TW202126461A - Composition, method for producing antenna, and molded article - Google Patents

Abstract

Provided are: a composition which has excellent dielectric properties and adhesiveness and can be injection-molded or compression-molded on a substrate; a method for producing a high-performance antenna including the substrate molded from the composition; and a molded article molded from a molding. The composition according to the present invention includes a heat-meltable polymer containing a unit based on a tetrafluoroethylene, and is used for forming a substrate having a dielectric loss tangent of at most 0.05 by means of injection molding or compression molding. In addition, a method for producing an antenna according the present invention is: a method for producing an antenna provided with a molded portion holding an antenna pattern formed by means of an injection molding; or a method for producing an antenna provided with a matching layer covering an antenna pattern formed by means of a compression molding.

Description

Composition, antenna manufacturing method and molded product

The present invention relates to a composition containing a specific hot-melt polymer, and a manufacturing method and molded article of an antenna using the composition.

With the miniaturization of portable communication devices such as mobile phones and smart phones, the antennas (chip antennas) mounted in them continue to be miniaturized. This small antenna generally has an antenna pattern that includes a conductor; and a base (dielectric base) that holds the antenna pattern and includes a dielectric such as resin (see Patent Document 1). In Patent Document 1, an antenna pattern is used as an embedded part, and a dielectric body is injection-molded to form a base, and a small antenna in which the antenna pattern and the base are integrated is manufactured. Prior art literature Patent literature

Patent Document 1: International Publication No. 2013/137404

[The problem to be solved by the invention]

From the viewpoint of further enhancement of antenna performance (an increase in antenna gain), a dielectric body with excellent dielectric properties is required. However, according to research conducted by the inventors of the present invention, the dielectric body (dielectric substrate) of Patent Document 1 is still insufficient. In addition, in Patent Document 1, although the antenna pattern and the dielectric substrate are integrated, the adhesiveness between them is also insufficient. The inventors of the present invention conducted intensive research to improve these situations. As a result, it was found that if a specific hot-melt polymer is contained, a composition having excellent electrical properties and adhesiveness and suitable for injection molding or compression molding can be prepared. The object of the present invention is to provide a composition capable of forming a matrix with excellent adhesion and low dielectric loss tangent by injection molding or compression molding, a method for manufacturing a high-performance antenna having a matrix formed from the composition, and A molded product formed from the above molded product. [Technical means to solve the problem]

The present invention has the following aspects. <1> A composition containing a hot-melt polymer containing tetrafluoroethylene-based units and used for forming a matrix with a dielectric loss tangent of 0.05 or less by injection molding or compression molding. <2> The composition as in the above <1>, wherein the substrate is the molded part or the integrated layer of the antenna. <3> The composition as in the above <1> or <2>, wherein the substrate is the molded part or the integrated layer of the antenna, and the thickness of the molded part or the integrated layer is 1 cm or less. <4> The composition according to any one of the above <1> to <3>, which further contains a dielectric filler having a dielectric constant of 1.5 or more, and the dielectric constant of the substrate exceeds 1.5. <5> The composition according to the above <4>, wherein the dielectric filler is a spherical filler having an average particle diameter of 2 μm or less, or a fibrous filler having a length of 30 μm or less and a diameter of 2 μm or less. <6> The composition of the above <4> or <5>, wherein the ratio of the dielectric filler in the composition to the ratio of the hot melt polymer in the composition is The ratio of the mass meter is 1/10 to 1/1. <7> The composition according to any one of the above <1> to <6>, wherein the hot melt polymer contains a unit based on perfluoro(alkyl vinyl ether), hexafluoropropylene or fluoroalkyl ethylene. <8> The composition according to any one of the above <1> to <7>, which further contains polytetrafluoroethylene. <9> The composition according to any one of the above <1> to <8>, which further contains polytetrafluoroethylene, and the proportion of the polytetrafluoroethylene in the composition relative to the hot melt polymer The ratio by mass of the ratio in the above composition is 1 or less, and the composition is used to form the above matrix by injection molding. <10> The composition according to any one of the above <1> to <9>, which further contains polytetrafluoroethylene, and the ratio of the polytetrafluoroethylene in the composition to the hot melt polymer The ratio by mass of the ratio in the above composition is 1 or more, and the composition is used to form the above matrix by compression molding. <11> A method of manufacturing an antenna, which is a method of manufacturing an antenna having an antenna pattern and a dielectric loss tangent of 0.05 or less and maintaining a molded part of the antenna pattern, and it is set as the above-mentioned <1> to When the composition of any one of <10> is injected into a mold having a shape corresponding to the molded part to form the molded part, the antenna pattern is already placed in the molded mold, or the molded part is formed The molded part and the antenna pattern are assembled. <12> A manufacturing method of an antenna, which is a method of manufacturing an antenna with an antenna pattern and a dielectric loss tangent of 0.05 or less and covering the integrated layer of the antenna pattern, and it is based on the above-mentioned <1> to <8 After the composition of any one of> and <10> is supplied into a mold having a shape corresponding to the integration layer and compressed to form an integration layer, the integration layer and the antenna pattern are assembled. <13> The manufacturing method of the above <12>, in which a metal layer is further formed on the surface of the integration layer opposite to the antenna pattern. <14> A molded product formed from the composition of any one of the above <1> to <10> by injection molding or compression molding. <15> The molded product of the above-mentioned <14>, wherein the molded product is an antenna. [Effects of Invention]

