employed. For example, in the case where fluororesin particles are heat-fused to the surface of the inorganic filler, the method may include at least a mixing step of mixing the inorganic filler and the fluororesin particles, a heating step of heating the mixture of the inorganic filler and the fluororesin particles, and a cooling step of cooling the mixture after heating. The heating method in the heating step is not particularly limited, and known methods can be employed. Furthermore, the heating temperature is not particularly limited as long as it is above the melting point of the fluororesin particles and below the boiling point, and can be set appropriately depending on the type of fluororesin, etc., if the melting point of the fluororesin particles is lower than that of the inorganic filler. Furthermore, the heating time is not particularly limited and can be set appropriately depending on the heating temperature, the type of material of the fluororesin particles, etc. The cooling method in the cooling step is not particularly limited, and can be carried out by, for example, natural cooling or rapid cooling.

[0052] (Low Dielectric Loss Resin Composition) Next, the low dielectric loss resin composition of this embodiment will be described below. The low dielectric loss resin composition of this embodiment comprises at least the filler and polymer resin described above.

[0053] Regarding the filler content, the lower limit is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, based on the total mass of the low dielectric loss resin composition. On the other hand, the upper limit of the filler content is preferably 85% by mass or less, more preferably 82% by mass or less, and even more preferably 79% by mass or less, based on the total mass of the low dielectric loss resin composition. When the lower limit of the filler content is 1% by mass or more, the loss coefficient of the low dielectric loss resin composition becomes smaller, and dielectric loss is reduced. On the other hand, when the upper limit of the filler content is 85% by mass or less, deterioration of physical strength such as brittleness can be prevented, and it becomes possible to improve hardness, reduce the coefficient of thermal expansion, and improve weather resistance.

[0054] The polymer resin preferably comprises at least one thermoplastic resin and / or at least one thermosetting resin. More specifically, polymer resins include, for example, olefin resins such as polyethylene resin and polypropylene resin; polycarbonate resin; polyphenylene ether resin; polysulfone resin; polyethersulfone resin; polyphenylene sulfide resin; polyetheretherketone resin; liquid crystal polymer resin; polyimide resin; fluororesins such as polytetrafluoroethylene resin (PTFE), polytetrafluoroethylene and perfluoroalkoxyethylene copolymer (PFA), polychlorotrifluoroethylene resin (PCTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (ETFE); phenolic resin; epoxy resin; silicone resin; and modified versions thereof. These polymer resins can be used individually or in mixtures 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 an epoxy resin and polyphenylene ether resin, processability can be improved by increasing fluidity. Furthermore, the degree of polymerization of the polymer resin is not particularly limited and can be appropriately selected depending on the application of the low dielectric loss resin composition.

[0055] The polymer resin content is preferably in the range of 15% by mass or more and 99% by mass or less, more preferably in the range of 18% by mass or more and 90% by mass or less, and even more preferably in the range of 21% by mass or more and 80% by mass or less, based on the total mass of the low dielectric loss resin composition. By setting the polymer resin content to 15% by mass or more, the properties of the polymer resin, such as adhesion and water resistance, can be fully expressed. On the other hand, by setting the polymer resin content to 99% by mass or less, the thermal expansion coefficient and dielectric loss of the low dielectric loss resin composition can be reduced by including inorganic fillers while maintaining the properties of the polymer resin.

[0056] The low dielectric loss resin composition of this embodiment exhibits a reduced coefficient of thermal expansion compared to, for example, the low dielectric loss resin composition of this embodiment that does not contain an inorganic filler. Reducing the coefficient of thermal expansion is particularly effective when using polymer resins with a relatively high coefficient of thermal expansion, such as epoxy resins. The reduction rate of the coefficient of thermal expansion in the low dielectric loss resin composition of this embodiment is preferably 20% or more, more preferably 40% or more, even more preferably 60% or more, and particularly preferably 80% or more, based on the coefficient of thermal expansion of a low dielectric loss resin composition consisting only of polymer resin. By reducing the coefficient of thermal expansion of the low dielectric loss resin composition by 20% or more, it is possible to extend the lifespan and improve the functionality of electronic components and the like for high-frequency applications where dimensional stability is required. The reduction rate of the coefficient of thermal expansion of the low dielectric loss resin composition can be calculated using the following formula: (Reduction rate of the coefficient of thermal expansion of the low dielectric loss resin composition) (%) = (β ０ -β １ )β ０ ×100 (in the formula, β ０ β represents the thermal expansion coefficient of a low dielectric loss resin composition consisting solely of polymer resins, １ (This represents the thermal expansion coefficient of the low dielectric loss resin composition of this embodiment.) The thermal expansion coefficient of the low dielectric loss resin composition can be controlled by appropriately setting the content of inorganic fillers and polymer resins, etc.

