JP2003342431A - Thermoplastic resin composition and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of obtaining a molding having a large dielectric constant, a small dielectric loss tangent, and a small temperature coefficient of dielectric constant in a high frequency region not smaller than 1 GHz. <P>SOLUTION: This thermoplastic resin composition contains a thermoplastic resin selected at least either one of a styrenic polymer having syndiotactic structure or a liquid crystal polymer resin, and an inorganic filler which is a solid solution having a characteristic at sintering of a dielectric constant at 1 MHz of 18-130, an fQ value of not smaller than 2,000, and a resonance frequency temperature coefficient at -20°C-80°C of -2 to 35 ppm. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition used for a high frequency circuit board and a molded article.

[0002]

2. Description of the Related Art In the advanced information age, information transmission tends to be faster and higher in frequency. Especially in recent years, IT
1 including S (Intelligent Transport Systems) related
Frequency bands of GHz and above tend to be actively used. For example, 5.8G for ETC (Automatic Charge Payment System)
Hz, 5.8 GHz for smart plate (electronic license plate), 5.2 GHz for wireless LAN (IEEE (Institute of Electrical and Electronics Engineers) 811.01a standard). In addition, downsizing of devices used for transmitting such information is desired, and downsizing is particularly desired due to limited space for installation in ITS-related in-vehicle applications.

In order to cope with this miniaturization, the size of the circuit board for high frequency is based on the wavelength of the electromagnetic wave used, so that the circuit board may be formed using a material having a large relative permittivity εr. Required. This means that the wavelength λ of an electromagnetic wave when propagating in a dielectric having a relative permittivity εr is a wavelength represented by the following formula (1) when the propagation wavelength in vacuum is λ ₀ :
This is because the wavelength λ decreases as the relative permittivity εr of the material used for the circuit board increases, which allows the circuit board to be downsized.

Λ = λ ₀ / (εr) ^1/2 (1) As the relative permittivity is increased, the circuit board for high frequency can be downsized. However, when manufacturing an antenna with such a circuit board for high frequencies, the antenna has a size effect, and if it is made too small, the antenna characteristics are extremely deteriorated, so there is a limit to the miniaturization of the antenna.

Further, as a characteristic of a material used for a circuit board for high frequency, it is essential that the dielectric loss tangent (tan δ) is small. This is expressed by the following equation (2):
When the dissipation factor (tan δ) becomes large, the loss P during transmission P
Because it becomes larger. In the formula (2) below, f represents frequency, V represents voltage, and C represents dielectric capacitance.

P = 2πfV ² Ctanδ (2) Further, as a characteristic of the material used for the circuit board for high frequency, it is essential that the temperature coefficient of the dielectric constant and the dielectric loss tangent are small.

The use of resin-based materials or ceramic-based materials as materials for these high-frequency circuit boards has been conventionally studied. However, although resin-based materials are extremely superior to ceramic-based materials in terms of price and post-processability, they generally have the problem of a low relative permittivity, and are compatible with antenna miniaturization. Difficult to do. Therefore, in order to increase the relative permittivity of the resin material, it has been considered to use a high relative permittivity resin such as polyvinylidene fluoride (relative permittivity 13) or cyano resin (relative permittivity 16 to 20). , These resins have a large dielectric loss tangent,
It is not suitable as a material for a high frequency circuit board.

Therefore, a composite technology for increasing the relative dielectric constant by dispersing inorganic dielectric particles in a resin has attracted attention and has been studied until now (for example, Japanese Patent Publication No. 49-25159 and Japanese Patent Publication No. 25159). 54-18754 and JP-A-5-128912). But,
Japanese Patent Publication No. 49-25159 and Japanese Patent Publication No. 54-1875
The resin-based material described in Japanese Patent No. 4 has not been devised for use in high-frequency applications, and has a large dielectric loss tangent, so it is completely unsuitable for high-frequency circuit board applications. Further, in JP-A-5-128912, polyphenylene ether or triallyl isocyanurate is used for the resin, and titania is used for the inorganic dielectric particles,
Resin-based materials have been proposed that reinforce it with glass cloth. In the case of this resin-based material, the dielectric loss tangent is improved, but even if this resin-based material is used, the dielectric loss tangent is 0.
The value is about 003, which is insufficient for a high-frequency circuit board. Also, from the viewpoint of the manufacturing method, the laminated material produced from glass cloth is not suitable because the thickness accuracy of the circuit board and the productivity are poor due to variations in thickness between the central portion and the end face portion.

Further, in order to improve the reliability of the circuit board, a technique for stabilizing the temperature characteristic of the relative permittivity has attracted attention and has been studied until now (for example, JP-A-4-16146).
1 gazette, special table 2000-510639 gazette). That is, Japanese Patent Application Laid-Open No. 4-161461 proposes a composite material that stabilizes the temperature coefficient of a ceramic having a positive relative dielectric constant temperature characteristic and a ceramic having a negative relative dielectric constant temperature characteristic and a polymer material. There is. In addition, special table 20
No. 00-510639 discloses a thermoplastic polymer,
A polymeric composition made from a high dielectric ceramic having a dielectric constant of at least about 50 at 1.0 GHz and 20 ° C. and a second ceramic material having a dielectric constant of at least about 5 at 1.0 GHz and 20 ° C. is proposed. Therefore, a polymer composition having a high dielectric constant that hardly changes with temperature is provided by using a high dielectric ceramic and a second ceramic material having positive and negative temperature coefficients. However, in these methods, since it is necessary to use at least three kinds of raw materials including two kinds of ceramics and polymer materials having greatly different dielectric properties, the dispersion state of the ceramics fluctuates and the characteristics tend to fluctuate. Not suitable for.

For the above reasons, a resin material having three characteristics of a larger relative permittivity, a smaller dielectric loss tangent, and a smaller temperature coefficient of the relative permittivity is strongly desired.
At present, such a resin material has not yet been provided at a practical level.

[0011]

The present invention has been made in view of the above points, and its object is to:
It is intended to provide a thermoplastic resin composition and a molded product having a large relative dielectric constant, a small dielectric loss tangent, and a small temperature coefficient of the relative dielectric constant in a high frequency region of 1 GHz or more.

[0012]

The thermoplastic resin composition according to claim 1 of the present invention comprises a thermoplastic resin mainly composed of at least one of a styrene polymer having a syndiotactic structure and a liquid crystal polymer resin, and a baking resin. Resulting characteristic is 1MH
The relative dielectric constant at z is 18 to 130, the f · Q value is 2000 or more, and the temperature coefficient of the resonance frequency at −20 ° C. to 80 ° C. is −
It is characterized by containing an inorganic filler which is a solid solution of 2 to 35 ppm / ° C.

