JP5136459B2 - Polycarbonate resin composition for dielectric and molded product - Google Patents

Description

  The present invention relates to a dielectric antenna suitable for use in a high frequency region and a polycarbonate resin composition for a dielectric suitable as a material for the dielectric antenna.

  2. Description of the Related Art Conventionally, surface-mounted dielectric antennas used for mobile communication devices such as cellular phones and wireless LANs have been proposed that are composed of a dielectric ceramic simple substance, a resin simple substance, and a ceramic-containing resin composition. For example, a surface mount dielectric antenna whose antenna base is made of a ceramic or a resin (Patent Document 1), a styrene resin having a syndiotactic structure with good plating properties and a real part of a relative dielectric constant of about 1.8 And a method of manufacturing the same (Patent Document 2). Furthermore, a resin composition (Patent Document 3) in which spherical dielectric ceramic powder is mixed with a resin material in a proportion of 40 vol% to 70 vol% in the composition makes the aspect ratio 3 to 5 to enable high filling. A composite material (Patent Document 4) in which an adjusted metal titanate salt fiber is combined with a thermoplastic resin or the like is disclosed.

JP-A-9-98015 JP 10-45936 A Japanese Patent No. 3930814 Japanese Patent No. 2992667

  By the way, in recent years, with the reduction in weight and size of mobile communication devices such as mobile phones, there is an increasing demand for weight reduction and size reduction of dielectric antennas. However, conventional antennas made of dielectric ceramics and antennas made of resin alone have the following problems.

  That is, in an antenna made of a dielectric ceramic alone, not only does the antenna substrate forming process and firing process take time, but the processability and formability are inferior, making it difficult to create an antenna having a complicated shape. . In addition, the antenna can be downsized by using ceramics with a high dielectric constant, but the antenna has a size effect. There is. Therefore, it is necessary to use a material with a small specific gravity in order to reduce the weight of the antenna. However, dielectric ceramics have a large specific gravity and have a problem that they cannot cope with the weight reduction of the antenna.

Furthermore, in an antenna made of a single resin, the resin has a small specific gravity and is excellent in moldability and workability, but has a problem that it cannot cope with the miniaturization of the antenna because of a small relative dielectric constant. In the case of a composite material in which a ceramic powder and a resin having a relatively small spherical or aspect ratio of 3 to 5 are combined, a high dielectric constant cannot be obtained unless the amount of the ceramic powder added is increased. There is a problem that the specific gravity becomes high and the antenna cannot be reduced in weight. Further, since the function of the dielectric antenna cannot be performed when the electric resistivity is lowered, the antenna material is required to have a volume resistivity of 1 × 10 ¹² Ωcm or more. Furthermore, as a resin for a dielectric antenna for a mobile phone, when the mobile phone is dropped, if the dielectric antenna is destroyed, the antenna function cannot be performed. Therefore, the Charpy impact strength with a notch may be 3 kJ / m ² or more. It has been demanded.

  Therefore, an object of the present invention is to provide a dielectric resin composition having a high real part of relative dielectric constant and a high volume resistivity, excellent mechanical strength, workability and moldability, and a low specific gravity, and a dielectric using the same. It is to provide a body antenna.

  According to the present invention, a resin composition obtained by melt-kneading a polycarbonate resin and a rutile-type fibrous titanium oxide, and the contained rutile-type fibrous titanium oxide has an average diameter of 0.2 to 2 μm. The above object can be achieved by a polycarbonate resin composition for dielectrics, wherein the average aspect ratio is 4.5 or more.

  Since the resin composition according to the present invention has a relatively small specific gravity and excellent properties as a dielectric, it also has excellent mechanical strength and workability. Is preferred.

  The polycarbonate resin composition for a dielectric according to the present invention is obtained by melt-kneading a polycarbonate resin and a rutile-type fibrous titanium oxide having a high aspect ratio.

(A) Polycarbonate resin The polycarbonate resin is excellent as molding processability and mechanical properties and has a low dielectric loss tangent, and is preferable as the resin substrate of the present invention.

  As the polycarbonate resin used in the present invention, an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin can be used, and among them, an aromatic polycarbonate resin is preferable. The aromatic polycarbonate resin is a thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4, 4-dihydroxybiphenyl etc. are mentioned, Preferably bisphenol A is mentioned. Further, for the purpose of further enhancing the flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a polymer or oligomer having a siloxane structure and containing both terminal phenolic OH groups is used. Can do.