According to the present invention, it is possible to obtain a composition for injection molding or compression molding suitable for molding a substrate with excellent adhesiveness and low dielectric loss tangent, and a high-performance antenna.

The following terms have the following meanings. The so-called "hot-melt polymer" means a polymer that exhibits melt fluidity. It means that under a load of 49 N, the melt flow rate becomes 0.1 at a temperature higher than the melting temperature of the polymer by 20°C or more. ~1000 g/10 minutes temperature polymer. The so-called "melt flow rate (MFR)" refers to the melt mass flow rate of the polymer specified in JIS K 7210: 1999 (ISO 1133: 1997). The "melting temperature (melting point) of the polymer" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method. The "melt viscosity of the composition" is the value measured at a shear rate of 1000/sec in accordance with JIS K 7199: 1999 (ISO 11443: 1995). "Average particle size" is to disperse the target particles (powders, fillers, etc.) in water by using a laser diffraction, scattering type particle size distribution measuring device (Horiba Manufacturing Co., Ltd., LA-920 measuring device). It is determined by analysis by diffraction and scattering methods. That is, the particle size distribution of particles is measured by laser diffraction and scattering methods, and the total volume of the particle cluster is set to 100% to obtain a cumulative curve. The point on the cumulative curve where the cumulative volume becomes 50% is the average particle diameter (D50 ). Furthermore, a cumulative curve is obtained by setting the total volume of the particle cluster to 100%, and the point on the cumulative curve at which the cumulative volume becomes 10% is D10. "Ten-point average roughness (Rzjis)" is the value specified in Annex JA of JIS B 0601: 2013. The "dielectric constant" in the present invention means the relative permittivity, which is also called the relative permittivity, relative to the permittivity of vacuum. The "unit" in a polymer can be an atomic group directly formed from a monomer by a polymerization reaction, or it can be a part of a structure obtained by processing a polymer obtained by a polymerization reaction by a specific method. Atomic group. The monomer A-based unit contained in the polymer is also abbreviated as "monomer A unit".

The composition of the present invention contains a hot-melt polymer containing tetrafluoroethylene (TFE)-based units (hereinafter also referred to as "F polymer"), and is used to form a dielectric loss tangent by injection molding or compression molding It is a matrix (dielectric matrix) of 0.05 or less. The F polymer in the present invention exhibits good thermal melting properties, and its melt viscosity converges within a specific range, so it can be easily filled with high density during injection molding or compression molding. As a result, it is considered that bubbles (air layer) are not easily formed in the formed substrate, and the decrease in dielectric properties due to the existence of bubbles is suppressed. In addition, when the composition contains fillers such as dielectric fillers, the fillers are easily dispersed uniformly and stably. As a result, it is presumed that a matrix exhibiting a lower dielectric loss tangent can be formed.