According to a second aspect of the present invention, in the first aspect, the inorganic filler is a solid solution of MgO, CaO, TiO ₂ , BaO, TiO ₂ , Nd ₂ O ₃ , Sm ₂ O ₃ ,
Bi ₂ O ₃ solid solution, BaO, TiO ₂ , Nd ₂
O ₃ , Sm ₂ O ₃ , Bi ₂ O ₃ , solid solution composed of MnCO, Nd ₂ O ₃ , LiCO ₃ , solid solution composed of TiO ₂ , Nd ₂ O ₃ , LiCO ₃ , SrTiO ₃ , CaTi.
It is characterized in that it is at least one kind of solid solution selected from O ₃ and TiO ₂ .

According to a third aspect of the present invention, in the first or second aspect, the inorganic filler is contained in an amount of 90 to 90 parts by weight with respect to 10 to 90 parts by weight of the thermoplastic resin in a total of 100 parts by weight of the thermoplastic resin and the inorganic filler. It is characterized by containing 10 parts by mass.

The invention of claim 4 is characterized in that, in any one of claims 1 to 3, in addition to the thermoplastic resin and the inorganic filler, an oxidant-soluble inorganic filler is contained. .

According to a fifth aspect of the present invention, in the fourth aspect, the thermoplastic resin and the oxidizer-soluble inorganic filler are added in a total amount of 10
It is characterized by containing 5 to 30 parts by mass of the oxidizer-soluble inorganic filler in 0 part by mass.

The invention of claim 6 is the same as in claim 4 or 5, wherein the oxidizing agent-soluble inorganic filler has an average particle size of 6 μm.
It is characterized by being m or less.

The invention of claim 7 is characterized in that, in any one of claims 4 to 6, the oxidizing agent-soluble inorganic filler is calcium carbonate.

According to the invention of claim 8, in any one of claims 1 to 7, the styrene-based polymer mainly having a syndiotactic structure is subjected to a parallel plate method at a temperature of 300 ° C. and an angular velocity of 100 rad / s. The melt viscosity measured is from 1 to 250 Pa · s.

The invention of claim 9 is the styrene polymer according to any one of claims 1 to 8, wherein the styrene-based polymer mainly having a syndiotactic structure has a mass decrease at a temperature rising rate of 10 ° C / min and a temperature of 330 ° C. It is characterized by being 5 mass% or less.

Further, the invention of claim 10 is based on claims 1 to 9.
The liquid crystal polymer resin is a liquid crystalline aromatic polyester of type I, type II, or type III obtained from the cocondensation of acetylated p-hydroxybenzoic acid and polyethylene terephthalate. Is.

The invention of claim 11 relates to claims 1 to 1.
In any one of 0, the liquid crystal polymer resin is characterized in that the mass reduction at a temperature rising rate of 10 ° C./min and a temperature of 330 ° C. is 5% by mass or less.

The invention of claim 12 is the same as claims 1 to 1.
In any one of 1, the liquid crystal polymer resin has a melting point of 3
It is characterized in that the temperature is 00 ° C. or higher.

Further, the invention of claim 13 is based on claims 1 to 1.
In any one of No. 2, the inorganic filler has an average particle size of 0.
It is characterized in that it is 1 to 15 μm.

Further, the invention of claim 14 is based on claims 1 to 1.
3 is characterized in that an inorganic coating layer composed of at least one of an inorganic hydroxide and an inorganic oxide is formed on the surface of the inorganic filler.

According to a fifteenth aspect of the invention, in the fourteenth aspect, the inorganic hydroxide or the inorganic oxide is selected from the group consisting of titanium, aluminum, silicon, zirconium, tin, zinc, antimony and magnesium. It is characterized by being a hydroxide or an oxide of at least one element.

According to a sixteenth aspect of the present invention, in the fourteenth or fifteenth aspect, the inorganic coating layer contains a hydroxide and an oxide of the same metal element as the metal element contained in the inorganic compound constituting the inorganic filler. It is characterized by containing at least one.

The invention of claim 17 is characterized in that, in any one of claims 13 to 16, the inorganic filler is treated with a coupling agent having an amino group, an epoxy group, or a mercapto group. It is a thing.

[0029] The invention of claim 18 is the method of claim 17, wherein the inorganic filler is (N-
It is a phenyl-γ-aminopropyl) trimethoxysilane.

A molded article according to a nineteenth aspect of the present invention is characterized by being obtained by injection molding the thermoplastic resin composition according to any one of the first to eighteenth aspects.

The invention of claim 20 is characterized in that, in claim 19, the relative dielectric constant at 1 GHz is 3 to 20.

The invention of claim 21 is characterized in that, in claim 19 or 20, the dielectric loss tangent at 1 GHz is 0.002 or less.

The invention according to claim 22 is the method according to any one of claims 19 to 21, wherein the temperature at -20 ° C to 80 ° C is 1 ° C.
Temperature coefficient of relative permittivity in MHz is -1000 to 100
It is characterized in that it is 0 ppm / ° C.

According to a twenty-third aspect of the present invention, in any one of the nineteenth to twenty-second aspects, an electrode is formed by integrating at least one kind of electrode material when the thermoplastic resin composition is injection molded. It is characterized by being present.

The invention of claim 24 is characterized in that in claim 23, the electrode material is a metal foil having a matte surface.

The invention of claim 25 is characterized in that, in any one of claims 19 to 22, the electrode is formed by plating.

The invention of claim 26 is based on any one of claims 19 to 25, wherein the specific resistance of the electrode is 1 × 10.
It is characterized by being ⁻⁵ Ω · cm or less.

The invention of claim 27 is characterized in that in any one of claims 23 to 26, the material of the electrode is copper.

According to a twenty-eighth aspect of the present invention, in any one of the twenty-third to twenty-seventh aspects, the electrode has a thickness of 10 to 110 μm.
It is characterized by being m.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

The thermoplastic resin composition according to the present invention contains a thermoplastic resin and an inorganic filler as main components, and is used for producing a circuit board or the like by injection molding.

In the present invention, as the thermoplastic resin, a styrene polymer having a syndiotactic structure and a liquid crystal polymer are mainly used. Either one may be used alone, or both may be used in combination. May be.