  The aromatic polycarbonate resin used in the present invention is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatics. And a polycarbonate copolymer derived from an aromatic dihydroxy compound. Further, two or more kinds of polycarbonate resins may be used in combination.

  The molecular weight of the polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and is in the range of 14,000 to 30,000, preferably 15,000 to 28. 16,000, more preferably 16,000-26,000. If the viscosity average molecular weight is less than 14,000, the mechanical strength is insufficient, and if it exceeds 30,000, the moldability tends to be difficult, which is not preferable.

  The method for producing such an aromatic polycarbonate resin is not limited, and the aromatic polycarbonate resin can be produced by a phosgene method (interfacial polymerization method), a melting method (transesterification method), or the like. Furthermore, the aromatic polycarbonate resin which adjusted the amount of OH groups of the terminal group manufactured by the melting method can be used.

  Furthermore, as the aromatic polycarbonate resin, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins can be used. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. In addition, as the regenerated aromatic polycarbonate resin, non-conforming product, pulverized product obtained from sprue or runner, or pellets obtained by melting them can be used.

(B) Rutile-type fibrous titanium oxide Since rutile-type titanium oxide has a large relative dielectric constant real part compared to anatase-type titanium oxide, when it is contained in a resin material, a resin composition having a large relative dielectric constant real part is provided. In addition, rutile titanium oxide can be made into a fibrous shape, that is, a shape with a high aspect ratio, so that when it is contained in a resin, the relative permittivity real part in the fiber major axis direction can be effectively improved. Is possible.

  As the rutile type fibrous titanium oxide, the one having a high aspect ratio can express a high dielectric constant with a small content. This is considered to be because the fiber length direction of the fibrous titanium oxide is easily oriented in the flow direction during molding such as injection molding, and the fibers are aligned in one direction. In the present invention, the average aspect ratio in the resin composition is 4.5 or more, preferably 5.0 or more, particularly 6.0 or more. However, the size of the aspect ratio and the dielectric constant are not necessarily proportional, and even if a rutile-type fibrous titanium oxide having an aspect ratio that is too large is used, it is difficult to melt and knead or the titanium oxide is remarkably produced by melt kneading. Since it breaks, it is preferable to use one having an average aspect ratio of 200 or less, particularly 100 or less.

  The average diameter of the rutile fibrous titanium oxide is 0.2 to 2 μm. If the average diameter is too small, the bulk specific gravity becomes small, so that it becomes difficult to obtain a uniform resin composition by melt kneading. Further, in a conventional single-screw or twin-screw kneader, there is a problem that when kneading is attempted, the screw is idle and kneading cannot be performed, or the discharge rate is lowered and productivity is lowered. Furthermore, since the specific surface area increases, the resin material may be deteriorated.

  Conversely, if the average diameter is too large, the fiber length must be increased to ensure the aspect ratio. However, if the fiber length is long, the fiber tends to break during melt-kneading or injection molding, and there is a problem that the aspect ratio of the rutile-type fibrous titanium oxide in the resin composition or molded product cannot be maintained high. Furthermore, since it takes time to grow the rutile fibrous titanium oxide, there is a problem that a product having a large diameter and a large aspect ratio is expensive to manufacture. The average diameter of the rutile fibrous titanium oxide is preferably 0.3 to 0.7 μm.

  In the present specification, the average diameter and average aspect ratio of the rutile-type fibrous titanium oxide used can be determined by the following method. Magnified and observed with a scanning electron microscope (1,500 to 20,000 times), the diameter and fiber length of 500 rutile-type fibrous titanium oxides were measured, and the arithmetic average of the diameter and the phase of the fiber length An arithmetic average was calculated, and an average aspect ratio was obtained as the ratio.

  The content of (B) rutile-type fibrous titanium oxide in the resin composition is preferably 5% by volume to 40% by volume, particularly preferably 10% by volume to 30% by volume. If it is 5% by volume or less, the effect of improving the relative dielectric constant is small, and if it is 40% by volume or more, there is a problem that the mechanical strength of the resin composition is lowered and the productivity is also lowered.

