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

Abstract

Provided are: a filler for a low dielectric loss resin composition which is an inorganic filler having excellent low dielectric characteristics and a negative thermal expansion coefficient and can be applied to electronic components such as a circuit board, information communication equipment, etc.; 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 a low dielectric loss resin composition, characterized by containing a first inorganic filler having a negative thermal expansion coefficient and by the dielectric loss tangent of the first inorganic filler being 0.002 or less at a frequency of 1 GHz or more and a temperature of 25° C.

Description

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

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

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

[0003] In particular, in electronic components for high-frequency applications, the attenuation of electrical signals increases due to transmission loss in the transmission path as the frequency increases, which can lead to a decrease in transmission reliability. Therefore, materials with a small loss factor are required for high-frequency devices and their components. Here, the loss factor is calculated by dividing the dielectric constant (ε ｒ ) and the dielectric loss tangent (tan δ).

[0004] Furthermore, electronic components for high-frequency applications are becoming increasingly miniaturized and complex as frequencies increase. Therefore, differences in the thermal expansion coefficients between the different materials that make up electronic components are becoming a major issue. These differences in thermal expansion coefficients can cause distortion and delamination in electronic components, resulting in reduced structural stability and electrical properties. Therefore, it is necessary to control the thermal expansion coefficients of the main components, such as the substrate, resin film, and adhesive layer.

[0005] Generally, most solid materials exhibit thermal expansion, meaning that their volume and length increase with increasing temperature. However, some materials exhibit negative thermal expansion, meaning that their volume and length decrease with increasing temperature. These materials are sometimes used to suppress the coefficient of thermal expansion.

[0006] For example, Patent Document 1 discloses a vanadium compound (Cu) that exhibits negative thermal expansion for the purpose of suppressing the thermal expansion of a material that is required to have electrical insulation properties. ２－Ｘ Zn Ｘ ) V ２ O ７The document discloses a thermal expansion inhibitor filler containing a vanadium compound (0<x<2) and inorganic particles. The inorganic particles are said to have negative thermal expansion or a low thermal expansion coefficient, and the thermal expansion coefficient can be controlled by selecting the compounding ratio of the vanadium compound to the inorganic particles and the type of inorganic particles.

[0007] Patent Document 2 also describes ScF, which has negative thermal expansion properties. ３ Patent Document 2 discloses a copper-based composite material in which a copper-plated layer is coated with copper. According to Patent Document 2, by using this copper-based composite material in a microwave device or 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 has a negative thermal expansion coefficient at temperatures below the magnetic transition temperature of the nanoparticles. According to Patent Document 3, by blending this negative thermal expansion material with other compounds, it is possible to suppress changes in the expansion coefficient of a product due to temperature changes in thin film substrates and the like, which require stable product quality.

[0009] The techniques disclosed in Patent Documents 1 to 3 state that the overall coefficient of thermal expansion can be suppressed by using a material that exhibits negative thermal expansion. However, none of the materials disclosed in these patent documents improves low dielectric loss characteristics in the high-frequency band of 1 GHz or higher. Therefore, there is a need to develop a material that maintains good low dielectric loss characteristics even when used in the high-frequency band and has a negative coefficient of thermal expansion.

[0010] JP 2021-62994 A JP 2022-34528 A JP 2010-29990 A

[0011] The present invention aims to provide a filler for a low dielectric loss resin composition, a low dielectric loss resin composition, a molded article for a high-frequency device, and a high-frequency device, which are inorganic fillers that have excellent low dielectric properties and a negative coefficient of thermal expansion and can be applied to electronic components such as circuit boards and information and communication devices.

[0012] In order to solve the above-mentioned problems, the filler for a low dielectric loss resin composition of the present invention is a filler for a low dielectric loss resin composition, characterized in that it contains a first inorganic filler having a negative thermal expansion coefficient, and the dielectric dissipation factor of the first inorganic filler is 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C.

[0013] In the above-mentioned configuration, it is preferable that the composition further contains a second inorganic filler having a zero or positive thermal expansion coefficient, and that the dielectric loss tangent of the second inorganic filler is 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C.

[0014] Furthermore, in the above-described configuration, it is preferable that the mass ratio of the first inorganic filler to the second inorganic filler, that is, the first inorganic filler:the second inorganic filler, is in the range of 100:0 to 0.01:99.99.

[0015] In addition, in the above-mentioned configuration, it is preferable that the composite compound further comprises a base material made of an inorganic fluoride and fluororesin particles held on at least a portion of the surface of the base material, and that the dielectric loss tangent of the fluororesin particles is 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C.

[0016] Furthermore, in the above-described configuration, it is preferable that the mass ratio of the first inorganic filler to the complex compound be in the range of 100:0 to 0.01:99.99 (first inorganic filler:complex compound).

[0017] Furthermore, in the above-mentioned structure, the first inorganic filler is CaZrF ６ It is preferable that:

[0018] In order to solve the above-mentioned problems, the low dielectric loss resin composition of the present invention is characterized by containing at least a polymer resin and the above-mentioned filler for low dielectric loss resin compositions.

[0019] In the above-mentioned composition, 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.

[0020] In the above-mentioned configuration, it is preferable that the polymer resin contains at least one kind of thermoplastic resin and / or at least one kind of thermosetting resin.

[0021] Furthermore, in the above-mentioned 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, polyether sulfone resins, polyphenylene sulfide resins, polyether ether ketone resins, liquid crystal polymer resins, polyimide resins, fluororesins, phenolic resins, epoxy resins, silicone resins, and modified products thereof.

[0022] In order to solve the above-mentioned problems, the molded article for high-frequency devices of the present invention is a molded article for high-frequency devices used in a frequency band of 1 GHz or more, and is characterized in that it is a molded article containing the low dielectric loss resin composition.

[0023] 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 more, and is characterized by containing the low dielectric loss resin composition described above.

[0024] 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 more, and is characterized by including the above-mentioned molded article for high-frequency devices.

[0025] According to the present invention, by using a filler containing a first inorganic filler having a negative coefficient of thermal expansion and a dielectric loss tangent of 0.002 or less at a frequency of 1 GHz or more and a temperature of 25° C. in a low dielectric loss resin composition, it is possible to reduce the coefficient of thermal expansion of the low dielectric loss resin composition while maintaining good low dielectric loss properties 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 a molded article for high frequency devices or in high frequency devices, it is possible to reduce the coefficient of thermal expansion without impairing the low dielectric loss properties, even when used in the high frequency band of 1 GHz or more, and to improve the dimensional and structural stability.

[0026] CaZrF in the molded bodies of the low dielectric loss resin compositions of Examples 2 to 8 and Comparative Example 5 ６1 is a graph showing the relationship between the content of 1 and the coefficient of thermal expansion and the dielectric loss tangent.

[0027] (Filler for Low Dielectric Loss Resin Composition) First, the filler for low dielectric loss resin composition (hereinafter referred to as "filler") according to this embodiment will be described below. The filler of this embodiment can be added to, for example, a low dielectric loss resin composition (details of which will be described later) to suppress the loss factor 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.

[0028] The filler of this embodiment includes at least a first inorganic filler having a negative coefficient of thermal expansion. In addition to the case where the filler of this embodiment is composed only of the first inorganic filler, the filler may also include a second inorganic filler having a zero or positive coefficient of thermal expansion, or a composite compound including a base material made of an inorganic fluoride and fluororesin particles held on at least a portion of the surface of the base material.

[0029] <First inorganic filler> The first inorganic filler is made of powder-like solid particles and has a negative thermal expansion coefficient as described above. Therefore, when the first inorganic filler is contained in a low dielectric loss resin composition, the thermal expansion of the low dielectric loss resin composition can be suppressed. Specifically, the thermal expansion coefficient of the first inorganic filler is −1×10 －6 (1 / K) or less, and preferably −3×10 －6 (1 / K) or less is more preferable, and −5×10 －6 It is more preferable that the thermal expansion coefficient is -1×10 (1 / K) or less. －6 If the coefficient of thermal expansion is (1 / K) or less, for example, when the first inorganic filler is contained in the low dielectric loss resin composition, the coefficient of thermal expansion of the low dielectric loss resin composition itself can be reduced. In this specification, "thermal expansion" means that the area or volume of a substance or object increases or the shape expands in response to an increase in temperature without a phase transition. Furthermore, "negative coefficient of thermal expansion" means that the coefficient of thermal expansion is a negative value, and can be measured by the method described in the Examples below.

[0030] Relative dielectric constant ε of the first inorganic filler ｒ１ The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3.5 or less at a frequency of 1 GHz or more and a temperature of 25°C. ｒ１ When the loss factor is 6 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0031] In addition, the dielectric loss tangent tanδ of the first inorganic filler １ The upper limit of [-] is preferably 0.002 or less, more preferably 0.00195 or less, and even more preferably 0.0019 or less, at a frequency of 1 GHz or more and a temperature of 25°C. １ When the loss factor is 0.002 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0032] Furthermore, the upper limit of the loss factor of the first inorganic filler is preferably less than 6, more preferably not more than 5, and particularly preferably not more than 4. When the loss factor is less than 6, the loss factor can be reduced, and the dielectric loss can be reduced.