Here, the above-mentioned styrene-based polymer mainly having a syndiotactic structure (hereinafter sometimes referred to as SPS resin), which is used as a thermoplastic resin in the present invention, has a syndiotactic structure of polystyrene-based resin. The steric structure is mainly a syndiotactic structure, that is, a steric structure in which a phenyl group or a substituted phenyl group, which is a side chain with respect to a main chain formed from a carbon-carbon bond, is alternately located in opposite directions. I have. The tacticity can be quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon.
Tacticity measured by the ¹³ C-NMR method may be represented by the presence ratio of a plurality of continuous constitutional units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. However, the polystyrene-based resin having a predominantly syndiotactic structure as referred to in the present invention is usually 75% or more, preferably 85% or more in dyad, or 30% or more in pentad (racemic pentad), preferably , Polystyrene having a syndiotacticity of 50% or more, poly (alkylstyrene), poly (halogenated styrene),
The term refers to poly (alkoxystyrene), poly (vinyl benzoate) and mixtures thereof, or copolymers containing these as the main components. Incidentally, as poly (alkylstyrene), poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene),
Examples of the poly (t-butyl styrene) include poly (t-butyl styrene), and examples of the poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferable polystyrene-based resins in the present invention are polystyrene and poly (p
-Methylstyrene), poly (m-methylstyrene), poly (pt-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), and A copolymer of styrene and p-methylstyrene can be mentioned.

In the present invention, these SPS resins have a melt viscosity of 1 to 250 as measured by the parallel plate method at a temperature of 300 ° C. and an angular velocity of 100 rad / s.
Those having Pa · s are preferably used. Melt viscosity
If it is less than this range, the mechanical strength of the obtained molded product is significantly lowered, and if it exceeds this range, the fluidity during molding is poor and unfilling easily occurs during molding. Here, in the parallel plate method, pellets having a thickness of 1 mm and a diameter of 25 mm are produced by a hand press, the pellets are placed on a lower parallel plate having a diameter of 25 mm, the upper parallel plate is lowered and sandwiched, and after holding at 300 ° C. for 10 minutes, It is done by measuring, for example,
The measurement with Ares (trade name) manufactured by Rheometric Scientific is suitable.

In the present invention, these SPS resins have a temperature rising rate of 10 ° C./min and a temperature of 3 in thermogravimetric analysis.
Those having a mass reduction of 5% by mass or less at 30 ° C. are preferably used. If the mass reduction exceeds 5 parts by mass, mold deposit (dirt) may occur on the surface of the obtained molded product, which is not preferable. The smaller the decrease in mass is, the more preferable, and 0% is ideal, but it is practically 0.1% by mass because of availability.

The molecular weight distribution of SPS is not particularly limited, and various kinds can be applied. The SPS resin as described above has a high melting point and is significantly superior in heat resistance to the conventional polystyrene resin having an atactic structure. Such an SPS resin is, for example, a styrene-based monomer (corresponding to an SPS resin in the presence of an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. Monomer)
It can be produced by polymerizing
2-18708).

The above-mentioned liquid crystal polymer resin used as the thermoplastic resin in the present invention is not particularly limited as long as it has been conventionally used for molding material applications, but an acetylated product of p-hydroxybenzoic acid and polyethylene terephthalate. Form I, II obtained from the co-condensation of
Type and type III liquid crystalline aromatic polyesters and the like. Obtained from the cocondensation of this acetylated p-hydroxybenzoic acid and polyethylene terephthalate,
The I-type, II-type, and III-type liquid crystalline aromatic polyesters are particularly preferable because the molded products obtained by molding have high mechanical properties and excellent moldability.

In the present invention, this liquid crystal polymer resin has a temperature rising rate of 10 ° C./min and a temperature of 3 in thermogravimetric analysis.
Those having a mass reduction of 5% by mass or less at 30 ° C. are preferably used. If the mass reduction exceeds 5 mass%, mold deposit (dirt) may occur on the surface of the obtained molded product, which is not preferable. The smaller the mass loss is, the more preferable, and 0% is ideal, but 0.1 mass% is the lower limit in practical use due to availability and the like.

Further, in the present invention, the liquid crystal polymer resin having a melting point of 300 ° C. or higher is preferable. By using a liquid crystal polymer having a melting point of 300 ° C. or higher as described above, the solder heat resistance of the obtained molded product can be increased. If the melting point of the liquid crystal polymer is too high, it is necessary to use a special injection molding machine, so the melting point is preferably 400 ° C. or lower.

As the liquid crystal polymer resin as described above,
For example, “Sumika Super” (trade name) manufactured by Sumitomo Chemical Co., Ltd., “Xyda” manufactured by Nippon Petrochemical Co., Ltd./Amoco
r "(trade name), Polyplastics Co., Hoechst Ce
"Vectra" (trade name) manufactured by lanese, "UENOLCP" (trade name) manufactured by Ueno Pharmaceutical Co., Ltd., "Novaculate" manufactured by Mitsubishi Engineering Plastics Co., Ltd.
(Commercial name), “Rod Run” (commercial name) manufactured by Unitika Ltd., “Tosoh LCP” (commercial name) manufactured by Tosoh Corp., and the like can be appropriately selected and used.

The inorganic filler used in the present invention has a dielectric constant of 18 to 130 at 1 MHz when sintered,
The solid solution has an f · Q value of 2000 or more and a resonance frequency temperature coefficient at −20 ° C. to 80 ° C. of −2 to 35 ppm / ° C. These evaluations can be performed by using a network analyzer to measure the relative permittivity by the short-circuit method at both ends, the FQ value by the transmission line method, and the temperature coefficient of the relative permittivity by the cavity resonance method. In order to increase the relative dielectric constant of the thermoplastic resin composition, the relative dielectric constant at 1 MHz as an inorganic filler is 1
It is necessary to use a material having a relative permittivity of 8 or more. The larger the relative dielectric constant is, the more preferable. In addition, the inorganic filler has an fQ value of 2000.
It is above, and the larger the better, the more preferable, but the practical upper limit is about 60,000. Furthermore, by using an inorganic filler having a resonance frequency temperature coefficient of −20 to 80 ° C. of −2 to 35 ppm / ° C., the temperature coefficient of relative permittivity can be stabilized.

Although this inorganic filler is composed of a plurality of components, since it is a solid solution, the components are uniformly mixed and the dielectric characteristics are stable. Among the solid solutions used as the inorganic filler, particularly preferred are MgO, CaO,
Solid solution of TiO ₂ , BaO, TiO ₂ , Nd ₂ O
₃ , Sm ₂ O ₃ , Bi ₂ O ₃ solid solution, BaO,
_{TiO 2, Nd 2 O 3,} Sm 2 O 3, Bi 2 O 3, Mn
Solid solutions consisting of _{CO, Nd 2 O 3, LiCO} 3, TiO
Solid solution consisting of ₂ , Nd ₂ O ₃ , LiCO ₃ , SrTi
A solid solution consisting of O ₃ , CaTiO ₃ , and TiO ₂ ,
One of these may be used alone, or two or more may be used in combination. These solid solutions are particularly suitable for the present invention in terms of dielectric properties. In addition, a small amount component of about 5% by mass or less in these solid solution components may be omitted as long as the effects of the present invention are not impaired.