[0057] Relative permittivity ε of low dielectric loss resin composition ｒ２The upper limit value of [−] is preferably 5 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. The relative permittivity ε of the low dielectric loss resin composition ｒ２ being 5 or less can reduce the loss coefficient and achieve reduction of dielectric loss.

[0058] Further, the upper limit value of the dielectric tangent tan δ of the low dielectric loss resin composition ２ is preferably 0.010 or less, more preferably 0.0090 or less, and even more preferably 0.0080 or less at a frequency of 1 GHz or higher and a temperature of 25 °C. The dielectric tangent tan δ of the low dielectric loss resin composition ２ being 0.010 or less can reduce the loss coefficient and achieve reduction of dielectric loss.

[0059] The upper limit value of the loss coefficient of the low dielectric loss resin composition is preferably less than 20, more preferably 17 or less, and particularly preferably 15 or less. When the loss coefficient is less than 20, the loss coefficient of the low dielectric loss resin composition can be reduced and the dielectric loss can be reduced.

[0060] Incidentally, the relative permittivity ε ｒ２ and the dielectric tangent tan δ ２ used for quantification of dielectric properties and dielectric loss are based on values obtained by measuring the low dielectric loss resin composition and converting from the measured values. The measurement method can be appropriately selected. Specifically, for example, they can be measured by methods according to the methods described in the examples below.

[0061] The loss coefficient can be calculated based on the following formula using the measured values of the relative permittivity ε ｒ２ and the dielectric tangent tan δ ２ of the low dielectric loss resin composition. (Loss coefficient) = (ε ｒ２ ) １／２ × tan δ ２ × 10 ３ (In the formula, ε ｒ２ [−] represents the relative permittivity of the low dielectric loss resin composition, and tan δ ２ [−] represents its dielectric tangent.)

[0062] Relative permittivity ε ｒ２ δ is a parameter indicating the degree of polarization of a low dielectric loss resin composition; the higher the relative permittivity, the greater the delay in electrical signal propagation. Therefore, a lower relative permittivity is preferable to increase the signal propagation speed. Dielectric loss tangent tanδ ２ This parameter indicates the amount of signal loss that occurs when a signal propagating through a low dielectric loss resin composition is converted into heat. Therefore, a lower dielectric loss tangent results in less signal loss and improved signal transmission efficiency.

[0063] Next, a method for producing 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 a filler and any other additives to a polymer resin in any order and uniformly mixing or kneading them. Alternatively, it can be produced by adding a filler and any other additives to a polymer resin or a solution in which monomers forming the polymer resin are dissolved or dispersed in an organic solvent (for example, a varnish or dispersion) in any order and dispersing them.

[0064] In the low dielectric loss resin composition of this embodiment, impurities may be included to the extent that they do not contradict the objectives of the present invention. Examples of such impurities include metal impurities having elements other than those constituting the filler, and metal oxides. The content of impurities is preferably 100 ppm or less, more preferably 10 ppm or less, based on the total mass of the low dielectric loss resin composition.

[0065] Furthermore, the low dielectric loss resin composition of this embodiment may contain other additives to the extent that they do not contradict the objectives of the present invention. These other additives are not particularly limited and include, for example, curing agents, curing accelerators, lubricants, nucleating agents, UV inhibitors, colorants, flame retardants, stabilizers, plasticizers, reinforcing agents, and dispersants. The content of these other additives is not particularly limited and can be appropriately set depending on the application and purpose.

[0066] The low dielectric loss resin composition of this embodiment can be used as an insulating film resin composition (solder resist), a semiconductor encapsulation resin composition, an adhesive, a paint, a covering material for wiring for power supplies and communications, etc.