[0033] The relative permittivity ε used to quantify the dielectric properties and dielectric loss ｒ１ and dielectric tangent tanδ １ Each numerical value is based on a value obtained by measuring the first inorganic filler and converting the measured value. The measurement method can be selected appropriately. Specifically, for example, each can be measured by the method described in the Examples below.

[0034] The loss factor is the relative dielectric constant ε of the first inorganic filler ｒ１ and dielectric tangent tanδ １ The loss coefficient can be calculated using the measured values ​​of (loss coefficient) = (ε ｒ１ ) １／２ ×tan δ １ x10 ３ (In the formula, ε ｒ１ [-] represents the relative dielectric constant of the first inorganic filler, and tan δ １ [-] represents the dielectric tangent.)

[0035] Relative permittivity ε ｒ１ is a parameter indicating the degree of polarization of the first inorganic filler, and the higher the relative dielectric constant, the greater the delay in propagation of an electrical signal. Therefore, in order to increase the signal propagation speed, a lower relative dielectric constant is preferable. １ is a parameter that indicates the amount of a signal propagating inside the first inorganic filler that is converted into heat and lost as a result. Therefore, the lower the dielectric loss tangent, the less signal loss there is, and the more improved the signal transmission rate is.

[0036] The shape of the first inorganic filler is not particularly limited and may be appropriately selected in consideration of, for example, the fluidity when mixed with different solid particles, the fluidity and viscosity of the mixture when mixed with a polymer resin (details of which will be described later), etc. The shape may also be appropriately selected depending on the purpose, such as controlling the mechanical strength, thermal conductivity, gas diffusibility, etc. of a molded article containing the low dielectric loss resin composition.

[0037] The shape of the first inorganic filler can be, for example, any shape such as spherical, approximately spherical, elliptical, rod-like, needle-like, spindle-like, or plate-like. It may also have any of these shapes and be hollow with an internal space. Furthermore, in this embodiment, in addition to using first inorganic fillers of the same shape, it is also possible to use two or more first inorganic fillers of different shapes in combination.

[0038] Specific examples of the first inorganic filler include CaZrF ６ CaZrF etc. ６ can exhibit excellent low dielectric loss characteristics in the high frequency band of 1 GHz or more. ６ By incorporating the above as a constituent component of the low dielectric loss resin composition, not only can the low dielectric loss properties of the low dielectric loss resin composition be improved, but also the thermal expansion coefficient can be reduced, which is a significant effect.

[0039] Furthermore, CaZrF ６ can be produced, for example, by the following method: ６ is CaF ２ and ZrF ４The powder mixture can be produced by a production method including at least a mixing step of producing a powder mixture containing the above and a heating step of heating the powder mixture.

[0040] In the mixing step, CaF ２ and ZrF ４ The method for mixing is not particularly limited, and examples thereof include a mortar, a shaker, a dry bead mill, a mixer, etc. The average particle size, bulk density, etc. of the resulting mixed powder can be appropriately set as needed.

[0041] In the mixing process, the raw material CaF ２ and ZrF ４ Preferably, the method includes a step of reducing (or removing) oxygen-containing components contained in the above. Examples of oxygen-containing components include CaF ２ and ZrF ４ These include hydroxyl groups present on the surface of the powder, adsorbed moisture present on the surface, and oxides and oxyfluorides as impurities. By carrying out a step of reducing (or removing) oxygen atom-containing components, it is possible to obtain CaZrF ６ During the production of (I), 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 examples thereof include heat treatment and reduced pressure treatment. When heat treatment is performed, the heating temperature is preferably in the range of 80°C or higher and 400°C or lower, more preferably in the range of 100°C or higher and 350°C or lower, and even more preferably in the range of 120°C or higher and 300°C or lower. The heating time is preferably in the range of 1 hour or higher and 48 hours or lower, more preferably in the range of 6 hours or higher and 36 hours or lower, and even more preferably in the range of 12 hours or higher and 24 hours or lower.

[0042] The heating method in the heating step is not particularly limited, and known methods can be employed. The heating temperature is preferably in the range of 400°C or higher and 800°C or lower, more preferably in the range of 500°C or higher and 800°C or lower, and even more preferably in the range of 600°C or higher and 800°C or lower. By setting the heating temperature to 400°C or higher, it is possible to remove or reduce impurities such as remaining moisture and organic matter. On the other hand, by setting the heating temperature to 800°C or lower, it is possible to reduce the amount of CaZrF produced. ６ This can prevent thermal fusion and thermal decomposition between the particles. The heating time is preferably in the range of 1 hour to 24 hours, more preferably in the range of 3 hours to 8 hours. By setting the heating time to 3 hours or more, it is possible to remove or reduce impurities such as remaining moisture and organic matter. On the other hand, by setting the heating time to 24 hours or less, it is possible to prevent the CaZrF produced. ６ This can prevent thermal fusion and thermal decomposition between the materials.

[0043] <Second Inorganic Filler> The second inorganic filler is made of powdery solid particles and has a zero or positive thermal expansion coefficient, as described above. By using the second inorganic filler having a zero or positive thermal expansion coefficient in combination with the first inorganic filler having a negative thermal expansion coefficient, the thermal expansion coefficient and dielectric properties of the low dielectric loss resin composition can be controlled as desired.

[0044] Specifically, the thermal expansion coefficient of the second inorganic filler is preferably in the range of 0 (1 / K) or more and 65 (1 / K) or less, more preferably in the range of 0 (1 / K) or more and 60 (1 / K) or less, and even more preferably in the range of 0 (1 / K) or more and 55 (1 / K) or less. Here, "zero thermal expansion coefficient" means that the thermal expansion coefficient is 0, and "positive thermal expansion coefficient" means that the thermal expansion coefficient is a positive value. These thermal expansion coefficients can be measured by the method described in the Examples below.

[0045] Relative dielectric constant ε of the second inorganic filler ｒ２ The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3.5 or less at a frequency of 1 GHz or more and a temperature of 25°C.ｒ２ When the loss factor is 6 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0046] The dielectric loss tangent tanδ of the second inorganic filler ２ The upper limit of [-] is preferably 0.003 or less, more preferably 0.0025 or less, and even more preferably 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C. ２ When the loss factor is 0.003 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0047] Furthermore, the upper limit of the loss factor of the second inorganic filler is preferably less than 6, more preferably not more than 5, and particularly preferably not more than 4. When the loss factor is less than 6, the loss factor can be reduced, and the dielectric loss can be reduced.

[0048] The relative permittivity ε used to quantify the dielectric properties and dielectric loss ｒ２ and dielectric tangent tanδ ２ The values ​​are based on values ​​obtained by measuring the second inorganic filler and converting the measured values. The measurement method can be selected appropriately. Specifically, for example, each can be measured by the method described in the Examples below.

[0049] The loss factor is the relative dielectric constant ε of the second inorganic filler ｒ２ and dielectric tangent tanδ ２ The loss coefficient can be calculated using the measured values ​​of (loss coefficient) = (ε ｒ２ ) １／２ ×tan δ ２ x10 ３ (In the formula, ε ｒ２ [-] represents the relative dielectric constant of the second inorganic filler, and tan δ ２ [-] represents the dielectric tangent.)

[0050] Relative permittivity ε ｒ２ is a parameter indicating the degree of polarization of the second inorganic filler, and the higher the relative dielectric constant, the greater the delay in the propagation of an electrical signal. Therefore, in order to increase the signal propagation speed, a lower relative dielectric constant is preferable. ２is a parameter that indicates the amount of a signal propagating inside the second inorganic filler that is converted into heat and lost as a result. Therefore, the lower the dielectric loss tangent, the less signal loss there is, and the more the signal transmission rate improves.

[0051] The shape of the second inorganic filler is not particularly limited and may be appropriately selected in consideration of, for example, the fluidity when different solid particles are mixed, the fluidity and viscosity of the mixture when mixed with a polymer resin, etc. The shape may also be appropriately selected depending on the purpose, such as controlling the mechanical strength, thermal conductivity, gas diffusivity, etc. of a molded article containing the low dielectric loss resin composition.

[0052] The shape of the second inorganic filler can be, for example, any shape such as spherical, approximately spherical, elliptical, rod-like, needle-like, spindle-like, or plate-like. It may also have any of these shapes and be hollow with an internal space. Furthermore, in this embodiment, in addition to using second inorganic fillers of the same shape, it is also possible to use two or more second inorganic fillers of different shapes in combination.

[0053] Examples of the second inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, zirconium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, zirconium borate, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and fluorine compounds. Further, examples of the fluorine compounds include AlF ３ (aluminum fluoride), K ２ SiF ６ (potassium silicofluoride), NaF (sodium fluoride), KF (potassium fluoride), MgF ２ (Magnesium 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), YF３ (yttrium fluoride), ZrF ４ (zirconium fluoride), SnF ２ (Tin Fluoride), BaF ２ (barium fluoride), LaF ３ (lanthanum fluoride), CeF ３ (cerium fluoride), YbF ２ (ytterbium difluoride), YbF ３ (ytterbium trifluoride), HfF ４ (Hafnium fluoride) and BiF ３ (bismuth fluoride), etc. In addition, as the second inorganic filler, for example, a fibrous inorganic filler such as paper, glass nonwoven fabric, synthetic fiber, cellulose fiber, carbon fiber, and carbon nanotube can also be used. The fibrous inorganic filler can be used without being limited by the shape, etc., of the low dielectric loss resin composition.