  The fibrous titanium oxide used in the present invention may have a surface treated with an inorganic compound other than titanium oxide, specifically, for example, alumina, silica, zirconia or the like. These inorganic compounds other than titanium oxide are usually used in the production process of fibrous titanium oxide when treating the fibrous titanium oxide for the purpose of improving the handling of the fibrous titanium oxide.

In the fibrous titanium oxide used in the present invention, the content of inorganic substances other than these titanium oxides may be appropriately selected and determined, but is usually 2 to 5% by mass in the fibrous titanium oxide used in the present invention. If the content of the inorganic compound is too large, especially if the amount of the silica component is too large, the adsorbed water in the inorganic compound used for the treatment may cause problems due to poor appearance or dripping during combustion.
Therefore, when treating the fibrous titanium oxide used in the present invention with an inorganic compound, it is preferable to treat with alumina or zirconia without using silica.

  Furthermore, the fibrous titanium oxide used in the present invention is preferable because the thermal stability is greatly improved by surface treatment with an organosilicon compound such as an organosilane compound or an organosilicone compound. Prior to the surface treatment with the organosilicon compound, the titanium oxide surface may be surface treated with an inorganic compound or the like. A smaller amount of the inorganic compound used for the surface treatment is preferable. For example, it is preferably 2% by mass or less with respect to fibrous titanium oxide.

  Examples of the surface treatment agent for fibrous titanium oxide include an organosilane compound or an organosilicone compound having an alkoxy group, an epoxy group, an amino group, or a Si—H bond. Among these, it is preferable to use a silicone compound (hydrogen polysiloxane) having a Si—H bond. The amount of the organic silicone compound used as the surface treatment agent is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on fibrous titanium oxide. 5 to 2% by mass is particularly preferable.

  In the present invention, a flame retardant can be used to impart flame retardancy. The flame retardant is not particularly limited as long as it improves the flame retardancy of the composition, but a phosphoric acid ester compound, an organic sulfonic acid metal salt, and a silicone compound are preferable.

  As a phosphoric acid ester compound used by this invention, the compound shown by following formula (1) is preferable, for example.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は互いに独立して、置換されていても良いアリール基を示し、Ｘは他に置換基を有していても良い２価の芳香族基を示す。ｎは０〜５の数を示す。） 上記式（１）においてＲ1〜Ｒ4で示されるアリール基としては、フェニル基、ナフチル基等が挙げられる。またＸで示される２価の芳香族基としては、フェニレン基、ナフチレン基や、例えばビスフェノールから誘導される基等が挙げられる。これらの置換基としては、アルキル基、アルコキシ基、ヒドロキシ基等が挙げられる。ｎが０の場合はリン酸エステルであり、ｎが０より大きい場合は縮合リン酸エステル（混合物を含む）である。

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an aryl group which may be substituted, and X is a divalent aromatic which may have another substituent. In the formula (1), examples of the aryl group represented by R1 to R4 include a phenyl group and a naphthyl group. Examples of the divalent aromatic group represented by X include a phenylene group, a naphthylene group, and a group derived from, for example, bisphenol. Examples of these substituents include an alkyl group, an alkoxy group, and a hydroxy group. When n is 0, it is a phosphate ester, and when n is greater than 0, it is a condensed phosphate ester (including a mixture).

  Specific examples include bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, and substituted and condensates thereof. Examples of commercially available condensed phosphate compounds that can be suitably used as such components include, for example, “CR733S” (resorcinol bis (diphenyl phosphate)), “CR741” (bisphenol A bis ( Diphenyl phosphate)) and “PX-200” (resorcinol bis (dixylenyl phosphate)) and are readily available.

  The content of the phosphate ester flame retardant in the composition of the present invention is 1 to 50 parts by weight, preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight, based on 100 parts by weight of the (A) polycarbonate resin. Part. If the content of the phosphate ester flame retardant is less than 1 part by mass, the flame retardancy is insufficient, and if it exceeds 50 parts by mass, the heat resistance is excessively lowered, which is not preferable.

  The organic sulfonic acid metal salt used in the present invention is preferably an aliphatic sulfonic acid metal salt or an aromatic sulfonic acid metal salt. The metal constituting the organic sulfonic acid metal salt is preferably an alkali metal, an alkaline earth metal, etc., and the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium. , Calcium, strontium and barium. The organic sulfonic acid metal salt can also be used by mixing two or more kinds of salts.