[0067] (Molded article for high-frequency equipment and method for manufacturing the same) The molded article for high-frequency equipment of this embodiment (hereinafter referred to as "molded article") consists of a molded article containing a low dielectric loss resin composition. The molded article may consist of only the low dielectric loss resin composition.

[0068] The reduction rate of the thermal expansion coefficient of the molded article is the same as the reduction rate of the thermal expansion coefficient in the low dielectric loss resin composition described above. That is, the reduction rate of the thermal expansion coefficient of the molded article is preferably 20% or more, more preferably 40% or more, even more preferably 60% or more, and particularly preferably 80% or more, when compared to the thermal expansion coefficient of a molded article made only of polymer resin. Furthermore, the reduction rate of the thermal expansion coefficient of the molded article can be calculated by the following formula: (Reduction rate of thermal expansion coefficient of molded article) (%) = (β ０ '-β １ ')β ０ '×100 (in the formula, β ０ ' represents the thermal expansion coefficient of a molded article made solely of polymer resin, β １ ' represents the thermal expansion coefficient of the molded article in this embodiment.

[0069] Relative permittivity ε of the molded body ｒ３ The upper limit of [-] is preferably 5 or less, more preferably 4 or less, and particularly preferably 3.5 or less at frequencies of 1 GHz or higher and temperatures of 25°C. Relative permittivity ε of the molded article ｒ３ If the value is 5 or less, the loss coefficient can be reduced, thereby reducing dielectric loss.

[0070] Furthermore, the dielectric loss tangent tanδ of the molded body ３ The upper limit of [-] is preferably 0.010 or less, more preferably 0.0090 or less, and even more preferably 0.0080 or less at frequencies of 1 GHz or higher and temperatures of 25°C. Dielectric loss tangent tanδ of the molded body ３ If the value is 0.010 or less, the loss coefficient can be reduced, and dielectric loss can be reduced.

[0071] The upper limit of the loss factor of the molded article is preferably less than 20, more preferably 17 or less, and particularly preferably 15 or less. A loss factor of less than 20 reduces the loss factor of the molded article and thus reduces dielectric loss.

[0072] Furthermore, the relative permittivity ε used to quantify dielectric properties and dielectric loss is... ｒ３ and dielectric loss tangent tanδ ３ Each of these values ​​is based on measurements of the molded body and conversions derived from those measurements. The measurement method can be selected as appropriate. Specifically, for example, each can be measured by the method described in the examples below.

[0073] The loss factor is the relative permittivity ε of the molded body. ｒ３ and dielectric loss tangent tanδ ３ Using the measured values, it can be calculated based on the following formula: (Loss factor) = (ε ｒ３ ) １／２ ×tanδ ３ ×10 ３ (In the formula, ε ｒ３ [-] represents the relative permittivity of the molded body, tanδ ３ [-] represents the dielectric loss tangent.

[0074] Molded articles can be manufactured, for example, by using known kneaders and extruders. For kneaders, for example, a closed-type pressure kneader or an open-roll kneader can be used. After producing a sheet-like low-dielectric-loss resin composition material using these kneaders, a molded article can be manufactured using this low-dielectric-loss resin composition material. Alternatively, a pellet-like low-dielectric-loss resin composition material can be produced using an extruder, and then a molded article can be manufactured using an injection molding machine. When mixing polymer resin with fillers and other additives using a molding machine such as an extruder, the number of steps can be reduced, and production efficiency can be improved. Furthermore, the fillers may be subjected to appropriate drying treatments before mixing with the polymer resin.

[0075] Furthermore, sheet-shaped molded articles can be manufactured by known methods. For example, a varnish tank filled with a solution containing a polymer resin (resin varnish) is filled with a filler and any other additives, which are then uniformly dispersed, and the dispersion is heated under predetermined temperature conditions. The cured material produced by heating is then stretched into a sheet, thereby producing a sheet-shaped molded article.