[0054] The mass ratio of the first inorganic filler to the second inorganic filler is preferably in the range of 100:0 to 0.01:99.99 (first inorganic filler:second inorganic filler). From the viewpoint of effectively reducing the thermal expansion coefficient of the low dielectric loss resin composition, the mass ratio of the first inorganic filler to the second inorganic filler is more preferably in the range of 80:20 to 0.005:99.995 (first inorganic filler:second inorganic filler), even more preferably in the range of 40:60 to 0.01:99.99, and particularly preferably in the range of 39:61 to 0.1:99.9. In particular, when the mass ratio of the first inorganic filler to the second inorganic filler is in the range of 40:60 to 0.01:99.99, the thermal expansion coefficient can be reduced more effectively than the content of the first inorganic filler, even though the content of the first inorganic filler relative to the second inorganic filler is low. Furthermore, from the viewpoint of effectively improving the low dielectric loss characteristics of the low dielectric loss resin composition, the mass ratio of the first inorganic filler to the second inorganic filler is more preferably in the range of 99.99:0.01 to 40:60, and even more preferably in the range of 99.9:0.1 to 41:59.

[0055] <Composite Compound> The composite compound includes a base material (hereinafter referred to as "base material") made of an inorganic fluoride and fluororesin particles (hereinafter referred to as "fluororesin particles") held on at least a portion of the surface of the base material. By using the composite compound in combination with a first inorganic filler, it is possible to further reduce the coefficient of thermal expansion while maintaining a good dielectric loss in a high-frequency band of 1 GHz or more. Furthermore, depending on the blending ratio of the composite compound and the first inorganic filler, it is also possible to further reduce the loss factor in a high-frequency band of 1 GHz or more.

[0056] In this specification, the phrase "fluororesin particles held" on at least a portion of the surface of a base material refers to a case where the fluororesin particles are held (fixed) by chemical bonding to the surface of the base material, as well as a case where the fluororesin particles are thermally fused to the surface of the base material by thermal melting, thereby physically holding (fixing). In this embodiment, the composite compound is preferably a case where the fluororesin particles are held on the surface of the base material by thermal fusion. Furthermore, in this specification, "thermal fusion" refers to a state in which fluororesin particles, at least the surface of which has been thermally melted by heating, come into contact with a base material made of an inorganic fluoride, and the fluororesin particles are fixed to the base material at the contact surface. The melting point of a fluororesin is usually lower than that of an inorganic fluoride.

[0057] In the composite compound of this embodiment, by supporting fluororesin particles on the surface of an inorganic fluoride matrix, the dielectric constant and dielectric dissipation factor in the high frequency band can be further reduced, improving low dielectric loss characteristics, compared to when a low dielectric loss resin composition contains a first inorganic filler and an inorganic fluoride. In general, inorganic fluorides have higher dielectric constants and dielectric dissipation factors in the high frequency band than silica. Therefore, it is possible to use silica as a matrix and support the fluororesin on its surface. However, it has been found that in this case, although the dielectric constant can be reduced, the dielectric dissipation factor cannot be reduced. Furthermore, it has been found that poor affinity with polymer resins makes it difficult to obtain a low dielectric loss resin composition in which the fluororesin is uniformly dispersed in the polymer resin. Furthermore, when such a low dielectric loss resin composition is used as a material for electronic components, for example, it has been found that the chemical resistance (alkali) is poor, e.g., silica elutes when contacted with an alkaline solution during alkaline etching or the like.

[0058] On the other hand, the composite compound of this embodiment is constructed by selecting an inorganic fluoride from among many inorganic fillers as the matrix and further combining it with a fluororesin from among many polymer resins as the polymer resin supported on the matrix surface. By using the composite compound of this embodiment in combination with a first inorganic filler, the relative dielectric constant and dielectric loss tangent in the high frequency band can be further reduced compared to, for example, using silica alone as the second inorganic filler in combination with the first inorganic filler or using a composite compound with a fluororesin supported on the surface of the silica in combination with the first inorganic filler. Furthermore, the composite compound of this embodiment has good affinity with the polymer resin, so that a low dielectric loss resin composition in which the composite compound is uniformly dispersed can be obtained, and the chemical resistance is also excellent.

[0059] Dielectric constant ε of composite compound ｒ３ The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less at a frequency of 1 GHz or more and a temperature of 25°C. ｒ３ When the loss factor is 6 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0060] In addition, the dielectric loss tangent tanδ of the composite compound ３ The upper limit of [-] is preferably 0.002 or less, more preferably 0.00195 or less, and even more preferably 0.0019 or less, at a frequency of 1 GHz or more and a temperature of 25°C. ３ When the loss factor is 0.002 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0061] Furthermore, the upper limit of the loss factor of the composite compound is preferably less than 6, more preferably not more than 4, and particularly preferably not more than 3. When the loss factor is less than 6, the loss factor can be reduced, and the dielectric loss can be reduced.

[0062] The relative permittivity ε used to quantify the dielectric properties and dielectric loss ｒ３ and dielectric tangent tanδ ３ Each value is based on a value obtained by measuring the composite compound and converting the measured value. The measurement method can be selected appropriately. Specifically, for example, each can be measured by the method described in the Examples below.

[0063] The loss factor is the relative permittivity ε of the composite compound. ｒ３ and dielectric tangent tanδ ３ The loss coefficient can be calculated using the measured values ​​of (loss coefficient) = (ε ｒ３ ) １／２ ×tan δ ３ x10 ３ (In the formula, ε ｒ３ [-] represents the relative dielectric constant of the composite compound, and tan δ ３ [-] represents the dielectric tangent.)

[0064] Relative permittivity ε ｒ３ is a parameter that indicates the degree of polarization of a composite compound, and the higher the relative dielectric constant, the greater the delay in the propagation of an electric signal. Therefore, in order to increase the signal propagation speed, a lower relative dielectric constant is preferable. ３is a parameter that indicates the amount of signal that propagates inside a composite compound and is converted into heat and lost as a result. Therefore, the lower the dielectric tangent, the less signal loss there is, and the better the signal transmission rate.

[0065] The shape of the composite compound is not particularly limited and may be appropriately selected in consideration of, for example, the fluidity when different solid particles are mixed, the fluidity and viscosity of the mixture when mixed with a polymer resin, etc. The shape may also be appropriately selected depending on the purpose, such as controlling the mechanical strength, thermal conductivity, gas diffusivity, etc. of a molded article containing the low dielectric loss resin composition.

[0066] The shape of the composite compound can be, for example, any shape such as spherical, approximately spherical, elliptical, rod-like, needle-like, spindle-like, or plate-like. It may also have any of these shapes and be hollow with an internal space. Furthermore, in this embodiment, in addition to using composite compounds of the same type of shape, it is also possible to use two or more composite compounds of different shapes in combination.

[0067] The mass ratio of the first inorganic filler to the composite compound is preferably in the range of 100:0 to 0.01:99.99 (first inorganic filler:composite compound). From the viewpoint of effectively reducing the thermal expansion coefficient of the low dielectric loss resin composition, the mass ratio of the first inorganic filler to the composite compound is more preferably in the range of 80:20 to 0.005:99.995 (first inorganic filler:composite compound), even more preferably in the range of 40:60 to 0.01:99.99, and particularly preferably in the range of 39:61 to 0.1:99.9. In particular, when the mass ratio of the first inorganic filler to the composite compound is in the range of 40:60 to 0.01:99.99, the thermal expansion coefficient can be reduced more effectively than the content of the first inorganic filler, despite the low content of the first inorganic filler relative to the composite compound. Furthermore, from the viewpoint of effectively improving the low dielectric loss characteristics of the low dielectric loss resin composition, the mass ratio of the first inorganic filler to the composite compound is more preferably in the range of 99.99:0.01 to 40:60, and even more preferably in the range of 99.9:0.1 to 41:59.

[0068] 1. Inorganic Fluoride The base material of the composite compound is preferably an inorganic fluoride in the form of powdered solid particles. The inorganic fluoride is preferably one represented by MFn (wherein M is at least one element 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 of 1 to 4). More specifically, examples of inorganic fluorides include NaF (sodium fluoride), KF (potassium fluoride), and 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 (lanthanum fluoride), CeF ３ (cerium fluoride), YbF ２ (ytterbium difluoride), YbF ３ (ytterbium trifluoride), HfF ４ (Hafnium fluoride) and BiF ３ (bismuth fluoride), etc.