The particle size of the inorganic filler is not particularly limited, but an average particle size of 0.1 to 15 μm is preferable. If the average particle size is less than 0.1 μm, the specific surface area of the inorganic filler becomes relatively large,
There is a possibility that the wettability with the thermoplastic resin may be lowered and air may be entrained, a void may be generated at the interface with the thermoplastic resin, and water may enter the void. Conversely, if the average particle size exceeds 15 μm,
It becomes difficult to uniformly disperse the inorganic filler in the thermoplastic resin.

The inorganic filler which is a solid solution that can be used in the present invention is a known one, and it is possible to obtain and use a commercially available one such as Kyoritsu Material Co., Ltd. If it is manufactured by a known method, for example, M
A solid solution composed of gO, CaO, and TiO ₂ can be obtained by mixing the raw materials of the respective components at a predetermined stoichiometric ratio and then calcining at 800 to 1200 ° C., for example.

In the present invention, the inorganic filler is preferably particles having an inorganic coating layer made of an inorganic hydroxide and / or an inorganic oxide formed on the surface thereof.
By forming an inorganic coating layer composed of an inorganic hydroxide or an inorganic oxide on the surface of the inorganic filler in this way, the inorganic filler easily becomes compatible with the thermoplastic resin through the inorganic coating layer, and the thermoplastic resin The adhesiveness with the inorganic filler is improved.

The inorganic hydroxide or inorganic oxide forming the inorganic coating layer is water of at least one element selected from the group consisting of titanium, aluminum, silicon, zirconium, tin, zinc, antimony and magnesium. Oxides and oxides are preferred. These inorganic hydroxides and inorganic oxides are preferable because they are particularly excellent in compatibility with the thermoplastic resin.

The inorganic coating layer formed on the surface of the inorganic filler is preferably formed of a hydroxide and / or an oxide of the same metal element as the metal element contained in the inorganic compound forming the inorganic filler. . That is, when the inorganic filler is lanthanum titanate, a titanium-based inorganic coating layer is formed on the surface of the inorganic filler, and when the inorganic filler is barium titanate, an aluminum-based inorganic coating layer is formed on the surface of the inorganic filler. Preferably. In this case, the bond between the inorganic filler and the inorganic coating layer becomes stronger.

Further, the inorganic coating layer is formed in a multi-layered structure, and the side in contact with the inorganic filler is an inorganic coating layer which is well compatible with the inorganic filler and the side in contact with the thermoplastic resin is a thermoplastic resin or a coupling described later. You may make it the inorganic coating layer with which an agent is familiar.
By doing so, the bond between the inorganic filler and the thermoplastic resin becomes stronger.

Examples of the method for forming the inorganic coating layer on the surface of the inorganic filler include a vapor phase treatment method (CVD method) and a liquid phase treatment method (method utilizing a liquid phase reaction). In the case of the liquid phase treatment method, the inorganic coating layer can be formed as follows. For example, in the case of an inorganic coating layer of titanium oxide, the inorganic filler is put into an aqueous solution containing titanium tetrachloride and titanium sulfate, and the aqueous solution is
By adjusting to H8.5 to 10.5, the inorganic coating layer of titanium oxide can be formed. At this time, the thickness (volume amount) of the inorganic coating layer of titanium oxide formed on the surface of the inorganic filler can be adjusted by the concentration of titanium ions in the aqueous solution. In the case of a coating layer of aluminum oxide, the coating layer of aluminum oxide can be formed by introducing the inorganic filler into an aqueous solution containing sodium aluminate, aluminum chloride and aluminum sulfate and adjusting the pH of the aqueous solution to about 7. . At this time, the thickness of the inorganic coating layer of aluminum oxide formed on the surface of the inorganic filler can be adjusted by the concentration of aluminum ions in the aqueous solution. Further, when forming a coating layer of silicon oxide, an aqueous solution containing silicate may be used.

When an inorganic coating layer containing two or more kinds of inorganic oxides or hydroxides is formed stepwise or simultaneously, a film containing two or more kinds of salts is used to form a film. This can be done by adjusting the pH. When the inorganic coating layers are formed in multiple layers stepwise, for example, by using a solution in which titanium tetrachloride is dissolved and adjusting the pH with sodium hydroxide, the titanium-based first coating is applied to the surface of the inorganic filler. After forming a layer, and then dissolving sodium aluminate and sodium silicate in the liquid, by adjusting the pH with sulfuric acid,
A second coating layer based on aluminum-silicon may be formed on the second coating layer. Alternatively, the second coating layer may be an aluminum-based layer, and the silicon-based third coating layer may be formed thereon.

It is desirable to wash and dry the surface after forming the inorganic coating layer on the surface of the inorganic filler as described above. In particular, it is important that the cleaning is performed thoroughly while paying close attention so that the conductive components do not remain.

Further, in the present invention, the surface of the inorganic filler is
Alternatively, the surface of the inorganic coating layer formed on the inorganic filler is preferably treated with a coupling agent. By thus surface-treating with the coupling agent, the compatibility between the inorganic filler and the thermoplastic resin is further improved, and the adhesiveness between the inorganic filler and the thermoplastic resin is excellent. As the coupling agent, a coupling agent having an amino group, an epoxy group, or a mercapto group can be used, and examples thereof include (N-phenyl-γ-aminopropyl) trimethoxysilane and (2
-Aminoethyl) aminopropyltrimethoxysilane,
(2-aminoethyl) aminopropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane,
N-vinylbenzylaminoethyl-aminopropyltrimethoxysilane hydrochloride, glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane,
Vinyltriacetoxysilane, chloropropyltrimethoxysilane, anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3-
(Trimethoxysilyl) propyl] ammonium chloride, chloropropylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, glycidoxypropylmethyldimethoxysilane, ureidopropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, isopropyltriisostearoyl titanate, isopropyl Examples thereof include tris (dioctypyrophosphate) titanate, isopropyl tris (N-aminoethyl-aminoethyl) titanate, isopropyltrioctanoyl titanate, and acetoalkoxyaluminum diisopropylate. Among these, (N-phenyl-γ-aminopropyl) trimethoxysilane is particularly preferable because it has a high effect of enhancing the adhesiveness between the inorganic filler and the thermoplastic resin. This is considered to be an effect due to the fact that it has a chemical structure similar to that of the thermoplastic resin.