[0076] Furthermore, a sheet-like substrate, such as glass cloth or bonding sheet, is passed through a liquid tank containing a dispersion liquid comprising a polymer resin, filler, and any other additives, while immersed in the dispersion liquid, thereby impregnating the sheet-like substrate. Subsequently, the sheet impregnated with the dispersion liquid is subjected to a drying treatment to produce an impregnated sheet containing a low dielectric loss resin composition. It is also possible to produce a laminate in which multiple layers of low dielectric loss resin composition are laminated by passing the sheet-like substrate through the liquid tank of dispersion liquid multiple times.

[0077] (High-frequency equipment) The high-frequency equipment according to this embodiment includes a low dielectric loss resin composition or comprises a molded body of a low dielectric loss resin composition.

[0078] The high-frequency equipment of this embodiment is used for information processing and information communication, which are performed by electronically exchanging signals. In particular, the high-frequency equipment of this embodiment is used in high-frequency bands of 1 GHz or higher, more preferably 10 GHz or higher, where the frequency band of radio waves and signals used during communication is 1 GHz or higher. Furthermore, the high-frequency equipment of this embodiment uses an inorganic filler with excellent moisture resistance, and since the generation of water vapor originating from the inorganic filler and the absorption / adsorption of moisture by the inorganic filler can be suppressed, it can be used well even in atmospheres with thermal loads. The high-frequency equipment of this embodiment also includes high-frequency electronic components used in such high-frequency bands.

[0079] Examples of high-frequency equipment include housings for information processing and information communication equipment, circuit boards, printed wiring boards, transmission lines, high-frequency electronic components such as capacitors and inductors, and ceiling and wall materials for rooms where high-frequency equipment is installed. High-frequency equipment of this embodiment also includes insulating films and semiconductor encapsulating resins formed from low dielectric loss resin compositions, and wiring coated with low dielectric loss resin compositions as a covering material.

[0080] Preferred embodiments of this invention will be described in detail below. However, unless otherwise specified, the materials and proportions described in these embodiments are not intended to limit the scope of this invention to those materials alone.

[0081] (Example 1) <Calculation of relative permittivity, dielectric loss tangent and loss coefficient> First, MgZrF as a filler ６ The powder (average particle size D50: 20 μm) was subjected to vacuum drying. Vacuum drying was carried out under reduced pressure, at a drying temperature of 100°C for a drying time of 14 hours. Next, the vacuum-dried MgZrF ６ The powder was packed into a quartz tube, and the relative permittivity and dielectric loss tangent were measured using the cavity resonator method in the 10 GHz frequency range under environmental conditions of 25°C and 40% relative humidity. A vector network analyzer (Anritsu Corporation, product name: MS46122B) was used for the measurements. Subsequently, MgZrF ６ For the measured values ​​of the relative permittivity and dielectric loss tangent of a quartz tube filled with MgZrF, ６ The bulk density and true density of MgZrF as a percentage of the packing volume. ６ Using the filling amount, the void portion is corrected, and MgZrF ６ Relative permittivity ε ｒ１ [-] and dielectric loss tangent tanδ １ [-] was calculated. In addition, the loss factor was calculated using the following formula. Note that the relative permittivity, dielectric loss tangent, and loss factor were calculated before and after the moisture resistance test described below. The results are shown in Table 1. (Loss factor) = (ε ｒ１ ) １／２ ×tanδ １ ×10 ３ (In the formula, ε ｒ１ [-] represents the relative permittivity of the filler, tanδ１ [-] represents the dielectric loss tangent.

[0082] <Oxygen content> Next, MgZrF ６ The oxygen content was measured. A fluorescent X-ray analyzer (X-ray Fluorescence, product name: ZSX Primus II, manufactured by Rigaku Corporation) was used for the measurement. The results are shown in Table 1.