[0069] Among the exemplified inorganic fluorides, aluminum fluoride, cerium fluoride, and magnesium fluoride are preferred, with aluminum fluoride being more preferred, from the viewpoint of reducing the dielectric loss of the composite compound. Furthermore, aluminum fluoride containing crystalline aluminum fluoride having an α-phase as a main component is preferred. Crystalline aluminum fluoride having an α-phase exhibits excellent low dielectric loss characteristics in the high frequency band of 1 GHz or higher. Therefore, by using a base material containing aluminum fluoride as a main component as a constituent material of a low dielectric loss resin composition, a remarkable effect of reducing the dielectric loss of the low dielectric loss resin composition can be achieved.

[0070] The half-width of the peak at the (012) plane of the α phase in the X-ray diffraction pattern of aluminum fluoride is 0.3° or less, preferably 0.25° or less, and more preferably 0.2°. Generally, as the average particle size of inorganic compound particles decreases, the proportion of the surface layer in the entire particle increases. Because the energy state of the particle surface is higher than that of the interior, structural order is easily disrupted, resulting in reduced crystallinity. As a result, the physical and chemical properties derived from the bulk change, and the dielectric loss tangent at the particle surface tends to increase. Therefore, regardless of the average particle size of the inorganic compound, high crystallinity is desirable. Here, in this embodiment, the degree of crystallinity can be evaluated by the half-width of the X-ray diffraction peak at the (012) plane derived from aluminum fluoride. Generally, the smaller the half-width, the higher the crystallinity and the smaller the fluctuation of the crystal structure, resulting in a smaller dielectric loss tangent. Therefore, in the case of aluminum fluoride, its crystallinity can be improved by reducing the half-width of the peak at the (012) plane in the X-ray diffraction pattern. From this viewpoint, in the present embodiment, the upper limit of the half-width is set to 0.3° or less, thereby preventing the crystallinity of aluminum fluoride from becoming too high and suppressing an increase in the dielectric loss tangent, thereby reducing the loss factor and enabling a reduction in the dielectric loss.

[0071] Furthermore, the lower limit of the half-width is preferably 0.12° or more, more preferably 0.15° or more. By setting the lower limit of the half-width to 0.12° or more, excessive grain growth during crystallization or crystal growth of amorphous aluminum fluoride can be prevented, thereby preventing the grain size of the crystal grains from becoming excessively large. This prevents the average particle diameter D50 of aluminum fluoride from becoming large, and suppresses the crystallinity of aluminum fluoride from becoming too high. As a result, when the composite compound of this embodiment is applied to a low dielectric loss resin composition together with a first inorganic filler and formed into a film- or sheet-shaped molded product, even when used in electronic components such as thin-layered printed wiring boards, flexible circuit boards, and high-frequency boards, surface irregularities can be reduced or suppressed, preventing deterioration of electrical properties. Furthermore, film- or sheet-shaped molded products with sufficiently suppressed film thickness can be produced.

[0072] Here, in this specification, "half width" means full width at half maximum. Furthermore, "X-ray diffraction pattern" refers to a plot line of diffraction intensity measured at each incident angle in a two-dimensional graph in which the horizontal axis represents the incident angle and the vertical axis represents the diffraction intensity when a sample is measured by (powder) X-ray diffraction. The "(012) plane of the α-phase in the X-ray diffraction pattern of aluminum fluoride" refers to the oriented plane of the aluminum fluoride crystal, and refers to the (012) plane of the α-phase in the X-ray diffraction pattern. The peak of the diffraction intensity due to the (012) plane of the α-phase of aluminum fluoride is located at a 2θ of approximately 25.3°.

[0073] Relative permittivity ε of inorganic fluoride particles ｒ４ The upper limit of [-] is preferably 6 or less, more preferably 4 or less, and even more preferably 3.5 or less at a frequency of 1 GHz or more and a temperature of 25°C. ｒ４ When the loss factor is 6 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0074] In addition, the dielectric loss tangent tanδ of the inorganic fluoride particles ４The upper limit of [-] is preferably 0.008 or less, more preferably 0.005 or less, and even more preferably 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C. ４ When the loss factor is 0.008 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0075] The upper limit of the loss factor of the inorganic fluoride particles is preferably less than 6, more preferably not more than 4, and even more preferably not more than 3.5. When the loss factor is less than 6, the loss factor of the low dielectric loss resin composition can be reduced, and the dielectric loss can be reduced.

[0076] The relative permittivity ε used to quantify the dielectric properties and dielectric loss ｒ４ and dielectric tangent tanδ ４ The numerical values ​​of the above are based on the values ​​obtained by measuring inorganic fluoride particles made of powder. The measurement method can be selected appropriately. Specifically, for example, each of the values ​​can be measured by the method described in the Examples below.

[0077] The loss factor is the relative permittivity ε of the inorganic fluoride particles made of powder. ｒ４ and dielectric tangent tanδ ４ The loss coefficient can be calculated using the measured values ​​of (loss coefficient) = (ε ｒ４ ) １／２ ×tan δ ４ x10 ３ (In the formula, ε ｒ４ [-] represents the relative dielectric constant of the inorganic fluoride particles made of powder, and tan δ ４ [-] represents the dielectric tangent.)

[0078] Relative permittivity ε ｒ４ is a parameter that indicates the degree of polarization of inorganic fluoride particles, and the higher the relative dielectric constant, the greater the delay in the propagation of electrical signals. Therefore, in order to increase the signal propagation speed, a lower relative dielectric constant is preferable. ４is a parameter that indicates the amount of signal transmitted through the inorganic fluoride particle that is lost due to conversion to heat. Therefore, the lower the dielectric loss tangent, the less signal loss there is, and the better the signal transmission rate.

[0079] The average particle diameter D50 of the inorganic fluoride particles (particle diameter at 50% of the cumulative particle size in the volume-based cumulative particle size distribution) is not particularly limited and can be appropriately set depending on, for example, the shape (size, thickness, etc.) of the molded article containing the low dielectric loss resin composition, and the adjustment of the flowability of the material containing the inorganic fluoride particles in the preparation of the low dielectric loss resin composition. Generally, the upper limit of the average particle diameter D50 of the inorganic fluoride particles 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 diameter D50 of the inorganic fluoride particles 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 diameter D50 of the inorganic fluoride particles is too large, it becomes difficult to obtain a flat surface when the inorganic fluoride particles are applied to a film- or sheet-shaped molded article. As a result, for example, when forming a laminate, the electrical properties of the laminate may be impaired due to the unevenness of the surface of the molded article. On the other hand, if the average particle diameter D50 of the inorganic fluoride particles is too small, it may become difficult to mix the composite compound uniformly with the polymer resin, and the viscosity of the mixture may increase to such an extent that molding of the low dielectric loss resin composition becomes difficult.

[0080] Furthermore, when the low dielectric loss resin composition of this embodiment is formed into a film- or sheet-shaped molded product, the average particle diameter D50 of the inorganic fluoride particles is preferably set to 1 / 5 or less, more preferably 1 / 10 or less, of the thickness of the molded product within the above-mentioned numerical range. For example, when the molded product of the low dielectric loss resin composition is a film or sheet-shaped product with a thickness of approximately 20 μm, the average particle diameter D50 of the inorganic fluoride particles is preferably 10 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. This allows a film- or sheet-shaped molded product to be formed with the composite compound containing the inorganic fluoride particles aligned in a single layer. As a result, a molded product with reduced or prevented surface irregularities can be obtained. Furthermore, in a pre-cured slurry composition in which a composite compound containing inorganic fluoride particles is dispersed in a solvent, sedimentation of the composite compound can be suppressed, allowing a film- or sheet-shaped molded product in which the composite compound is uniformly filled.

[0081] The average particle diameter D50 of the inorganic fluoride particles is a value obtained by measurement by a laser diffraction / scattering method using, for example, Microtrac MT3300EXII (trade name: manufactured by Nikkiso Co., Ltd.).

[0082] The oxygen content of the inorganic fluoride particles is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less, based on the total mass of the inorganic fluoride particles. The content of oxygen-containing components (e.g., surface hydroxyl groups, adsorbed moisture, and oxides and oxyfluorides as impurities) contained in the inorganic fluoride particles can be reduced, thereby suppressing the influence on dielectric properties. More specifically, by reducing the content of oxygen-containing components as impurities, the crystallinity of the inorganic fluoride particles can be improved. Furthermore, by reducing the content of oxyfluorides as oxygen-containing components, the insulating properties of the inorganic fluoride particles can be improved. Furthermore, by reducing hydroxyl groups and adsorbed moisture, which have high polarizability as oxygen-containing components, the deterioration of dielectric properties can also be suppressed.

[0083] The oxygen content of the inorganic fluoride particles can be measured, for example, by using an X-ray fluorescence analyzer (trade name: ZSX Primus II, manufactured by Rigaku Corporation).

[0084] The shape of the inorganic fluoride particles is not particularly limited and may be appropriately selected in consideration of, for example, the fluidity of the mixture when mixed with fluororesin particles in producing a composite compound, or the fluidity of the mixture when the composite compound is mixed with a polymer resin. The shape may also be appropriately selected depending on the purpose, such as controlling the mechanical strength, thermal conductivity, gas diffusivity, etc. of a molded article containing the low dielectric loss resin composition.