The dielectric loss tangent of the substrate in the present invention is 0.05 or less. The dielectric loss tangent of the substrate is preferably 0.04 or less, and more preferably 0.03 or less. The lower limit is usually 0.001. In addition, the dielectric constant of the substrate in the present invention is preferably more than 1.5, more preferably 2 or more. Furthermore, 3 or more is preferable, and 4 or more is especially preferable. The upper limit is usually 10. The substrate in the present invention preferably has a dielectric constant exceeding 1.5 and a dielectric loss tangent of 0.05 or less, and more preferably a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less. Furthermore, the dielectric constant and dielectric loss tangent in this specification are the values measured at 20 GHz. The base in the present invention can be particularly used as a forming part or an integrated layer of an antenna and is well used to improve the performance of the antenna. The antenna is easy to exert higher performance (antenna gain). Here, the molded part of the antenna is preferably a member (holding member) that holds the antenna pattern including the conductor. The integrated layer of the antenna is a layer arranged to cover the antenna pattern in order to suppress the attenuation of the current flowing through the antenna pattern. The thickness of the molded part and the integrated layer of the antenna is preferably 1 cm or less, more preferably 0.5 mm or less, and still more preferably 0.01 mm or less. The composition of the present invention has excellent moldability, and can form the thinner molded part or integrated layer with excellent dielectric properties.

The F polymer in the present invention is a hot melt polymer containing TFE-based units (TFE units). The F polymer can be a homopolymer of TFE, or a copolymer of TFE and other monomers (comonomers) copolymerizable with TFE. That is, the F polymer may be polytetrafluoroethylene (PTFE) as long as it exhibits hot melt properties. The F polymer preferably has 90-100 mol% of TFE units with respect to all units constituting the polymer. The fluorine content of the F polymer is preferably 70 to 76% by mass, more preferably 72 to 76% by mass. If the F polymer with the fluorine content in the above range is used, the dielectric properties of the matrix can be improved (especially low dielectric loss tangent).

Examples of F polymers include: copolymers of TFE and ethylene (ETFE), copolymers of TFE and propylene, copolymers of TFE and perfluoro (alkyl vinyl ether) (PAVE) (PFA), TFE and six Copolymer of fluoropropylene (HFP) (FEP), copolymer of TFE and fluoroalkyl ethylene (FAE), copolymer of TFE and chlorotrifluoroethylene (CTFE). Furthermore, these copolymers may further contain units based on other comonomers.

The F polymer preferably contains a TFE unit, and a PAVE unit, HFP unit or FAE unit. Examples of PAVE include: CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ , CF ₂ =CFOCF ₂ CF ₂ CF ₃ (PPVE), CF ₂ =CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ =CFO (CF ₂ ) ₈ F. Examples of FAE include: CH ₂ =CH(CF ₂ ) ₂ F, CH ₂ =CH(CF ₂ ) ₃ F, CH ₂ =CH(CF ₂ ) ₄ F, CH ₂ =CF(CF ₂ ) ₃ H , CH ₂ =CF(CF ₂ ) ₄ H.

F melt viscosity of the polymer is preferably at 380 deg.] C of ^{1 × 10 2 ~ 1 × 10} 6 Pa · s, more preferably at 300 deg.] C of ^{1 × 10 2 ~ 1 × 10} 6 Pa · s. In this case, it is easy to inject at a lower temperature to form a matrix. The melting temperature of the F polymer is preferably 260 to 320°C, more preferably 285 to 320°C. In this case, the deterioration and deterioration of the dielectric filler can be prevented well. The MFR of the F polymer is preferably 20 g/10 minutes or less, more preferably 10 g/10 minutes or less. In this case, it is easy to form a matrix with a more complicated shape. The melt viscosity of the composition is preferably 50-1000 Pa·s, and preferably 75-750 Pa·s at a shear rate of 1000/sec. In this case, it is also easy to form a matrix with a more complicated shape.