The blending amount of the thermoplastic resin and the inorganic filler is 90 parts by weight of the inorganic filler with respect to 10 to 90 parts by weight of the thermoplastic resin in a total of 100 parts by weight of the thermoplastic resin and the inorganic filler. It is preferably set to 10 parts by mass. When the amount of the thermoplastic resin is less than 10 parts by mass, the melt viscosity of the thermoplastic resin composition may increase and the moldability may decrease. On the other hand, when the thermoplastic resin exceeds 90 parts by mass, the content of the inorganic filler becomes small and the relative dielectric constant becomes relatively small, so that the circuit board cannot be formed in a small size, which contributes to downsizing of the device. May not be expected.

Next, the thermoplastic resin composition according to the present invention may contain an oxidizer-soluble inorganic filler in addition to the above-mentioned thermoplastic resin and inorganic filler. Thus molding a thermoplastic resin composition prepared by blending an oxidizer-soluble inorganic filler, and treating the resulting molded article with an oxidant,
The oxidizer-soluble inorganic filler exposed on the surface of the molded product is eluted into the oxidizer, and fine irregularities are generated on the surface of the molded product, so that the surface can be roughened. Therefore, when plating is applied to the surface of the molded product, it is possible to obtain high adhesion of the plating film due to the anchor effect of the roughened surface.

This oxidizer-soluble inorganic filler is composed of dichromic acid, permanganate, dichromic acid / sulfuric acid mixture, chromic acid,
It is possible to arbitrarily select and use from those soluble in an oxidant solution such as chromic acid / sulfuric acid mixed solution, and it is possible to use various shapes such as fibrous, granular, powdery and flake-like. it can. Examples of the fibrous oxidant-soluble inorganic filler include whiskers and the like. Further, as the material of the granular or flaky oxidant-soluble inorganic filler, for example, calcium carbonate, basic magnesium oxysulfate, magnesium carbonate, dolomite, dawsonite, magnesium hydroxide, kaolin, pioferrite, zeolite, neferrite, adamine, Examples thereof include palygorskite, antimony trioxide, titanium oxide, iron oxide, magnesium oxide, zinc oxide and metal powder. These may be used alone or in combination of two or more. Of these, calcium carbonate is particularly preferable because it does not show deterioration in electrical characteristics as compared with other oxidant-soluble inorganic fillers.

The average particle size of the oxidizer-soluble inorganic filler is
It is preferably 6 μm or less, more preferably 5 μm or less, and further preferably 4 μm or less.

The compounding amount of the oxidizer-soluble inorganic filler is 10 in total of the thermoplastic resin and the oxidizer-soluble inorganic filler.
It is preferable that the content of the oxidizer-soluble inorganic filler is 5 to 30 parts by mass in 0 part by mass. When the compounding amount of the oxidizer-soluble inorganic filler is less than 5 parts by mass, when the molded product is plated, the roughening of the surface of the molded product is insufficient, and the lack of anchors causes the occurrence of plating skips. , The adhesion strength of the plating film may be insufficient. On the other hand, if it exceeds 30 parts by mass, the melt viscosity of the thermoplastic resin composition may increase, and the moldability may decrease.

If necessary, the thermoplastic resin composition of the present invention contains 3 parts of the above-mentioned thermoplastic resin, inorganic filler, and oxidizer-soluble inorganic filler unless the purpose of the present invention is impaired.
Other than components, thermoplastic resins, elastomers, inorganic substances, components imparting flame retardancy, antioxidants, crystal nucleating agents, crystallization accelerators, coupling agents, release agents, lubricants, colorants, UV absorbers, An antistatic agent or the like can be added.

Examples of the above-mentioned thermoplastic resins and elastomers include norbornene resins, polyolefin resins, polyester resins, polyoxymethylene resins, polymethylpentene resins, polyvinylidene chloride resins, polyvinylidene fluoride resins, polyamide resins (nylon 6). Resin, nylon 66 resin, nylon 610 resin, copolymer nylon resin), polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polyacetal resin, polyetherimide resin, Polyamideimide resin, polyimide resin, polystyrene resin, AS resin, ABS resin, phenoxy resin, polyether nitrile resin, polytetrafluoroethylene resin, petroleum resin, Charcoal resin, norbornene resin, epoxy resin, phenol resin, silicone resin,
Examples thereof include synthetic resins such as urethane resin, and elastomers such as polyolefin rubber, olefin copolymer, and hydrogenated rubber. These can also be used as a mixture of two or more kinds.

As the above-mentioned inorganic material, glass fiber or the like can be used. In particular, the aspect ratio is 5 to 5.
Containing 1500 glass short fibers is preferable because the mechanical strength of a circuit board or the like obtained by molding is improved. The blending amount of this glass short fiber is 1 in total of the thermoplastic resin, the inorganic filler, the oxidizer-soluble inorganic filler and the glass short fiber.
The range of 5 to 30 parts by mass of glass short fibers is preferable with respect to 00 parts by mass. If the amount of short glass fibers is less than 5 parts by mass, the effect of addition cannot be sufficiently obtained, and conversely, if it exceeds 30 parts by mass, moldability and the dielectric properties of the molded product may deteriorate.