  Preferred examples of the aliphatic sulfonate include a metal fluoroalkane sulfonate, and more preferably a metal metal perfluoroalkane sulfonate. Preferred examples of the fluoroalkanesulfonic acid metal salt include an alkali metal salt of fluoroalkanesulfonic acid, an alkaline earth metal salt of fluoroalkanesulfonic acid, and more preferably a fluoroalkanesulfonic acid having 4 to 8 carbon atoms. Alkali metal salts, alkaline earth metal salts, and the like. Specific examples of the fluoroalkane-sulfonic acid metal salt include sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate, potassium perfluoromethylbutanesulfonate, and sodium perfluorooctanesulfonate. And potassium perfluorooctane sulfonate.

  The aromatic sulfonic acid metal salt is preferably an aromatic sulfonic acid alkali metal salt, an aromatic sulfonic acid alkaline earth metal salt, an aromatic sulfone sulfonic acid alkali metal salt, or an aromatic sulfone sulfonic acid alkaline earth metal. Salts, and the like, and the aromatic sulfonesulfonic acid alkali metal salt and the aromatic sulfonesulfonic acid alkaline earth metal salt may be a polymer. Specific examples of the aromatic sulfonic acid metal salt include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, benzenesulfonic acid sodium salt, diphenylsulfone-3-sulfonic acid. Sodium salt, potassium salt of diphenylsulfone-3-sulfonic acid, sodium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid, potassium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid calcium salt, diphenylsulfone-3,3′-disulfonic acid disodium salt, diphenylsulfone-3,3′-disulfonic acid dipotassium salt, and the like. Can be mentioned.

  The compounding amount of the organic sulfonic acid metal salt is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and particularly preferably 0.03 to 2 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. Part by mass. When the amount of the organic sulfonic acid metal salt is less than 0.01 parts by mass, sufficient flame retardancy is difficult to obtain, and when it exceeds 5 parts by mass, the thermal stability tends to be lowered.

The silicone flame retardant used in the present invention is preferably a polyorganosiloxane having a linear or branched structure. The organic group possessed by the polyorganosiloxane includes hydrocarbons such as alkyl groups and substituted alkyl groups having 1 to 20 carbon atoms, vinyl and alkenyl groups, cycloalkyl groups, and aromatic hydrocarbon groups such as phenyl and benzyl. Chosen from.
Even if polydiorganosiloxane does not contain a functional group, it may contain a functional group. In the case of a polydiorganosiloxane containing a functional group, the functional group is preferably a methacryl group, an alkoxy group or an epoxy group.
These polyorganosiloxanes may be supported on silica.

  Further, in the present invention, for the purpose of preventing dripping at the time of combustion, an anti-dripping agent can be included, and a fluororesin is preferably used. Here, the fluororesin is a polymer or copolymer containing a fluoroethylene structure, for example, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene and fluorine. It is a copolymer with an ethylene monomer that does not contain. Polytetrafluoroethylene (PTFE) is preferable, and the average molecular weight is preferably 500,000 or more, and particularly preferably 500,000 to 10,000,000.

In addition, when polytetrafluoroethylene having a fibril forming ability is used, it is possible to impart higher melt dripping prevention property. Although there is no restriction | limiting in particular in the polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTM standard is mentioned. Specific examples thereof include, for example, Teflon (registered trademark) 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries, Ltd.), CD076 ( Asahi IC Fluoropolymers Co., Ltd.). Other than those classified as type 3, for example, Argoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. These polytetrafluoroethylene (PTFE) may be used independently and may combine 2 or more types. Polytetrafluoroethylene (PTFE) having the fibril-forming ability as described above is prepared by, for example, using tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, at a pressure of 1 to 100 psi, at a temperature of 0. It is obtained by polymerizing at ˜200 ° C., preferably 20˜100 ° C.
Alternatively, Teflon (registered trademark) 30-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) dispersed in a solvent may be used.

  Further, it may be a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and organic polymer particles. Specific examples of monomers for producing organic polymer particles include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene. Styrene monomers such as 2,4-dimethylstyrene, α-methylstyrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate (Meth) acrylic acid ester-based single quantities such as 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridodecyl acrylate, tridodecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether, vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate, ethylene, propylene, isobutylene Examples thereof include, but are not limited to, olefin monomers such as diene monomers such as butadiene, isoprene and dimethylbutadiene. Preferably, two or more types of polymers or copolymers of these monomers can be used to obtain organic polymer particles.