Preferred specific examples of the F polymer include modified PTFE, FEP, and PFA. Furthermore, modified PTFE is a copolymer of TFE and a very small amount of comonomers (HFP, PAVE, FAE, etc.), and it is PTFE that exhibits hot melt properties. As the F polymer, an F polymer having a polar functional group is preferred. The polar functional group may be contained in the monomer unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. As the latter polymer, a polymer having a polar functional group in the form of a terminal group derived from a polymerization initiator, a chain transfer agent, etc. can be mentioned. In addition, an F polymer having a polar functional group obtained by performing plasma treatment or ionizing radiation treatment on the F polymer can also be exemplified. The F polymer having a polar functional group is preferably an F polymer containing a monomer unit having a polar functional group (hereinafter also referred to as "polar unit"). Hereinafter, a monomer having a polar functional group that becomes a polar unit by polymerization is also referred to as a "polar monomer".

The polar functional group is preferably a hydroxyl group-containing group, a carbonyl group-containing group, an acetal group and a phosphonic acid group (-OP(O)OH ₂ ), which further improves the adhesion to other members (antenna patterns, etc.) From a viewpoint, a carbonyl group-containing group is more preferable. The hydroxyl group-containing group is preferably an alcoholic hydroxyl group-containing group, more preferably -CF ₂ CH ₂ OH, -C(CF ₃ ) ₂ OH, and 1,2-diol group (-CH(OH)CH ₂ OH). The carbonyl group-containing group is a group containing a carbonyl group (>C(O)). As the carbonyl group-containing group, a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a urethane group (- OC(O)NH ₂ ), acid anhydride residues (-C(O)OC(O)-), imine residues (-C(O)NHC(O)- etc.) and carbonate groups (-OC( O)O-).

The monomer having a carbonyl group-containing group is more preferably itaconic anhydride, citraconic anhydride, 5-norene-2,3-dicarboxylic anhydride (another name: bicycloheptene dicarboxylic anhydride, also referred to as " NAH”) and maleic anhydride. As a preferable specific example of the F polymer having a polar functional group, there can be mentioned: an F polymer having a TFE unit, an HFP unit, a PAVE unit or an FAE unit, and a unit having a polar functional group.

The F polymer preferably contains 90 to 99 mol% of TFE units, 0.5 to 9.97 mol% of HFP units, PAVE units or FAE units, and 0.01 to 3 mol% of polar units relative to all units constituting the polymer. . As a specific example of the F polymer, the polymer described in International Publication No. 2018/16644 can be cited. When the F polymer has a polar functional group (especially a carbonyl group-containing group), the adhesion of the matrix to other members (antenna patterns, etc.) is further improved.

The composition of the present invention preferably further contains polytetrafluoroethylene (PTFE) in addition to the F polymer. As PTFE other than the F polymer, non-hot-melt PTFE is preferable. The PTFE is preferably low molecular weight PTFE, electron beam treated PTFE, or gamma ray treated PTFE. The mass ratio of PTFE to the F polymer in the composition for forming the matrix by injection molding is preferably 1 or less, more preferably 0.5 or less, and still more preferably 0.25 or less. The above-mentioned ratio is usually 0.1 or more. In this case, a sufficient amount of F polymer is contained relative to PTFE, and it is easy to form a matrix highly filled with F polymer by injection molding. The mass ratio of PTFE to the F polymer in the composition for forming the matrix by compression molding is preferably 1 or more, more preferably 1.5 or more, and still more preferably 2 or more. The upper limit of the above ratio is usually 5. In this case, if a sufficient amount of PTFE is contained relative to the F polymer, it is not only easy to exhibit the physical properties of PTFE with excellent compression moldability, but also to form a matrix with excellent adhesion.

The shape of the F polymer in the composition of the present invention is preferably granular. The shape of the F polymer used in the composition for forming the matrix by injection molding is preferably in the form of pellets, more preferably in the form of blocks of 3 to 5 mm. In this case, it is not easy to impair the injection moldability, and it is easy to form a matrix highly filled with F polymer. The shape of the F polymer used in the composition for forming a matrix by compression molding is preferably a powder. In the case of powder, the volume-based cumulative 10% diameter is preferably 0.1-10 μm, and the volume-based cumulative 50% diameter is preferably 0.3-50 μm. In this case, it is easy to form a matrix with excellent adhesion.