As the flame retardant of the above-mentioned component imparting flame retardancy, those commercially available in general can be used,
Tetrabromobutane, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, pentabromochlorocyclohexane, tetrabromobisphenool S, tris (2,3dibromopropyl-1) isocyanurate, 2,2-bis [4 ( 2,3 dibromopropoxy) -3,5-dibromophenyl] propane, halogenated acetylene alcohol, brominated epoxy, decabromodiphenyl ether, derivatives including tetrabromobisphenol A and its carbonate oligomer, octabromodiphenyl oxide, pentabromo Diphenyl oxide, tetrabromophenol, dibromostyrene, pentabromobenzyl acrylate, tetrabromostyrene, polydibromophenylene oxide, bisto Bromophenoxy ethane, tetrabromobisphenol feta Lethe preparative diol, tetrabromophthalic anhydride, dibromo-cresyl-glycidyl ether, epibromohydrin, dibromo neopentyl glycol,
Tribromoneopentyl alcohol, bromide such as ethylenebistetrabromophthalimide, brominated polystyrene, chlorinated paraffin, chlorinated polyolefin, dimethyl chlorendate, chlorendic anhydride, tetrachlorophthalic anhydride, phenylphosphonic acid dichloride, etc. Chlorine-based flame retardants, fluorine compounds such as polytetrafluoroethylene, red phosphorus, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2, 6 Xylenyl phosphate, tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl phosphate, tris (trib Moneopentyl) phosphate, diethyl phenyl phosphonate, dimethyl phenyl phosphonate, bisphenol A-bis (dicresyl phosphate), phosphorus compounds such as condensed phosphoric acid ester, melamine, melamine cyanurate, melamine phosphate, guanidine sulfamate, etc. Nitrogen compounds, barium metaborate, zinc borate, boron-based compounds such as anhydrous zinc borate, silicone powder flame retardants, silicon-containing compounds such as silicone resins, aluminum hydroxide,
Inorganic flame retardants such as magnesium hydroxide, calcium hydroxide, calcium carbonate, kaolin clay, calcium aluminate, titanium hydroxide, zinc hydroxide, dawsonite, dihydrate gypsum, antimony silico oxide, and metals such as antimony oxide. There are oxides, low melting point glass, and the like. These may be used alone or in combination of two or more. Among these, bromide, especially brominated polystyrene, is preferable. Regarding the form, in terms of enhancing dispersibility,
Brominated polystyrene in powder form is preferred. With pellets having a large particle size, it is difficult to disperse uniformly, and there is a risk that dispersion will occur in the thermoplastic resin composition.

Examples of the above-mentioned antioxidants include phosphorus-based antioxidants and phenol-based antioxidants. These may be used alone or in combination of two or more. Examples of the crystal nucleating agent include dibenzylidene sorbitol compounds, aluminum salts of t-butylbenzoic acid, sodium salts of phosphoric acid esters, and the like. These may be used alone or in combination of two or more.

As the above-mentioned lubricant, both an internal lubricant and an external lubricant can be used, and examples thereof include a hydrocarbon type, a fatty acid type, a fatty acid amide, a fatty acid ester and the like. These may be used alone or in combination of two or more. Further, as the colorant, various known pigments or dyes can be used, for example, black pigments such as carbon black, orange pigments such as red-mouth yellow lead, red dyes and pigments such as Benji, purple dyes such as cobalt violet. Pigments, blue dyes such as cobalt blue, green dyes such as phthalocyanine green, and the like can be used. More specifically,
The latest pigment handbook (edited by Japan Pigment Technology Association, published in 1977)
You can use the ones listed in this handbook with reference to.

The thermoplastic resin composition used in the present invention is prepared by mixing the above-mentioned components with a mixer such as a Henschel mixer, or if necessary, preparing a part of the necessary components into a masterbatch in advance. After mixing, a method of pelletizing by melt-kneading with a kneader such as an extruder can be adopted. Of course, it is not limited to this.

A molded article can be obtained by injection molding the thermoplastic resin composition according to the present invention obtained as described above. This molded product can be mainly processed and used as a circuit board, and this circuit board can be mainly processed and used as an antenna.

Thus, when the molded product is used as a circuit board for high frequency applications, the relative dielectric constant at 1 GHz is 3 to 20, and the dielectric loss tangent at 1 GHz is 0.002 or less.
The temperature coefficient of the relative dielectric constant at 1 MHz at 20 ° C to 80 ° C is preferably -1000 to 1000 ppm / ° C. Setting the relative dielectric constant at 1 GHz to 3 to 20 is preferable for downsizing the high frequency circuit board. Further, it is preferable to set the dielectric loss tangent at 1 GHz to 0.002 or less because the loss P during transmission is reduced. Furthermore, it is preferable to set the temperature coefficient of the relative dielectric constant at 1 MHz at −20 ° C. to 80 ° C. to −1000 to 1000 ppm / ° C., because the substrate can be highly reliable.

When the molded product is used as a circuit board, it is necessary to provide electrodes on the surface of the molded product. Thus, in providing the electrode on the surface of the molded product, the thermoplastic resin composition according to the present invention and the electrode material at the time of injection molding should be integrated at the same time to form the electrode on the surface of the molded product with the electrode material. Can be done by. For example, by using a metal foil such as a copper foil as an electrode material, setting the metal foil in a mold, injection-molding a thermoplastic resin, and filling the mold with the metal foil, the metal foil is formed on the surface of the molded product. It can be integrated, and the electrode can be formed on the surface of the molded product with the metal foil. . When a metal foil having a glossy surface and a matte surface such as an electrolytic copper foil is used as the electrode material, it is preferable to use it so that the matte surface, which is a rough surface, is adhered to the surface of the molded article. It is possible to obtain strong adhesion between them. This is due to the anchor effect of the matte surface and the effect of pressure during molding.

After molding the molded product, the surface of the molded product may be plated to form the electrodes.
In performing plating on the surface of the molded product in this manner, by using the molded product obtained by molding the thermoplastic resin composition containing the oxidant-soluble inorganic filler as described above, the pre-plating step is performed. The molded product can be treated with an oxidizing agent to roughen the surface, and the adhesion of the plating film can be increased.

Here, the electrode formed on the molded product as described above preferably has a specific resistance of 1 × 10 ⁻⁵ Ω · cm or less. If the specific resistance is higher than this range, the high frequency characteristics may deteriorate. The smaller the specific resistance, the more desirable. Copper is most preferable as the electrode material satisfying such conditions. The thickness of the electrode is preferably 10 to 110 μm. When the thickness of the electrode is 10 μm or less, it becomes difficult to receive radio waves when the circuit board is used as an antenna. On the contrary, when the thickness of the electrode exceeds 110 μm, peeling of the electrode may occur in a temperature cycle test or the like.

[0080]

EXAMPLES Next, the present invention will be explained by examples.

(Examples 1 to 20, Comparative Example 1) The following were used as the thermoplastic resin, the inorganic filler, the soluble inorganic filler and the coupling agent, and blended in the blending amounts shown in Tables 1 to 3. A thermoplastic resin composition was obtained by melt-kneading. The coupling agent was used to treat the surface of the inorganic filler by directly spraying the inorganic filler. Then, a molded article was produced by injection molding the thermoplastic resin composition.