  In the present invention, an elastomer can be included as an impact resistance improver for improving impact strength. The elastomer is not particularly limited, but a multilayer structure polymer is preferable. As a multilayer structure polymer, the thing containing an alkyl (meth) acrylate type polymer is mentioned, for example. These multi-layered polymers include, for example, polymers produced by continuous multi-stage seed polymerization in which a polymer in a previous stage is sequentially coated with a polymer in a subsequent stage, and a basic polymer. As a structure, it is a polymer having an outermost core layer made of a polymer compound that improves the adhesion between the inner core layer, which is a crosslinking component having a low glass transition temperature, and the matrix of the composition. A rubber component having a glass transition temperature of 0 ° C. or lower is selected as a component that forms the innermost core layer of these multilayer polymers. These rubber components include rubber components such as butadiene, rubber components such as styrene / butadiene, rubber components of alkyl (meth) acrylate polymers, polyorganosiloxane polymers and alkyl (meth) acrylate polymers. Or a rubber component using these in combination. Furthermore, examples of the component that forms the outermost core layer include an aromatic vinyl monomer, a non-aromatic monomer, or a copolymer of two or more thereof. Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, monochloro styrene, dichloro styrene, bromo styrene, and the like. Of these, styrene is particularly preferably used. Examples of non-aromatic monomers include alkyl (meth) acrylates such as ethyl (meth) acrylate and butyl (meth) acrylate, vinyl cyanide such as acrylonitrile and methacrylonitrile, and vinylidene cyanide.

  Other components can be further added to the resin composition of the present invention as necessary. Examples of such additives include fillers, reinforcing agents, weather resistance improvers, foaming agents, lubricants, fluidity improvers, impact resistance improvers, dyes, pigments, dispersants, ultraviolet absorbers, mold release agents, and the like. Is mentioned.

  For example, as a filler or a reinforcing agent, both organic and inorganic can be used. Usually, glass fiber, mica (white mica, black mica, gold mica, etc.), alumina, talc, wollastonite, potassium titanate, It is preferable to use inorganic substances such as calcium carbonate and silica. These are blended so as to be 1 to 80 parts by mass, preferably 5 to 60 parts by mass with respect to 100 parts by mass of the polycarbonate resin. When these are blended, generally rigidity, heat resistance, dimensional accuracy, etc. can be improved. Among these, white mica and alumina are more preferable because they have an effect of reducing the dielectric loss tangent. 5-100 mass parts is preferable with respect to 100 mass parts of polycarbonate resin, and, as for the compounding quantity of white mica and an alumina, 10-50 mass parts is more preferable.

  Although the manufacturing method of the resin composition of this invention is not limited, The melt kneading method is preferable. For example, after mixing rutile type fibrous titanium oxide with polycarbonate resin and additives as described above if necessary, uniformly mixed with a Henschel mixer, ribbon blender, V type blender, etc., then uniaxial or multiaxial kneading It can manufacture by kneading | mixing with an extruder, a roll, a Banbury mixer, a lab plast mill (Brabender), etc. Instead of mixing and kneading all the components at once, some components can be mixed in advance or supplied in the middle of kneading without mixing in advance. In kneading, it is inevitable that rutile-type fibrous titanium oxide is usually broken to some extent. Therefore, rutile-type fibrous titanium oxide having an aspect ratio larger than the desired aspect ratio is used as the resin composition. Used as a raw material. When there is a high risk of breakage, for example, when a twin-screw kneading extruder is used, it is preferable to perform so-called side feed, in which the rutile fibrous titanium oxide is supplied from the middle of the extruder.

  The kneading temperature and the kneading time vary depending on the intended resin composition and the type of the kneader, but usually the kneading temperature is 240 to 350 ° C, preferably 260 to 320 ° C, and the kneading time is preferably 20 minutes or less. When the temperature exceeds 350 ° C. or 20 minutes, the resin material has a problem of thermal deterioration, which may cause deterioration of physical properties and appearance defects of the molded product.