The composition of the present invention preferably further contains a dielectric filler. As the dielectric constant of the dielectric filler at 25°C, it is preferably 1.5 or more, more preferably 6 or more. It is more preferably 18 or more, and particularly preferably 25 or more. The upper limit of the dielectric constant is usually 1000. If a dielectric filler having a dielectric constant in the above range is used, excellent dielectric properties (high dielectric constant and low dielectric loss tangent) can be easily imparted to the substrate. The composition of the present invention preferably contains a dielectric filler with a dielectric constant of 1.5 or more, and is used to form a matrix with a dielectric constant of more than 1.5 and a dielectric loss tangent of 0.05 or less by injection molding or compression molding. Furthermore, the composition of the present invention preferably contains a dielectric filler having a dielectric constant of 6 or more, and is used to form a dielectric filler having a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less by injection molding or compression molding. Matrix. For this dielectric filler, any one of an organic dielectric filler and an inorganic dielectric filler can be used.

As the organic dielectric filler, a cured product containing a curable resin or a filler of a non-curable resin can be exemplified. Examples of curable resins or non-curable resins include epoxy resins, polyimide resins, polyimide resins, acrylic resins, phenol resins, liquid crystalline polyester resins, and polyimide precursors. Olefin resin, modified polyphenylene ether resin, polyfunctional cyanate resin, polyfunctional maleimide-cyanate resin, polyfunctional maleimide resin, vinyl ester resin, urea resin, phthalic acid Diallyl formate resin, melanin resin, guanamine resin, melamine-urea co-condensation resin, styrene resin, polycarbonate resin, polyarylate resin, polyarylene, polyarylene, aromatic polyamide resin, aromatic Group polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamide imide, polyphenylene ether, polybenzoxazole, aromatic polyamide, polyethylene.

As the inorganic dielectric, it preferably contains at least one selected from the group consisting of magnesium, silicon, titanium, zinc, calcium, strontium, zirconium, barium, tin, neodymium, samarium, bismuth, lead, lanthanum, lithium and tantalum A metal oxide of a metal element, and glass. Specific examples of inorganic dielectrics include barium titanate, lead zirconate titanate, lead titanate, zirconium oxide, titanium oxide, strontium bismuth tantalate, strontium bismuth niobate, and bismuth titanate. In addition, as a dielectric filler, it can be a composite filler formed by covering an inorganic dielectric filler with a coating layer of an organic dielectric, or a composite filler in which fine particles of an inorganic dielectric are dispersed in an organic dielectric filler. .

In addition, the dielectric filler may be ceramic (sintered body) of an inorganic dielectric. As a low-dielectric constant ceramic filler with a dielectric constant of 1.5 to 18, examples include powders of sintered bodies of alumina, calcium carbonate, and magnesium silicate. As a high-dielectric constant ceramic filler with a dielectric constant of 100 to 200, examples include powders of sintered bodies of rutile-type titanium oxide and calcium titanate. When ceramic fillers are used, from the viewpoint of suppressing the dielectric anisotropy of the substrate obtained by injection molding, it is preferable to use the powder of low dielectric constant ceramics and the powder of high dielectric constant ceramics in combination. . In this case, the ratio of the latter powder to the ceramic powder is preferably 50% by volume or less. Furthermore, from the viewpoint of the arrangement of the ceramic filler in the obtained matrix, it is preferable that the particle size of the former powder is 1-7 μm, and the particle size of the latter powder is 0.1-2 μm, and the former is more preferable The particle size of the powder is larger than the particle size of the latter powder.