The inorganic filler A of Example 20 was obtained by the following method. First, solid solution particles composed of MgO, CaO, and TiO were added to and mixed with a solution containing sodium hexametaphosphate to be suspended and dispersed. Then, in the solution, as a raw material of the inorganic coating layer, titanium tetrachloride,
After adding sodium aluminate and sodium silicate, the pH was adjusted using sulfuric acid to form an inorganic coating layer on the surface. Then, wash and 120
The titania particles having the inorganic coating layer formed on the surface thereof were obtained by drying at 24 ° C. for 24 hours. Subsequently, the particles having the inorganic coating layer formed thereon are dispersed in an aqueous solution to which N-phenyl-γ-aminopropyl) trimethoxysilane has been added as a coupling agent, so that the coupling agent is provided on the surface of the inorganic coating layer. Deposited. Then, it was filtered and dried to obtain an inorganic filler A in which an inorganic coating layer was formed on the surface of the particles and the surface of which was treated with a coupling agent. 1. Thermoplastic resin / Resin A: A styrene-based polymer mainly having a syndiotactic structure (Zarek “30 manufactured by Idemitsu Petrochemical Co., Ltd.”
0ZC ”, melting point 270 ° C., melt viscosity 98 Pa · s (parallel plate method, 300 ° C., 100 rad / s), 33
Weight loss at 0 ° C.-3.5% by mass) Resin B: A styrene polymer mainly having a syndiotactic structure (“S100” manufactured by Idemitsu Petrochemical Co., Ltd.,
Melting point 270 ° C., melt viscosity 54 Pa · s (parallel plate method, 300 ° C., 100 rad / s), mass reduction at 330 ° C.-4.5% by mass) Resin C: liquid crystal polymer resin (manufactured by Sumitomo Chemical Co., Ltd.) "E6000", melting point 320 ° C, mass reduction at 330 ° C-0.2 mass%) 1. Inorganic filler / filler A: solid solution consisting of MgO, CaO, and TiO ₂ (“Hf-20HQ” manufactured by Kyoritsu Material Co., Ltd., 1MH
z relative dielectric constant 20, fQ value 55000, -20 ° C ~
Resonance frequency temperature coefficient at 80 ° C. 10 ppm / ° C., average particle size 1.3 μm) Filler B: BaO, TiO ₂ , Nd ₂ O ₃ , Sm ₂ O
₃ , a solid solution composed of Bi ₂ O ₃ (Kyoritsu Material Co., Ltd.)
"Hf-120" made, relative permittivity 119, f at 1MHz
-Q value 2500, temperature coefficient of resonance frequency at -20 ° C to 80 ° C: 25 ppm / ° C, average particle size 1.0 μm) -Filler C: BaO, TiO ₂ , Nd ₂ O ₃ , Sm ₂ O
Solid solution consisting of ₃ , Bi ₂ O ₃ and MnCO (“Hf-90HQ” manufactured by Kyoritsu Material Co., Ltd., relative permittivity 91 at 1 MHz, f · Q value 5000, temperature coefficient of resonance frequency at −20 ° C. to 80 ° C. 7 ppm / ° C, average particle size 1.1μ
m) -Filler D: Nd ₂ O ₃ , LiCO ₃ , TiO ₂ (“LINDT” manufactured by Kyoritsu Materials Co., Ltd., relative permittivity of 75 at 1 MHz, f / Q value of 5000, average particle diameter of 2.5 μm). Filler E: Nd ₂ O ₃ , LiCO ₃ , SrTiO ₃ ,
Solid solution consisting of CaTiO ₃ and TiO ₂ (“Hf-200” manufactured by Kyoritsu Material Co., Ltd.), relative permittivity 2 at 1 MHz
00, f · Q value 2000, temperature coefficient of resonance frequency at −20 ° C. to 80 ° C. 80 ppm / ° C., average particle size 0.9 μ
m) -Filler F: magnesium titanate ("MT-1F" manufactured by Kyoritsu Materials Co., Ltd., relative permittivity at 1 MHz, 18,
Filler G: calcium titanate (“CT” manufactured by Kyoritsu Material Co., Ltd., average particle diameter 1.5 μm) 3. Oxidizing agent Soluble inorganic filler-Soluble filler A: Calcium carbonate ("Silver (product number W)" manufactured by Shiraishi Industry Co., Ltd., average particle size 3.3 µm) ・ Soluble filler B: Calcium carbonate (Shiroishi Industry Co., Ltd.) Made by "WHITON (product number P30)", average particle size 5.5μ
m) -Soluble filler C: calcium carbonate (“WHITON (product number P50)” manufactured by Shiraishi Industry Co., Ltd., average particle size 16.3μ)
m) 4. Coupling agent / Coupling agent A: Aminosilane-based coupling agent (manufactured by Nippon Unicar Co., product number “Y9669”: (N-phenyl-γ-aminopropyl) trimethoxysilane) -Coupling agent B: Aminosilane-based coupling agent (Nippon Unicar, product number “A1100”: γ-aminopropyltriethoxysilane) Coupling agent C: Epoxysilane-based coupling agent (Shin-Etsu Silicone product number “KBM403”: γ-glycidoxypropyltrimethoxy Silane) -Coupling agent D: Mercaptosilane-based coupling agent (manufactured by Toshiba Silicone, product number "TSL8380E":
3-Mercaptopropyltrimethoxysilane) -Coupling agent E: Vinylsilane coupling agent (Toray Silicone Co., product number "SZ6300": vinyltrimethoxysilane) <Evaluation> (1) Dielectric properties (dielectric constant, dielectric loss tangent) Molded articles obtained in Examples 1 to 20 and Comparative Example 1 (shape, φ5
(0 mm × 1 mm), the relative permittivity and dielectric loss tangent at 1 MHz were measured. In addition, the molded product is cut and polished to 1.
It is processed into a shape of 7 mm x 1.7 mm x 78.0 mm and is perturbed by a network analyzer and a dielectric resonator test fixture by 1 GHz, 3 GHz, 10 G
The relative permittivity and dielectric loss tangent at Hz were measured. (2) Dielectric Properties (Temperature Coefficient of Permittivity) Regarding the molded products obtained in Examples 1 to 20 and Comparative Example 1, −
The temperature coefficient of relative permittivity at 1 MHz from 20 ° C. to 80 ° C. was measured with a network analyzer.

The results are shown in Tables 1 to 3.

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[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

As described above, the thermoplastic resin composition of the present invention comprises a thermoplastic resin mainly composed of at least one of a styrene polymer having a syndiotactic structure and a liquid crystal polymer resin, and has a sintering property of 1 MHz. Relative permittivity of 18 to 130, f · Q value of 2000 or more, −20 ° C.
Resonance frequency temperature coefficient at 80 ℃ is -2 to 35ppm
Since it contains an inorganic filler which is a solid solution of 1 / ° C, 1G
It is possible to easily obtain a molded product having a large relative dielectric constant, a small dielectric loss tangent, and a small temperature coefficient of the relative dielectric constant in a high frequency region of Hz or higher.