[0083] <Measurement of thermal expansion coefficient> Next, MgZrF ６ The coefficient of thermal expansion (CTE) of MgZrF was measured. For the measurement, an X-ray diffractometer (product name: SmartLab SE, manufactured by Rigaku Corporation) was used to measure MgZrF ６ The powder was heated to a target temperature of 40°C at a heating rate of 10°C / min. After maintaining the temperature at 40°C for 1 minute, the MgZrF was obtained from the X-ray diffraction pattern. ６ The lattice constants of the powder with respect to the a-axis, b-axis, and c-axis were measured. Next, the lattice constants of the powder at 100°C, 200°C, 300°C, and 400°C were measured in the same manner. After that, the changes in the obtained lattice constants were converted to a linear value and calculated as MgZrF ６ The thermal expansion coefficient was determined. The results are shown in Table 1. If different thermal expansion coefficients were observed in the a-axis, b-axis, and c-axis directions, the average thermal expansion coefficient was calculated. The detailed measurement conditions for the thermal expansion coefficient are as follows: • X-ray tube: Cu • Tube voltage: 40kV • Tube current: 50mA • Step size: 0.02° • Measurement range: 2θ = 15° to 90° • Heating rate: 10°C / min • Measurement temperatures: 40°C, 100°C, 200°C, 300°C, 400°C

[0084] <Moisture resistance test> Furthermore, MgZrF ６ The moisture absorption (mass change rate) of the substance was measured to evaluate its moisture resistance. Specifically, first, an electronic balance was used to measure MgZrF ６ The initial mass M of the powder ０ The measurements were taken under conditions of 25°C and 50% relative humidity. Subsequently, MgZrF ６ The powder was placed in a glass petri dish and left to stand for 48 hours in an atmosphere of 85°C and 85% relative humidity, and then MgZrF ６ The mass of the powder was measured again, and the mass after standing was M.１ The mass change rate was measured. The mass change rate was calculated using the following formula. The results are shown in Table 1. Mass change rate (mass%) = [(M １ -M ０ ) / M ０ ] × 100

[0085] (Comparative Example 1) In this comparative example, MgZrF ６ Instead, MgF ２ (Manufactured by Stella Chemifa Co., Ltd., average particle size D50: 23 μm) was used. Otherwise, the relative permittivity, dielectric loss tangent, loss coefficient, thermal expansion coefficient, and mass change rate were determined in the same manner as in Example 1. The results are shown in Table 1.

[0086] (Comparative Example 2) In this comparative example, MgZrF ６ Instead of ZrF ４ (Manufactured by Stella Chemifa Co., Ltd., average particle size D50: 30 μm) was used. Otherwise, the relative permittivity, dielectric loss tangent, loss coefficient, thermal expansion coefficient, and mass change rate were determined in the same manner as in Example 1. The results are shown in Table 1.

[0087] (Comparative Example 3) In this comparative example, MgZrF ６ Instead of MnZrF ６ (Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, the thermal expansion coefficient and mass change rate were determined in the same manner as in Example 1. The results are shown in Table 1.

[0088] (Comparative Example 4) In this comparative example, MgZrF ６ FeZrF ６ (Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, the thermal expansion coefficient and mass change rate were determined in the same manner as in Example 1. The results are shown in Table 1.

[0089] (Comparative Example 5) In this comparative example, MgZrF ６ Instead of ZnZrF ６ (Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, the thermal expansion coefficient and mass change rate were determined in the same manner as in Example 1. The results are shown in Table 1.

[0090]

[0091] (Result 1) As shown in Table 1, the MgZrF of Example 1 ６Compared to the fillers in Comparative Examples 1 and 2, it was confirmed that not only does it have a negative coefficient of thermal expansion, but the relative permittivity and dielectric loss tangent values ​​measured at the same frequency are also small, indicating that it possesses excellent low dielectric properties. In particular, inorganic fluorides containing only one metal element have large relative permittivity and dielectric loss tangent values, but the MgZrF of Example 1 ６ It was confirmed that remarkable low dielectric properties can be achieved by using such a complex fluoride.

[0092] Also, the MgZrF of Example 1 ６ It was also confirmed that it possessed superior moisture resistance compared to the fillers in Comparative Examples 2 to 5. In particular, the fillers in Comparative Examples 3 and 4 were MgZrF ６ Compared to the other example, the thermal expansion coefficient is smaller, but the moisture absorption (mass change rate) is lower than that of MgZrF in Example 1. ６ The coefficient of thermal expansion was smaller, confirming that it not only had a good coefficient of thermal expansion but also excellent moisture resistance. Also, the MgZrF of Example 1 ６ Furthermore, it was confirmed that the dielectric properties, such as relative permittivity, dielectric loss tangent, and loss coefficient, remained almost unchanged before and after the humidity resistance test. On the other hand, in Comparative Example 2, ZrF ４ As shown above, in inorganic fillers where the rate of moisture absorption (mass change rate) increases significantly, the dielectric loss tangent increased after the humidity resistance test, confirming that moisture has a large effect. Furthermore, in Comparative Example 1, the filler was fixed after the humidity resistance test, and in Comparative Examples 3 to 5, each filler was in a slurry state (solid-liquid mixed state) after the humidity resistance test, so it was not possible to evaluate the dielectric properties of relative permittivity, dielectric loss tangent, and loss coefficient.