The shape of the dielectric filler can be granular, non-granular (scaly, layered), or fibrous. As the granular dielectric filler, a spherical inorganic oxide filler can be cited. As a specific example, it can be exemplified: a silica filler with an average particle diameter of 1 μm or less that has been surface-treated with a silane coupling agent (Admatechs "Admafine" series manufactured by the company), zinc oxide with an average particle size of 0.1 μm or less ("FINEX" series manufactured by Sakai Chemical Industry Co., Ltd.), average particle size treated with propylene glycol didecanoate and other esters Spherical fused silica with a diameter of 0.5 μm or less and a maximum particle size of less than 1 μm (SFP grade manufactured by Denka, etc.), rutile titanium oxide with an average particle diameter of 0.5 μm or less coated with polyols and inorganic substances ("Tipaque" series manufactured by Ishihara Sangyo Co., Ltd.), rutile-type titanium oxide with an average particle size of 0.1 μm or less that has been surface-treated with alkyl silane ("JMT" series manufactured by Tayca, etc.).

As a specific example of the scaly dielectric filler, a scaly boron nitride filler can be cited. The particle size is preferably 30-100 μm, and the aspect ratio is preferably 10-100. When the fibrous filler is an organic dielectric, the fiber length is preferably 0.5-10 mm, and the fiber diameter is preferably 5-20 μm. Specific examples of the fibrous filler include polybenzoxazole fibers, para-aromatic polyamide fibers, polyarylate fibers, and high molecular weight polyethylene. When the fibrous filler is glass fiber, the fiber length is preferably 10 μm to 5 mm. In addition, the cross-sectional shape may be any of a true circle, a cocoon, an ellipse, a semicircle, a polygon, and a star, and it is preferably a true circle. Furthermore, the aspect ratio (the ratio of the fiber length to the diameter of the cross-section perpendicular to the length direction of the fiber) is preferably 10 to 600.

From the viewpoint of densely and uniformly dispersing the dielectric filler to obtain a matrix with more excellent dielectric properties, it is preferable to use a dielectric filler having a fine structure as the dielectric filler. As a preferable form of the inorganic filler having a fine structure, a spherical filler having an average particle diameter of 2 μm or less, and a fibrous filler having a length of 30 μm or less and a diameter of 2 μm or less can be mentioned. The average particle diameter of the former dielectric filler is preferably 0.05-5 μm, more preferably 0.1-3 μm. In this case, the dielectric filler is likely to be more uniformly dispersed in the molten injection molding material and matrix. In the latter dielectric filler, the length is the fiber length and the diameter is the fiber diameter. The fiber length is preferably 1-30 μm, more preferably 10-20 μm. The fiber diameter is preferably 0.1 to 1 μm, more preferably 0.3 to 0.6 μm.

The ratio by mass of the dielectric filler in the composition to the F polymer is preferably 1/10 to 1/1, more preferably 1/8 to 1/2, and still more preferably 1/6 to 1 3. In this case, the dielectric properties of the substrate can be further improved. The specific ratio of the F polymer in the composition is preferably 10 to 80% by mass, more preferably 25 to 75% by mass, and still more preferably 50 to 70% by mass. In addition, the specific ratio of the dielectric filler in the composition is preferably 20 to 90% by mass, more preferably 25 to 75% by mass, and still more preferably 30 to 50% by mass. In addition, the composition of the present invention may contain a thixotropy imparting agent, a defoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, and a lubricant within a range that does not impair the effects of the present invention. Agent, antistatic agent, brightener, coloring agent, conductive agent, release agent, surface treatment agent, viscosity regulator, flame retardant.