The dielectric resin composition of the present invention thus obtained is suitable for dielectric antenna parts. For use in a derivative antenna component, the real part of relative permittivity is preferably 5 or more, and more preferably 6 or more. The dielectric loss tangent is preferably 0.3 or less, and more preferably 0.2 or less. Further, the volume resistivity is preferably 1 × 10 ¹² Ωcm or more, and more preferably 1 × 10 ¹⁴ Ωcm or more. Notched Charpy impact strength is preferably 3 kJ / ^{m 2} or more, 4 kJ / ^{m 2} or more is more preferable. A derivative antenna component using a component obtained by molding the resin composition of the present invention is, for example, a parallel molding in which the dielectric resin composition of the present invention is molded into a rectangular parallelepiped and a metal conductor is sandwiched between the molded products. There are flat antennas or microstrip line antennas. In addition, there is a surface-mounted antenna in which an electrode bent in a U-shape is disposed on the surface of a part formed by molding the dielectric resin composition of the present invention.

The molded article using the dielectric resin composition of the present invention can be suitably used even in the GHz band, and can have a high real part of relative dielectric constant when the frequency band is 2.45 GHz. In addition, it can have an electrical resistivity of 1 × 10 ¹² Ωcm or more while maintaining such high dielectric properties.
Therefore, a molded article using the dielectric resin composition of the present invention is used for a mobile antenna such as a mobile phone and a notebook personal computer, a dielectric antenna component used for a wireless LAN, particularly a surface mount type derivative antenna component. Is preferred.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following examples, the following components were used.

(A) Resin material (A-1) Polycarbonate resin: Poly-4,4-isopropylidenediphenyl carbonate, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon (registered trademark) S-3000, viscosity average molecular weight 21, 000

(B) Titanium compound rutile fibrous titanium oxide;
Ishihara Sangyo Co., Ltd., “trade name: FTL-400”, average diameter 0.5 μm, average fiber length 10 μm, average aspect ratio 20.
(B-1) 98% by mass of FTL-400 and 2% by mass of methylhydrogensiloxane (“trade name: SH1107” manufactured by Toray Dow Corning Co., Ltd.) are mixed and mixed with a Henschel mixer for surface treatment. Rutile fibrous titanium oxide.
(B-2) 99% by mass of FTL-400 and 1% by mass of methyl hydrogen siloxane (“trade name: SH1107” manufactured by Toray Dow Corning Co., Ltd.) are mixed and mixed with a Henschel mixer for surface treatment. Rutile fibrous titanium oxide.
(B-3) FTL-400 (methyl hydrogen siloxane untreated product)

(B-4) particulate titanium oxide;
Ishihara Sangyo Co., Ltd. “trade name: PC-3”, average diameter 0.18 μm, average aspect ratio 1.

(C) Mold release agent (C-1) manufactured by Clariant Japan Co., Ltd., trade name: LICOWAX PE520POWDER

[Examples 1-4, Comparative Examples 1-2]
A polycarbonate resin and a release agent other than the titanium compound were blended at the ratio shown in Table 1, and mixed uniformly with a tumbler mixer. This is put into the upstream part of a twin screw extruder (manufactured by Nippon Steel Works, “TEX30HSST”, screw diameter 30 mm, L / D = 42), and the titanium compound is fed from the middle of the cylinder of the twin screw extruder using a weight feeder. A so-called side feed was performed, and melt-kneading was performed at a cylinder temperature of 280 ° C., a screw rotation speed of 250 rpm, and a discharge rate of 15 kg / hour to produce resin composition pellets. In the case of the polycarbonate resin composition, the obtained resin composition was dried at 120 ° C. for 4 hours, and then the following (1) to (6) were evaluated. The evaluation results are shown in Table 1.

[Evaluation method]
(1) Average aspect ratio About 5 g of the resin composition pellets obtained by the above method were weighed and incinerated in an electric furnace at 600 ° C. (“Electric Muffle Furnace KM-28” manufactured by Toyo Seisakusho Co., Ltd.) for 2 hours. After burning only the components, the remaining rutile type fibrous titanium oxide is (1,500 to 20,000 times) using a scanning electron microscope (manufactured by Hitachi, Ltd., “S-4100”). The diameter and fiber length of 500 rutile fibrous titanium oxides were measured. The average aspect ratio was determined from the arithmetic average of the obtained diameters and the arithmetic average of the fiber lengths.