[0085] The shape of the inorganic fluoride particles can be, for example, any shape such as spherical, approximately spherical, elliptical, rod-like, needle-like, spindle-like, or plate-like. The inorganic fluoride particles may have any of these shapes and may be hollow with an internal space. Furthermore, in this embodiment, inorganic fluoride particles of the same shape may be used, or two or more inorganic fluoride particles of different shapes may be used in combination.

[0086] Furthermore, in the inorganic fluoride particles of this embodiment, for example, the mass loss after heat treatment at 400°C or higher is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less, relative to the mass of the inorganic fluoride particles before heat treatment. By using inorganic fluoride particles with a mass loss of 2% by mass or less after heat treatment, it is possible to prevent a decrease in the low dielectric loss characteristics and mechanical strength of the low dielectric loss resin composition due to heat generation during polymerization of the monomers that form the polymer resin, degassing of impurities during heat treatment, and thermal decomposition of the main component of the polymer resin. There are no particular limitations on the method for reducing the mass loss of inorganic fluoride particles after heat treatment to 2% by mass or less. For example, materials with high thermal decomposition temperatures, materials that do not undergo phase change upon heating, and impurities that cause mass loss during the synthesis of the inorganic fluoride particles may be removed or reduced by prior heat treatment or chemical treatment.

[0087] 2. Fluororesin Particles The fluororesin particles may be held on at least a portion of the surface of the base material. In an embodiment in which the fluororesin particles are held on a portion of the surface of the base material, the Lewis acid sites are exposed on the surface of the base material where the fluororesin particles are not held. Generally, fluororesins are not compatible with polymer resins. However, by preventing a portion of the surface of the base material from being covered with fluororesin particles, the affinity of the composite compound for the polymer resin in the low dielectric loss resin composition is well maintained, and a decrease in dispersibility in the polymer resin can be suppressed. On the other hand, in an embodiment in which a large amount of the fluororesin particles are held, for example, on the entire surface of the base material, the dielectric loss can be further reduced.

[0088] The fluororesin particles are not particularly limited, and examples thereof include those made of 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.

[0089] The average particle diameter d50 of the fluororesin particles (particle diameter at 50% of the cumulative particle size in the volume-based cumulative particle size distribution) is preferably in the range of 1 / 10 to 1 / 2 of the average particle diameter D50 of the inorganic fluoride particles. By making the average particle diameter d50 of the fluororesin particles 1 / 10 or more of the average particle diameter D50 of the inorganic fluoride particles, it is possible to entirely coat the base material. On the other hand, by making the average particle diameter d50 of the fluororesin particles 1 / 2 or less of the average particle diameter D50 of the inorganic fluoride particles, it is possible to prevent self-fusion.

[0090] The average particle diameter d50 of the fluororesin particles is a value obtained by measurement by a laser diffraction / scattering method using, for example, Microtrac MT3300EXII (trade name: manufactured by Nikkiso Co., Ltd.).

[0091] The shape of the fluororesin particles before being held in the base material is not particularly limited, and any shape can be used, such as spherical, approximately spherical, elliptical, rod-like, needle-like, spindle-like, plate-like, etc. In addition to using fluororesin particles of the same type of shape, it is also possible to use fluororesin particles of two or more different shapes in combination.

[0092] The content of the fluororesin particles is preferably in the range of 0.5% by mass or more and less than 26% by mass, more preferably in the range of 1% by mass or more and 25% by mass or less, even more preferably in the range of 1% by mass or more and 15% by mass or less, and particularly preferably in the range of 1% by mass or more and 10% by mass or less, relative to the total mass of the base material. By making the content of the fluororesin particles 0.5% by mass or more, the excellent low dielectric loss characteristics of the composite compound can be maintained. On the other hand, by making the content of the fluororesin particles less than 26% by mass, the affinity of the composite compound for the polymer resin can be well maintained, and a decrease in dispersibility in the polymer resin can be suppressed.

[0093] Relative dielectric constant εr of fluororesin particles ５ The upper limit of [-] is preferably 3.5 or less, more preferably 3.0 or less, and even more preferably 2.9 or less at a frequency of 1 GHz or more and a temperature of 25°C. ５ When the value is 3.5 or less, the loss factor of the composite compound and the low dielectric loss resin composition containing the composite compound can be reduced, and the dielectric loss can be suppressed and reduced.

[0094] In addition, the fluororesin particles have a dielectric loss tangent tanδ ５ The dielectric loss tangent tanδ of the fluororesin particles is 0.002 or less, preferably 0.001 or less, at a frequency of 1 GHz or more and a temperature of 25°C. ５ When the value is 0.002 or less, the dielectric loss tangent of the composite compound and the low dielectric loss resin composition containing the composite compound can be reduced, and the low dielectric loss characteristics can be further improved.

[0095] The upper limit of the loss factor of the fluororesin particles is preferably not more than 6, more preferably not more than 4, and even more preferably not more than 3. When the loss factor is not more than 6, the loss factor of the composite compound and the low dielectric loss resin composition can be reduced, and the low dielectric loss characteristics can be further improved.

[0096] The relative dielectric constant εr used to quantify the dielectric properties and dielectric loss ５ and dielectric tangent tanδ ５ The numerical values ​​are based on values ​​obtained by measuring the fluororesin particles and converting the measured values. The measurement method can be appropriately selected. Specifically, for example, each can be measured by the method described in the Examples below.

[0097] The loss factor is the relative dielectric constant εr of the fluororesin particles. ５ and dielectric tangent tanδ ５ Using the measured values, the loss factor can be calculated based on the following formula: (Loss factor) = (εr ５ ) １／２ ×tan δ ５ x10 ３ (In the formula, εr ５ [-] represents the relative dielectric constant of the fluororesin particles, and tan δ ５ [-] represents the dielectric tangent.)

[0098] Relative permittivity εr ５ is a parameter that indicates the degree of polarization of fluororesin particles, and the higher the relative dielectric constant, the greater the delay in the propagation of electrical signals. Therefore, in order to increase the signal propagation speed, a lower relative dielectric constant is preferable. ５ is a parameter that indicates the amount of signal transmitted through the fluororesin particle that is converted into heat and lost as a result. Therefore, the lower the dielectric loss tangent, the less signal loss there is, and the better the signal transmission rate.

[0099] 3. Manufacturing Method of Composite Compound Next, a manufacturing method of the composite compound will be described below. The manufacturing method of the composite compound of this embodiment is not particularly limited, and known methods can be used. For example, when manufacturing a composite compound in which fluororesin particles are thermally fused to the surface of a base material, the method may include a method (composite treatment) that includes at least a mixing step of mixing the fluororesin particles with an inorganic fluoride base material, a heating step of heating the mixture of the fluororesin particles and the inorganic fluoride base material, and a cooling step of cooling the mixture after heating.

[0100] The heating method in the heating step is not particularly limited, and known methods can be used. The heating temperature is not particularly limited as long as it is equal to or higher than the melting point and lower than the boiling point of the fluororesin particles, and can be appropriately set depending on the type of fluororesin, etc. The heating time is also not particularly limited, and can be appropriately set depending on the heating temperature and the type of material of the fluororesin particles, etc. The cooling method in the cooling step is not particularly limited, and can be, for example, natural cooling or rapid cooling.

[0101] 4. Others The surface of the inorganic fluoride base material of this embodiment may be chemically modified by introducing functional groups such as hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, amino groups, perfluoroalkane groups, ether groups, and ester groups, within the scope of not impairing the effects of the present invention. Furthermore, the surface of the fluororesin particles of this embodiment may also 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, within the scope of not impairing the effects of the present invention.

[0102] In this embodiment, the inorganic fluoride and the fluororesin particles can be any combination of the materials exemplified above, but it is preferable to use fluororesin particles that have a smaller relative permittivity, dielectric loss tangent, and loss factor than the inorganic fluoride, thereby further reducing the dielectric loss compared to when the first inorganic filler and the inorganic filler consisting of inorganic fluoride particles are used in the low dielectric loss resin composition.

[0103] (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 contains at least the above-mentioned filler and polymer resin.

[0104] The lower limit of the filler content is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total mass of the low dielectric loss resin composition. Meanwhile, 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, relative to the total mass of the low dielectric loss resin composition. When the filler content is 1% by mass or more, the loss factor of the low dielectric loss resin composition decreases, thereby reducing the dielectric loss. Meanwhile, when the filler content is 85% by mass or less, deterioration of physical strength such as brittleness can be prevented, and it is possible to improve hardness, reduce the thermal expansion coefficient, and improve weather resistance.

[0105] The polymeric resin preferably comprises at least one thermoplastic resin and / or at least one thermosetting resin.

[0106] More specifically, polymer resins include, for example, olefin-based resins such as polyethylene resins and polypropylene resins; polycarbonate resins; polyphenylene ether resins; polysulfone resins; polyethersulfone resins; polyphenylene sulfide resins; polyetheretherketone resins; liquid crystal polymer resins; polyimide resins; fluororesins such as polytetrafluoroethylene resin (PTFE), copolymers of polytetrafluoroethylene and perfluoroalkoxyethylene (PFA), polychlorotrifluoroethylene resin (PCTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (ETFE); phenolic resins; epoxy resins; silicone resins; and modified versions thereof. These polymer resins can be used alone or in combination of two or more types, depending on the processability and application of the low dielectric loss resin composition. For example, when using a polymer resin in which an epoxy resin is mixed with a polyphenylene ether resin, processability can be improved by increasing the fluidity. 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.