In addition to the thermoplastic resin and the inorganic filler,
Since it contains an oxidizer-soluble inorganic filler, the oxidizer-soluble inorganic filler is eluted by treating the molded product obtained by molding the thermoplastic resin composition with an oxidizer, and fine particles are formed on the surface of the molded product. Concavities and convexities can be formed, and high adhesion can be obtained by the anchor effect when plating the surface of the molded product.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // H05K 1/03 610 H05K 1/03 610R B29K 25:00 B29K 25:00 67:00 67:00 105 : 16 105: 16 F term (reference) 4F071 AA22 AA43 AB12 AB18 AB21 AF12 AF40 BC01 BC03 4F206 AA13 AA24 AB11 AB16 AC07 AD03 AD08 4J002 BC03W CF18X DC006 DE066 DE076 DE096 DE136 DE237 FB076 FB086 FB146 GQ05

Claims (28)

[Claims] 1. A thermoplastic resin mainly composed of at least one of a styrene-based polymer having a syndiotactic structure and a liquid crystal polymer resin, and has a relative dielectric constant of 18 to 130 and a f · Q value at a sintering characteristic of 1 MHz. Is more than 2000,-
Resonance frequency temperature coefficient at 20 ° C to 80 ° C is -2 to 3
A thermoplastic resin composition comprising an inorganic filler which is a solid solution of 5 ppm / ° C. 2. The inorganic filler is MgO, CaO, TiO.
_A solid solution consisting of ₂ , BaO, TiO ₂ , Nd ₂ O ₃ , S
BaO, TiO, a solid solution composed of m ₂ O ₃ and Bi ₂ O _3.
2 , Nd ₂ O ₃ , Sm ₂ O ₃ , Bi ₂ O ₃ and MnCO solid solution, Nd ₂ O ₃ , LiCO ₃ and TiO ₂ solid solution, Nd ₂ O ₃ , LiCO ₃ and SrTiO ₃ ,
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is at least one solid solution selected from CaTiO ₃ and TiO ₂ . 3. A total of 100 thermoplastic resins and inorganic fillers.
90 parts by mass of the inorganic filler is contained in 10 parts by mass to 90 parts by mass of the thermoplastic resin in the mass part, and the thermoplastic resin composition according to claim 1 or 2. 4. In addition to the thermoplastic resin and the inorganic filler,
The thermoplastic resin composition according to claim 1, further comprising an oxidizer-soluble inorganic filler. 5. The oxidizer-soluble inorganic filler is added in a total amount of 100 parts by mass of the thermoplastic resin and the oxidizer-soluble inorganic filler.
-30 mass parts is contained, The thermoplastic resin composition of Claim 4 characterized by the above-mentioned. 6. The thermoplastic resin composition according to claim 4, wherein the oxidizing agent-soluble inorganic filler has an average particle size of 6 μm or less. 7. The thermoplastic resin composition according to claim 4, wherein the oxidizing agent-soluble inorganic filler is calcium carbonate. 8. The melt viscosity of the styrene polymer mainly having a syndiotactic structure is 1 to 250 Pa · s when measured by a parallel plate method at a temperature of 300 ° C. and an angular velocity of 100 rad / s. The thermoplastic resin composition according to any one of claims 1 to 7. 9. A styrene-based polymer mainly having a syndiotactic structure is heated at a rate of 10 ° C./min and a temperature of 33.
The thermoplastic resin composition according to any one of claims 1 to 8, wherein the mass reduction at 0 ° C is 5 mass% or less. 10. The liquid crystal polymer resin is a type I, type II, or type III liquid crystalline aromatic polyester obtained from the cocondensation of acetylated p-hydroxybenzoic acid and polyethylene terephthalate. Item 10. The thermoplastic resin composition according to any one of items 1 to 9. 11. The liquid crystal polymer resin has a temperature rising rate of 10 ° C.
/ Min, the mass reduction at a temperature of 330 ° C. is 5% by mass or less, The thermoplastic resin composition according to claim 1. 12. The liquid crystal polymer resin has a melting point of 300 ° C.
It is above, The thermoplastic resin composition in any one of Claim 1 thru | or 11 characterized by the above-mentioned. 13. The inorganic filler has an average particle size of 0.1 to 1.
It is 5 micrometers, The thermoplastic resin composition in any one of Claim 1 thru | or 12 characterized by the above-mentioned. 14. The inorganic coating layer comprising at least one of an inorganic hydroxide and an inorganic oxide is formed on the surface of the inorganic filler.
The thermoplastic resin composition according to any one of 1. 15. The inorganic hydroxide or inorganic oxide is
Titanium, aluminum, silicon, zirconium, tin,
The thermoplastic resin composition according to claim 14, which is a hydroxide or an oxide of at least one element selected from the group consisting of zinc, antimony and magnesium. 16. The inorganic coating layer contains at least one of a hydroxide and an oxide of the same metal element as the metal element contained in the inorganic compound constituting the inorganic filler. Or the thermoplastic resin composition as described in 15 above. 17. The thermoplastic resin composition according to claim 1, wherein the inorganic filler is treated with a coupling agent having an amino group, an epoxy group, or a mercapto group. . 18. The thermoplastic resin composition according to claim 17, wherein the coupling agent used for treating the inorganic filler is (N-phenyl-γ-aminopropyl) trimethoxysilane. 19. A molded article obtained by injection molding the thermoplastic resin composition according to any one of claims 1 to 18. 20. The molded article according to claim 19, which has a relative permittivity of 3 to 20 at 1 GHz. 21. The molded product according to claim 19, wherein the dielectric loss tangent at 1 GHz is 0.002 or less. 22. The temperature coefficient of relative permittivity at −20 ° C. to 80 ° C. at 1 MHz is −1000 to 1000 ppm.
22. The molded article according to any one of claims 19 to 21, wherein the molded article has a temperature of / ° C. 23. The electrode is formed by integrating at least one kind of electrode material during injection molding of the thermoplastic resin composition.
23. The molded product according to any one of 22 to 22. 24. The molded product according to claim 23, wherein the electrode material is a metal foil having a matte surface. 25. The molded product according to claim 19, wherein the electrode is formed by plating. 26. The specific resistance of the electrode is 1 × 10 ⁻⁵ Ω · c.
The molded article according to any one of claims 19 to 25, characterized in that it is m or less. 27. The molded product according to claim 23, wherein the material of the electrode is copper. 28. The molded product according to claim 23, wherein the electrode has a thickness of 10 to 110 μm.