[0093] (Example 2) <Preparation of Low Dielectric Loss Resin Composition> 10 g of epoxy resin (product name: jER® 828, manufactured by Mitsubishi Chemical Corporation), 12 g of epoxy resin curing agent (product name: jER Cure® YH306, manufactured by Mitsubishi Chemical Corporation), 0.12 g of curing accelerator (2-ethyl-4-methylimidazole), and MgZrF ６ 22 g of the filler, consisting of the following, was placed in a container cup and mixed using a defoaming agitator to prepare a paste. ６The content of [component name] is 49.9% by mass of the total mass of the low dielectric loss resin composition. The content of epoxy resin is 22.7% by mass of the total mass of the low dielectric loss resin composition.

[0094] <Calculation of Relative Permittivity, Dielectric Loss Tangent, and Loss Factor> First, the prepared paste was placed in a mold and cured at room temperature for one day. Then, it was heated and cured at 80°C for 3 hours, and then further heated and cured at 120°C for 6 hours. Next, it was removed from the mold and a molded body (a cylindrical body with a diameter of 1 mm and a height of 15 cm) of the low dielectric loss resin composition according to this embodiment was produced. Subsequently, the relative permittivity ε of the obtained molded body was calculated using the cavity resonator method in the 10 GHz frequency range under an environmental atmosphere of 19°C and 50% relative humidity. ｒ３ and dielectric loss tangent tanδ ３ The following was measured. A network analyzer (product name: E8361A, manufactured by Keysight Technologies, Inc.) was used for the measurement. Furthermore, the loss factor of the molded body was calculated using the following formula. The results are shown in Table 2. (Loss factor) = (ε ｒ３ ) １／２ ×tanδ ３ ×10 ３ (In the formula, ε ｒ３ [-] represents the relative permittivity of the molded body, tanδ ３ [-] represents the dielectric loss tangent.

[0095] (Comparative Example 6) In this comparative example, MgZrF was used as the inorganic filler. ６ Instead, MgF ２ (Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, a molded body (a cylindrical body with a diameter of 1 mm and a height of 15 cm) of the low dielectric loss resin composition according to this comparative example was prepared in the same manner as in Example 2, and the relative permittivity of the molded body was further reduced ε ｒ３ , dielectric loss tangent tanδ ３ The loss coefficient was also measured. The results are shown in Table 2.

[0096] (Comparative Example 7) In this comparative example, MgZrF was used as the inorganic filler. ６ Instead, ZrF ４(Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, a molded body (a cylindrical body with a diameter of 1 mm and a height of 15 cm) of the low dielectric loss resin composition according to this comparative example was prepared in the same manner as in Example 2, and the relative permittivity of the molded body was further reduced ε ｒ３ , dielectric loss tangent tanδ ３ The loss coefficient was also measured. The results are shown in Table 2.

[0097] (Comparative Example 8) In this comparative example, MgZrF was used as the inorganic filler. ６ Instead, MnZrF ６ (Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, a molded body (a cylindrical body with a diameter of 1 mm and a height of 15 cm) of the low dielectric loss resin composition according to this comparative example was prepared in the same manner as in Example 2, and the relative permittivity of the molded body was further reduced ε ｒ３ , dielectric loss tangent tanδ ３ The loss coefficient was also measured. The results are shown in Table 2.

[0098] (Comparative Example 9) In this comparative example, MgZrF was used as the inorganic filler. ６ Instead, FeZrF ６ (Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, a molded body (a cylindrical body with a diameter of 1 mm and a height of 15 cm) of the low dielectric loss resin composition according to this comparative example was prepared in the same manner as in Example 2, and the relative permittivity of the molded body was further reduced ε ｒ３ , dielectric loss tangent tanδ ３ The loss coefficient was also measured. The results are shown in Table 2.