[0107] The content of the polymer resin is preferably in the range of 15% by mass or more and 99% by mass or less, more preferably 18% by mass or more and 90% by mass or less, and even more preferably 21% by mass or more and 80% by mass or less, based on the total mass of the low dielectric loss resin composition. By making the content of the polymer resin 15% by mass or more, the properties of the polymer resin, such as adhesiveness and water resistance, can be fully exhibited. On the other hand, by making the content of the polymer resin 99% by mass or less, the thermal expansion coefficient and dielectric loss of the low dielectric loss resin composition can be reduced by including a filler while maintaining the properties of the polymer resin.

[0108] The low dielectric loss resin composition of this embodiment has a reduced coefficient of thermal expansion compared to, for example, the low dielectric loss resin composition of this embodiment that does not contain a filler. The reduced coefficient of thermal expansion is particularly effective when using a polymer resin with a relatively high coefficient of thermal expansion, such as an epoxy resin. The reduction in the coefficient of thermal expansion of 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 solely of a polymer resin. Reducing the coefficient of thermal expansion of the low dielectric loss resin composition by 20% or more can enhance the life and functionality of electronic components for high-frequency applications that require dimensional stability. The reduction in the coefficient of thermal expansion of the low dielectric loss resin composition can be calculated using the following formula: (reduction in the coefficient of thermal expansion of the low dielectric loss resin composition) (%) = (β ０ -β １ ) β ０ ×100 (in the formula, β ０ represents the thermal expansion coefficient of a low dielectric loss resin composition consisting only of a polymer resin, and β １ 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 contents of the filler and polymer resin, the blending ratio of the first inorganic filler to the optional second inorganic filler or composite compound, the types of the second inorganic filler and composite compound, etc.

[0109] Relative dielectric constant ε of low dielectric loss resin composition ｒ６ The upper limit of [-] is preferably 6 or less, more preferably 5 or less, and particularly preferably 4 or less, at a frequency of 1 GHz or more and a temperature of 25°C. ｒ６ When the loss factor is 6 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0110] In addition, the dielectric loss tangent tanδ of the low dielectric loss resin composition ６The upper limit of [-] is preferably 0.02 or less, more preferably 0.019 or less, and even more preferably 0.018 or less at a frequency of 1 GHz or more and a temperature of 25°C. ６ When the loss factor is 0.02 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0111] The upper limit of the loss factor of the low dielectric loss resin composition is preferably less than 40, more preferably not more than 38, and particularly preferably not more than 35. When the loss factor is less than 40, the loss factor of the low dielectric loss resin composition can be reduced, and the dielectric loss can be reduced.

[0112] The relative permittivity ε used to quantify the dielectric properties and dielectric loss ｒ６ and dielectric tangent tanδ ６ The values ​​are based on values ​​obtained by measuring the low dielectric loss resin composition and converting the measured values. The measurement method can be selected appropriately. Specifically, for example, each can be measured by a method similar to the method described in the Examples below.

[0113] The loss factor is the relative dielectric constant ε of the low dielectric loss resin composition ｒ６ and dielectric tangent tanδ ６ The loss coefficient can be calculated using the measured values ​​of (loss coefficient) = (ε ｒ６ ) １／２ ×tan δ ６ x10 ３ (In the formula, ε ｒ６ [-] represents the relative dielectric constant of the low dielectric loss resin composition, and tan δ ６ [-] represents the dielectric tangent.)

[0114] Relative permittivity ε ｒ６ is a parameter that indicates the degree of polarization of a low dielectric loss resin composition, and the higher the relative dielectric constant, the greater the delay in the propagation of an electric signal. Therefore, in order to increase the signal propagation speed, a lower relative dielectric constant is preferable. Dielectric loss tangent tanδ ６is a parameter that indicates the amount of signal transmitted through the low dielectric loss resin composition that is converted into heat and lost as a result. Therefore, the lower the dielectric loss tangent, the less signal loss there is, and the better the signal transmission rate.

[0115] 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 according to this embodiment can be produced by adding a first inorganic filler, an optional second inorganic filler, an optional composite compound, and optional other additives to a polymer resin in any order and uniformly mixing or kneading them. Alternatively, the low dielectric loss resin composition can be produced by adding a first inorganic filler, an optional second inorganic filler, an optional composite compound, and optional other additives to a solution (e.g., a varnish or dispersion) in which a polymer resin or a monomer that forms the polymer resin is dissolved or dispersed in an organic solvent, and then dispersing the first inorganic filler, an optional second inorganic filler, an optional composite compound, and optional other additives in any order.

[0116] The low dielectric loss resin composition of this embodiment may contain impurities to the extent that it does not contradict the object of the present invention. Examples of such impurities include metal impurities containing elements other than those constituting the first inorganic filler, the second inorganic filler, and the inorganic fluoride, 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.

[0117] The low dielectric loss resin composition of the present embodiment may contain other additives as long as they do not interfere with the object of the present invention. The other additives are not particularly limited, and examples thereof include curing agents, lubricants, crystal nucleating agents, ultraviolet protection agents, colorants, flame retardants, stabilizers, plasticizers, reinforcing agents, and dispersants. The content of the other additives is not particularly limited, and can be appropriately determined depending on the application, purpose, etc.

[0118] The low dielectric loss resin composition of the present embodiment can be used as a resin composition for insulating films (solder resist), a resin composition for semiconductor encapsulation, an adhesive, a paint, a covering material for wiring for power supplies, communications, etc.

[0119] (Molded body for high-frequency device and manufacturing method thereof) The molded body for high-frequency device of the present embodiment (hereinafter referred to as "molded body") is made of a molded body containing a low dielectric loss resin composition. The molded body may be made of only the low dielectric loss resin composition.

[0120] The reduction rate of the thermal expansion coefficient of the molded body is the same as that of the low dielectric loss resin composition described above. That is, the reduction rate of the thermal expansion coefficient of the molded body 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 thermal expansion coefficient of a molded body made only of a polymer resin. The reduction rate of the thermal expansion coefficient of the molded body can be calculated using the following formula: (reduction rate of the thermal expansion coefficient of the molded body) (%) = (β ０ '-β １ ') β ０ '×100 (in the formula, β ０ ' represents the thermal expansion coefficient of a molded body made of polymer resin only, and β １ ' represents the thermal expansion coefficient of the molded body of this embodiment.)

[0121] Dielectric constant ε of molded body ｒ７ The upper limit of [-] is preferably 6 or less, more preferably 5 or less, and particularly preferably 4 or less, at a frequency of 1 GHz or more and a temperature of 25°C. ｒ７ When the loss factor is 6 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0122] In addition, the dielectric loss tangent tanδ of the molded body ７ The upper limit of [-] is preferably 0.02 or less, more preferably 0.019 or less, and even more preferably 0.018 or less at a frequency of 1 GHz or more and a temperature of 25°C. ７ When the loss factor is 0.02 or less, the loss factor can be reduced, and the dielectric loss can be reduced.

[0123] The upper limit of the loss factor of the molded article is preferably less than 40, more preferably not more than 38, and particularly preferably not more than 35. When the loss factor is less than 40, the loss factor of the molded article can be reduced, and the dielectric loss can be reduced.

[0124] The relative permittivity ε used to quantify the dielectric properties and dielectric loss ｒ７ and dielectric tangent tanδ ７ The numerical values ​​are based on values ​​obtained by measuring the molded body and converting the measured values. The measurement method can be selected appropriately. Specifically, for example, each can be measured by the method described in the Examples below.

[0125] The loss factor is the relative dielectric constant ε of the compact ｒ７ and dielectric tangent tanδ ７ The loss coefficient can be calculated using the measured values ​​of (loss coefficient) = (ε ｒ７ ) １／２ ×tan δ ７ x10 ３ (In the formula, ε ｒ７ [-] represents the relative dielectric constant of the molded body, and tan δ ７ [-] represents the dielectric tangent.)

[0126] The molded body can be produced, for example, by using a known kneader and extruder. Examples of kneaders that can be used include an internal pressure kneader and an open roll. A sheet-shaped low dielectric loss resin composition material can be produced using these kneaders, and then a molded body can be produced using the low dielectric loss resin composition material. Alternatively, a pellet-shaped low dielectric loss resin composition material can be produced using an extruder, and then a molded body can be produced using an injection molding machine. When a molding machine such as an extruder is used to mix a polymer resin with a filler and other additives, the number of steps can be reduced, and production efficiency can be improved. Furthermore, the filler may be appropriately dried before being mixed with the polymer resin.

[0127] Furthermore, a sheet-like molded product can be produced by a known method. For example, a filler and any other additives are added to a varnish tank filled with a solution (resin varnish) containing a polymer resin, and the resulting mixture is uniformly dispersed. The dispersion is then heated at a predetermined temperature. The cured product produced by heating is stretched into a sheet, thereby producing a sheet-like molded product.