(2) Dielectric properties Using the resin composition pellets obtained by the above method, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., “SH100”, mold clamping force 100 t), cylinder temperature 290 ° C. to 310 ° C., A plate-shaped molded article having a mold temperature of 100 ° C. and having a size of 100 mm × 100 mm × thickness 2 mm was produced. The plate-shaped molded product was machine-cut to a width of 0.5 mm so that the flow direction was the longitudinal direction, and processed into a rod-shaped molded product of 100 mm × 0.5 mm × thickness 2 mm. Using this rod-shaped molded product, a dielectric constant measuring device combining “Network Analyzer N5230A” manufactured by Agilent Technologies and “Cylinder Cavity Resonator CP481 for 2.45 GHz” manufactured by Kanto Electronics Application Development Co., Ltd. The real part of dielectric constant and the dielectric loss tangent were measured.

(3) Viscosity average molecular weight Using the resin composition pellets obtained by the above method, using methylene chloride as a solvent, and using an Ubbelohde viscometer, the intrinsic viscosity [η] at a temperature of 20 ° C. (unit: dl / g) Was calculated from the viscosity equation of Schnell, that is, η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

(4) Volume resistivity Using the resin composition pellets obtained by the above method, the cylinder temperature was 290 ° C to 310 ° C with an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., "SH100", mold clamping force 100t). A plate-shaped molded product having a size of 100 mm × 100 mm × thickness 2 mm was manufactured under the conditions of a mold temperature of 100 ° C. About the obtained plate-shaped molded article, volume resistivity was measured using Advantest Co., Ltd. product: R8340 digital super high resistance / micro ammeter and R12704 resiliency chamber.

(5) Charpy strength with notch Using the resin composition pellets obtained by the above method, the cylinder temperature at an injection molding machine (manufactured by Sumitomo Heavy Industries, “SG75 Cycap M-2”, clamping force 75 t) ISO test pieces were manufactured under conditions of 270 ° C. to 290 ° C. and a mold temperature of 110 ° C. Using the obtained ISO test piece, the notched Charpy strength was measured according to ISO standard 179-1 and ISO 179-2.

(6) Tensile properties Cylinder temperature of 270 ° C. using an injection molding machine (“SG75 Cycap M-2”, clamping force 75 t) manufactured by Sumitomo Heavy Industries, Ltd. using the resin composition pellets obtained by the above method. ISO test pieces were manufactured under conditions of ˜290 ° C. and mold temperature 110 ° C. Using the obtained ISO test piece, the yield strength, yield nominal strain, tensile strength, fracture nominal strain, and tensile elastic modulus were measured in accordance with ISO standard 527-1 and ISO527-2.

Claims (9)

A resin composition obtained by melt-kneading a polycarbonate resin (A) and a rutile-type fibrous titanium oxide (B), and the contained rutile-type fibrous titanium oxide has an average diameter of 0.2 to 2 μm. A polycarbonate resin composition for dielectrics, wherein the average aspect ratio is 4.5 or more. 2. The polycarbonate resin composition for a dielectric according to claim 1, wherein the rutile-type fibrous titanium oxide (B) is surface-treated with an organosilicon compound. The polycarbonate resin composition for a dielectric according to claim 2, wherein the organosilicon compound is at least one selected from an organosilane compound and an organosilicone compound. The polycarbonate resin composition for a dielectric according to claim 3, wherein the organic silicone compound is methylhydrogensiloxane. 5. The polycarbonate resin composition for a dielectric according to claim 2, wherein the treatment amount of the organosilicon compound with respect to the rutile-type fibrous titanium oxide (B) is 0.1 to 5% by mass. object. The polycarbonate resin for dielectrics according to any one of claims 1 to 5, wherein a ratio of rutile-type fibrous titanium oxide (B) in the resin composition is 5% by volume or more and 40% by volume or less. Composition. A polycarbonate resin molded article for a dielectric, wherein the volume resistivity obtained by molding the dielectric polycarbonate resin composition according to claim 1 is 1 × 10 ¹² Ωcm or more. A polycarbonate resin molded article for dielectrics having a notched Charpy strength of 3 kJ / m ² or more obtained by molding the polycarbonate resin composition for dielectrics according to any one of claims 1 to 6. A dielectric antenna formed by molding the dielectric resin composition according to claim 1.