[0099] (Comparative Example 10) In this comparative example, MgZrF was used as the inorganic filler. ６ Instead, ZnZrF ６ (Manufactured by Stella Chemifa Co., Ltd.) was used. Otherwise, a molded body (a cylindrical body with a diameter of 1 mm and a height of 15 cm) of the low dielectric loss resin composition according to this comparative example was prepared in the same manner as in Example 2, and the relative permittivity of the molded body was further reduced ε ｒ３ , dielectric loss tangent tanδ ３ The loss coefficient was also measured. The results are shown in Table 2.

[0100] (Comparative Example 11) In this comparative example, no filler was added. Otherwise, a molded body (a cylindrical body with a diameter of 1 mm and a height of 15 cm) of the low dielectric loss resin composition according to this comparative example was produced in the same manner as in Example 2, and the relative permittivity of the molded body was further adjusted ε ｒ３ , dielectric loss tangent tanδ ３ The loss coefficient was also measured. The results are shown in Table 2.

[0101]

[0102] (Result 2) As shown in Table 2, in Example 2, MgZrF was added to the epoxy resin. ６ By adding the MgZrF ６ Compared to Comparative Example 11, which used epoxy resin only without the addition of [the compound], it was confirmed that the dielectric loss tangent could be reduced. Also, as shown in Table 2, MgZrF ６ The molded article of the low dielectric loss resin composition of Example 2 using MgF ２ Comparative Example 6 and ZrF ４ Compared to the molded article of the low dielectric loss resin composition of Comparative Example 7, which used [the specified material], it showed good low dielectric properties. As a result, MgZrF ６ It was confirmed that it is excellent as a filler for low dielectric loss resin compositions. Furthermore, the MgZrF of Example 2 ６ Although it is the same zirconium-based complex fluoride as the fillers in Comparative Examples 8-10, its physical properties differ significantly due to the difference in metal cation species, and it showed good low dielectric properties even with these fillers. As a result, MgZrF ６ It was confirmed that this filler is superior to the fillers of Comparative Examples 8 to 10 as a filler for low dielectric loss resin compositions.

Claims

1. A filler for low dielectric loss resin compositions, 1 × 10 －６ A filler for a low dielectric loss resin composition, comprising an inorganic filler having a thermal expansion coefficient of (1 / K) or less, wherein the dielectric loss tangent of the inorganic filler is 0.002 or less at a frequency of 1 GHz or higher and a temperature of 25°C, and the rate of mass change of the inorganic filler is 0.5% by mass or less after standing for 48 hours in an environment of 85°C and 85% relative humidity.

2. The inorganic filler is at least one type of MXF ６ A filler for a low dielectric loss resin composition according to claim 1, wherein M represents at least one selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, V, Cr, Mn, Fe, Ni, Cu, and Zn. X represents at least one selected from the group consisting of Al, Si, P, Ti, Ge, Zr, Nb, Sn, Hf, and Ta.

3. The aforementioned MXF ６ However, MgZrF ６ The filler for a low dielectric loss resin composition according to claim 2.

4. A low dielectric loss resin composition comprising at least a polymer resin and a filler for low dielectric loss resin compositions according to any one of claims 1 to 3.

5. The low dielectric loss resin composition according to claim 4, wherein the content of the filler for the low dielectric loss resin composition is within the range of 1% by mass or more and 85% by mass or less, based on the total mass of the low dielectric loss resin composition.

6. The low dielectric loss resin composition according to claim 4, wherein the polymer resin comprises at least one thermoplastic resin and / or at least one thermosetting resin.

7. The low dielectric loss resin composition according to claim 4, wherein the polymer resin is at least one selected from the group consisting 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 modified versions thereof.

8. A molded article for high-frequency equipment used in a frequency band of 1 GHz or higher, comprising a molded article containing the low dielectric loss resin composition described in claim 4.

9. A high-frequency device used in a frequency band of 1 GHz or higher, comprising the low dielectric loss resin composition described in claim 4.

10. A high-frequency device used in a frequency band of 1 GHz or higher, comprising a molded body for high-frequency devices as described in claim 8.

Images