[0128] Alternatively, a sheet-like substrate such as glass cloth or a bonding sheet may be immersed in a bath of a dispersion containing a polymer resin, a filler, and any other additives, and passed through the bath to impregnate the sheet-like substrate with the dispersion. The sheet impregnated with the dispersion is then dried to produce an impregnated sheet impregnated with the low dielectric loss resin composition. By passing the sheet-like substrate through the bath of the dispersion multiple times, it is also possible to produce a laminate in which multiple low dielectric loss resin composition layers are stacked.

[0129] (High-Frequency Device) The high-frequency device according to this embodiment contains a low dielectric loss resin composition or includes a molded article of a low dielectric loss resin composition.

[0130] The high-frequency device of this embodiment is used for information processing and information communication performed by electronically exchanging signals. In particular, the high-frequency device of this embodiment is used in a high-frequency band in which the frequency band of radio waves and signals used during communication is 1 GHz or higher, more preferably 10 GHz or higher. The high-frequency device of this embodiment also includes high-frequency electronic components used in such high-frequency bands.

[0131] Examples of high-frequency devices include housings for information processing and information communication devices, circuit boards, printed wiring boards, transmission lines, high-frequency electronic components such as capacitors and inductors, and ceiling and wall materials for rooms in which high-frequency devices are installed.Furthermore, high-frequency devices including insulating films and semiconductor sealing resins formed from the low dielectric loss resin composition, and wiring coated with the low dielectric loss resin composition as a coating material are also included in the high-frequency devices of the present embodiment.

[0132] Preferred examples of the present invention are described in detail below. However, unless otherwise specified, the materials and blending amounts described in the examples are not intended to limit the scope of the present invention.

[0133] Example 1 <Calculation of relative permittivity, dielectric loss tangent and loss factor> First, CaZrF as the first inorganic filler ６ The powder was filled into a quartz tube, and the relative permittivity and dielectric loss tangent were measured in a 10 GHz frequency range by a cavity resonator method under an environmental atmosphere of 25°C and 40% relative humidity. A vector network analyzer (manufactured by Anritsu Corporation, product name: MS46122B) was used for the measurements. ６ The relative permittivity and dielectric loss tangent of the quartz tube filled with CaZrF ６ Bulk density and true density of CaZrF versus packing volume ６ The void portion is corrected using the filling amount of CaZrF ６ The relative permittivity ε ｒ１ [-] and dielectric tangent tanδ １ [-] was calculated. The loss factor was calculated using the following formula. The results are shown in Table 1. (Loss factor) = (ε ｒ１ ) １／２ ×tan δ １ x10 ３ (In the formula, ε ｒ１ [-] represents the relative dielectric constant of the first inorganic filler, and tan δ １ [-] represents the dielectric tangent.)

[0134] <Measurement of thermal expansion coefficient> Next, CaZrF ６ The coefficient of thermal expansion (CTE) of CaZrF was measured using an X-ray diffraction device (product name: RINT-ULTIMA, manufactured by Rigaku Corporation). ６ The powder was heated from 25°C to the target temperature of 100°C at a rate of 10°C / min. After that, it was maintained at 100°C for 2 minutes, and then the CaZrF obtained from the X-ray diffraction pattern was ６The 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 each temperature were measured in the same manner at 200°C, 300°C, and 400°C. The obtained lattice volume changes were then linearly converted to obtain CaZrF ６ The thermal expansion coefficient of each sample was determined. The results are shown in Table 1. The detailed conditions for measuring the thermal expansion coefficient are as follows: X-ray tube: Cu Tube voltage: 40 kV Tube current: 40 mA Step size: 0.02° Measurement range: 2θ = 10° to 70° Heating rate: 10°C / min Measurement temperatures: 25°C, 100°C, 200°C, 300°C, 400°C

[0135] (Comparative Example 1) In this comparative example, CaZrF ６ Instead of CaF ２ (manufactured by Stella Chemifa Corporation) was used. Otherwise, the relative permittivity, dielectric loss tangent, loss factor, and coefficient of thermal expansion were determined in the same manner as in Example 1. The results are shown in Table 1.

[0136] (Comparative Example 2) In this comparative example, CaZrF ６ Instead of ZrF ４ (manufactured by Stella Chemifa Corporation) was used. Otherwise, the relative permittivity, dielectric loss tangent, loss factor, and coefficient of thermal expansion were determined in the same manner as in Example 1. The results are shown in Table 1.

[0137] (Comparative Example 3) In this comparative example, CaZrF ６ Instead of K ２ ZrF ６ (manufactured by Stella Chemifa Corporation) was used. Otherwise, the relative permittivity, dielectric loss tangent, loss factor, and coefficient of thermal expansion were determined in the same manner as in Example 1. The results are shown in Table 1.

[0138] (Comparative Example 4) 95 parts by mass of α-AlF ３ (manufactured by Stella Chemifa Corporation, half-width: 0.17°, average particle diameter D50: 2 μm) was mixed with 5 parts by mass of PTFE particles (average particle diameter d50: 200 nm to 500 nm, relative dielectric constant: 3.0 [-] or less, dielectric loss tangent: 0.002 [-] or less), and then the PTFE particles were heated at a temperature equal to or higher than the melting point of the PTFE particles to form α-AlF ３The composite compound was heated so as to thermally fuse to the surface of the composite compound. The composite compound was then cooled to room temperature to produce a composite compound according to this comparative example. The dielectric constant, dielectric loss tangent, and loss factor of the composite compound were determined in the same manner as in Example 1. The results are shown in Table 1. It should be noted that measurement of the thermal expansion coefficient of the composite compound was omitted because it is difficult to measure it with the same accuracy as that of a single compound as in Example 1 and Comparative Examples 1 to 3.

[0139]

[0140] (Result 1) As shown in Table 1, the CaZrF of Example 1 ６ It was confirmed that, compared with the fillers of Comparative Examples 1 to 3, CaZrF not only had a negative coefficient of thermal expansion, but also had small values ​​of relative permittivity and dielectric loss tangent measured at the same frequency, and also had excellent low dielectric loss characteristics. In particular, CaZrF ６ is the K of Comparative Example 3 ２ ZrF ６ However, the physical properties vary greatly depending on the metal cation species, and it has been confirmed that this compound is an excellent inorganic filler for low dielectric loss resin compositions.

[0141] Example 2 Preparation of Low Dielectric Loss Resin Composition 10 g of epoxy resin (trade name: jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation), 5 g of epoxy resin curing agent (trade name: jER Cure (registered trademark), manufactured by Mitsubishi Chemical Corporation), and CaZrF as a first inorganic filler were mixed. ６ 15 g of the above was placed in a container cup and kneaded with a defoaming mixer to prepare a paste.

[0142] <Calculation of relative permittivity, dielectric loss tangent, and loss factor> The prepared paste was placed in a mold and cured at room temperature for 1 day, and then further heated and cured at 80°C for 3 hours. Next, it was removed from the mold and molded body A (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 example was prepared. Subsequently, the obtained molded body A was subjected to measurement of the relative permittivity ε by a cavity resonator method in the 10 GHz frequency range in an environmental atmosphere at a temperature of 19°C and a relative humidity of 50%. ｒ７ and dielectric tangent tanδ ７The loss factor of molded body A was calculated using the following formula. The results are shown in Table 2. (Loss factor) = (ε ｒ７ ) １／２ ×tan δ ７ x10 ３ (In the formula, ε ｒ７ [-] represents the relative dielectric constant of the molded body A, and tan δ ７ [-] represents the dielectric tangent.)

[0143] <Measurement of Thermal Expansion Coefficient> The prepared paste was placed in another mold and cured at room temperature for one day, and then further heated and cured at 80°C for three hours. The paste was then removed from the mold to prepare a molded body B (a cylindrical body with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition according to this example. The thermal expansion coefficient of the prepared molded body B was then measured. A thermomechanical analyzer (product name: TMA / SS-6100, manufactured by Seiko Instruments Inc.) was used for the measurement. The measurement was performed in a nitrogen atmosphere, with the temperature rising from 40°C to 150°C at a rate of 5°C / min. During the temperature rise, a measurement load of 20 mN was applied in the longitudinal direction of molded body B. The results are shown in Table 2.

[0144] (Example 3) In this example, 50% by mass of CaZrF ６ Instead of 40% by mass of CaZrF ６ A mixture of 10% by mass of a composite compound was used (mass ratio: CaZrF ６ : composite compound = 80:20). The composite compound used was the composite compound of Comparative Example 4. Except for these, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition of this example were produced in the same manner as in Example 2, and the relative dielectric constant ε ｒ７ , dielectric tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0145] Example 4 In this example, 50% by mass of CaZrF 2 was used as a filler. ６Instead of 25% by mass of CaZrF ６ A mixture of 25% by mass of a composite compound (mass ratio: CaZrF ６ : composite compound = 50:50). The composite compound used was the composite compound of Comparative Example 4. Except for these, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition of this example were produced in the same manner as in Example 2, and the relative dielectric constant ε ｒ７ , dielectric loss tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0146] (Example 5) In this example, 50% by mass of CaZrF ６ Instead of 20 mass% CaZrF ６ A mixture of 30 mass% of a composite compound (mass ratio: CaZrF ６ : composite compound = 40:60). The composite compound used was the composite compound of Comparative Example 4. Except for these, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition of this example were produced in the same manner as in Example 2, and the relative dielectric constant ε ｒ７ , dielectric loss tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0147] Example 6 In this example, 50% by mass of CaZrF 2 was used as a filler. ６ Instead of 15% by mass of CaZrF ６ A mixture of 35% by mass of a composite compound (mass ratio: CaZrF ６ : composite compound = 30:70). The composite compound used was the composite compound of Comparative Example 4. Except for these, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition of this example were produced in the same manner as in Example 2, and the relative dielectric constant ε ｒ７ , dielectric loss tangent tanδ ７The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0148] Example 7 In this example, 50% by mass of CaZrF 2 was used as a filler. ６ Instead of 10 mass% CaZrF ６ A mixture of 40% by mass of a composite compound (mass ratio: CaZrF ６ : composite compound = 20:80). The composite compound used was the composite compound of Comparative Example 4. Except for these, molded bodies A (cylindrical body with a diameter of 1 mm and a height of 15 cm) and B (cylindrical body with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition of this example were produced in the same manner as in Example 2, and the relative dielectric constant ε ｒ７ , dielectric tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0149] (Example 8) In this example, 50% by mass of CaZrF ６ Instead of 5 mass % CaZrF ６ A mixture of 45% by mass of a composite compound (mass ratio: CaZrF ６ : composite compound = 10:90). The composite compound used was the composite compound of Comparative Example 4. Except for these, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition of this example were produced in the same manner as in Example 2, and the relative dielectric constant ε ｒ７ , dielectric tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0150] Comparative Example 5 In this comparative example, CaZrF ６ Instead, the composite compound according to Comparative Example 4 was used. Molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition according to this Comparative Example were produced in the same manner as in Example 2, and the relative dielectric constant ε of molded body A was ｒ７ , dielectric tangent tanδ ７The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0151] Comparative Example 6 In this comparative example, no filler was added. Except for this, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition according to this comparative example were prepared in the same manner as in Example 2. Furthermore, the relative dielectric constant ε ｒ７ , dielectric tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 2.

[0152]

[0153] (Result 2) As shown in Table 2, in Example 2, CaZrF was added to the epoxy resin. ６ By adding CaZrF ６ It was confirmed that, compared with Comparative Example 6 in which only epoxy resin was used without adding CaZrF as a filler, not only was the dielectric loss tangent reduced, but the thermal expansion coefficient was also significantly reduced. ６ Example 2 using only CaZrF as a filler ６ It was confirmed that in Examples 3 to 8, in which CaZrF was used in combination with a composite compound, the coefficient of thermal expansion could be reduced while the increase in the dielectric loss tangent was well suppressed, compared to Comparative Example 5, in which only a composite compound was used as a filler. ６ 1 is a graph showing the relationship between the content of the resin composition and the coefficient of thermal expansion and the dielectric loss tangent. The reduction rate (%) of the coefficient of thermal expansion (CTE) of each molded body B in Table 2 was calculated by the following formula: (reduction rate of the coefficient of thermal expansion of molded body B of low dielectric loss resin composition) (%) = (β ２ -β ３ ) β ２ ×100 (in the formula, β ２ represents the thermal expansion coefficient of the molded body B of Comparative Example 6, and β ３ represents the thermal expansion coefficient of molded body B of Examples 2 to 8 or Comparative Example 5.)

[0154] (Example 9) In this example, 50% by mass of CaZrF６ Instead of 25% by mass of CaZrF ６ and 25 mass% AlF ３ A mixture of CaZrF (second inorganic filler, manufactured by Stella Chemifa Corporation, thermal expansion coefficient: 37 (1 / K), relative permittivity: 3.1 [-], dielectric loss tangent: 0.0018 [-], loss factor: 3.2) was used (mass ratio: ６ : AlF ３ = 50:50). Except for this, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition according to this example were prepared in the same manner as in Example 2. Furthermore, the relative dielectric constant ε ｒ７ , dielectric loss tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 3.

[0155] (Example 10) In this example, 50% by mass of CaZrF ６ Instead of 25% by mass of CaZrF ６ and 25 mass% K ２ SiF ６ A mixture of CaZrF (second inorganic filler, manufactured by Stella Chemifa Corporation, thermal expansion coefficient: 65 (1 / K), relative permittivity: 3.4 [-], dielectric loss tangent: 0.0020 [-], loss factor: 3.8) was used (mass ratio: ６ :K ２ SiF ６ = 50:50). Except for this, molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition according to this example were prepared in the same manner as in Example 2. Furthermore, the relative dielectric constant ε ｒ７ , dielectric loss tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 3.

[0156] Comparative Example 7 In this comparative example, CaZrF ６ Instead of AlF ３(manufactured by Stella Chemifa Corporation, coefficient of thermal expansion: 37 (1 / K), relative permittivity: 3.1 [-], dielectric dissipation factor: 0.0018 [-], loss factor: 3.2) was used. Molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition according to this comparative example were prepared in the same manner as in Example 2, and the relative permittivity ε ｒ７ , dielectric tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 3.

[0157] Comparative Example 8 In this comparative example, CaZrF ６ Instead, K ２ SiF ６ (manufactured by Stella Chemifa Corporation, coefficient of thermal expansion: 65 (1 / K), relative permittivity: 3.4 [-], dielectric dissipation factor: 0.0020 [-], loss factor: 3.8) was used. Molded bodies A (cylindrical bodies with a diameter of 1 mm and a height of 15 cm) and B (cylindrical bodies with a diameter of 7 mm and a height of 6 mm) of the low dielectric loss resin composition according to this comparative example were prepared in the same manner as in Example 2, and the relative permittivity ε ｒ７ , dielectric tangent tanδ ７ The loss factor and the thermal expansion coefficient of the molded body B were measured. The results are shown in Table 3.

[0158] (Result 3) As shown in Table 3, in Examples 9 and 10, AlF was used as the filler. ３ or K ２ SiF ６ In addition to CaZrF, which has a negative thermal expansion coefficient ６ By adding CaZrF ６ It was confirmed that the thermal expansion coefficient could be reduced while maintaining low dielectric loss characteristics in comparison with Comparative Examples 7 and 8, which did not contain the resin composition. The reduction rate (%) of the thermal expansion coefficient of each molded body B in Table 3 was calculated using the following formula: (reduction rate of the thermal expansion coefficient of molded body B of low dielectric loss resin composition) (%) = (β ２ -β ４ ) β ２ ×100 (in the formula, β ２ represents the thermal expansion coefficient of the molded body B of Comparative Example 6, and β ４represents the thermal expansion coefficient of the molded body B of Examples 9 and 10 or Comparative Examples 7 and 8.)

Claims

1. A filler for a low dielectric loss resin composition, comprising a first inorganic filler having a negative thermal expansion coefficient, the first inorganic filler having a dielectric tangent of 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C.

2. A filler for a low dielectric loss resin composition according to claim 1, further comprising a second inorganic filler having a zero or positive thermal expansion coefficient, the dielectric tangent of which is 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C.

3. A filler for a low dielectric loss resin composition as described in claim 2, wherein the mass ratio of the first inorganic filler to the second inorganic filler, i.e., first inorganic filler:second inorganic filler, is within the range of 100:0 to 0.01:99.

99.

4. A filler for low dielectric loss resin compositions according to claim 1, further comprising a composite compound comprising a base material made of an inorganic fluoride and fluororesin particles held on at least a portion of the surface of the base material, wherein the dielectric tangent of the fluororesin particles is 0.002 or less at a frequency of 1 GHz or more and a temperature of 25°C.

5. A filler for a low dielectric loss resin composition according to claim 4, wherein the mass ratio of the first inorganic filler to the composite compound, i.e., first inorganic filler:composite compound, is within the range of 100:0 to 0.01:99.

99.

6. The first inorganic filler is CaZrF ６ 2. The filler for a low dielectric loss resin composition according to claim 1, which is 7. A low dielectric loss resin composition comprising at least a polymer resin and the filler for low dielectric loss resin compositions according to any one of claims 1 to 6.

8. A low dielectric loss resin composition according to claim 7, wherein the content of the filler for the low dielectric loss resin composition is in the range of 1 mass % or more and 85 mass % or less relative to the total mass of the low dielectric loss resin composition.

9. The low dielectric loss resin composition according to claim 7, wherein the polymeric resin comprises at least one thermoplastic resin and / or at least one thermosetting resin.

10. The low dielectric loss resin composition according to claim 7, 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.

11. A molded article for use in a high-frequency device used in a frequency band of 1 GHz or more, comprising a molded article containing the low dielectric loss resin composition according to claim 7.

12. A high-frequency device used in a frequency band of 1 GHz or more, comprising the low dielectric loss resin composition according to claim 7.

13. A high-frequency device used in a frequency band of 1 GHz or more, comprising the molded article for high-frequency devices according to claim 11.

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