As the use of the substrate made from the composition of the present invention, examples include: antennas, connectors, sockets, relay parts, bobbins, optical pickups, oscillators, printed wiring boards, computer-related parts and other electrical and electronic parts, Semiconductor manufacturing process related parts such as IC (Integrated Circuit) trays, wafer carriers, VTR (video tape recorder), TVs, irons, air conditioners, stereo audio devices, vacuum cleaners, refrigerators, electric cookers, Parts for home appliances such as lighting equipment, parts for lighting equipment such as reflectors, lamp holders, optical discs, laser disks (registered trademarks), parts for audio products such as speakers, ferrules for optical cables, telephones, fax machines, modems, etc. Communication equipment parts, separation claws, heater brackets and other photocopier-related parts, moving impellers, fan gears, gears, bearings, motor parts and housings and other mechanical parts, automotive mechanical parts, engine parts, engine room parts, and electrical parts , Interior parts and other automotive parts, microwave cooking pots, heat-resistant tableware and other cooking utensils, floor plates, wall materials and other heat and sound insulation members, beams, pillars and other supporting members, roofing materials and other construction materials, or civil engineering Components, aircraft, spacecraft, spacecraft parts, nuclear reactors and other radiation facility components, marine facility components, cleaning fixtures, optical machine parts, valves, pipes, nozzles, filters, membranes, medical Machine parts, sensor parts, sanitary spare parts, etc.

Among them, the use of the substrate in the present invention is preferably an antenna (especially a small antenna). As a specific example of the antenna, one may cite: I: an antenna having an antenna pattern and a molded part holding the antenna pattern with a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less (the former antenna); and II: An antenna with an antenna pattern and an integrated layer covering the antenna pattern with a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less (the latter antenna).

The former antenna is preferably manufactured by injecting the composition of the present invention into a mold having a shape corresponding to the forming part to form the forming part. At this time, the antenna can be manufactured by forming the base body and the antenna pattern separately and then assembling (embedded) by external molding, or by injecting the forming material into the forming mold while the antenna pattern is placed in the forming mold. The inner insert molding is manufactured, preferably by the latter insert molding. By insert molding, an antenna with the antenna pattern and the height of the base can be obtained. The antenna has excellent performance and good durability. The heating temperature during injection molding may be set to a temperature higher than the melting point of the F polymer. Specifically, it is preferably 300 to 400°C, more preferably 320 to 380°C. In addition, the antenna may have only one antenna pattern, or may have two or more antenna patterns. The latter antenna is preferably formed by supplying the composition of the present invention into a mold having a shape corresponding to the integration layer and compressing it to form an integration layer, and then assemble (embed) the integration layer and the antenna pattern for external molding. manufacture. As described above, molded articles formed from the composition of the present invention by injection molding or compression molding have excellent dielectric properties and are useful as antennas.

A metal layer can be formed on the surface of the antenna obtained by the present invention (the surface of the substrate on the opposite side to the antenna pattern (hereinafter also referred to as "antenna surface")). The metal layer can be formed by a vapor phase film formation method, or can be formed by a metal plating method. Examples of metals constituting the metal layer include copper, copper alloys, stainless steel, nickel, nickel alloys (including 42 alloys), aluminum, and aluminum alloys. The thickness of the metal layer is preferably 1-50 μm, more preferably 10-25 μm. If it is a metal layer of this thickness, it is easy to suppress the warpage of the antenna as a whole, and it is easy to be used for various purposes. In addition, by the former method, it is easy to form a uniform metal layer with excellent adhesion to the surface of the antenna. Examples of the vapor phase film formation method include a sputtering method, a vacuum vapor deposition method, an ion plating method, and a laser ablation method, and the sputtering method is preferred.

The metal layer may be formed on the side of the polymer layer (the first part) by a vapor-phase film formation method, and the remaining part (the second part) may be formed by electroplating or the like. In particular, it is preferable that the metal layer form the first part by a vapor deposition method (especially a sputtering method) and form the second part by an electrolytic plating method. Specifically, the metal layer is preferably formed by forming the first part in the nm order by sputtering, using the first part as a seed layer, and growing it to the μm order by electroplating. Furthermore, it is preferable that in the first part, the crystal structure of the metal forms a columnar structure.

The ten-point surface roughness of the antenna surface is preferably 0.1 μm or more, more preferably 1 μm or more. The ten-point surface roughness is preferably 20 μm or less. If the surface of the antenna has this surface roughness, it is easy for the metal layer to be firmly laminated on the surface of the antenna. The base system forming the surface of the antenna of the present invention is formed from the composition of the present invention by injection molding or compression molding, so the surface roughness is easily controlled within the required range. In addition, if the composition of the present invention contains a dielectric filler, especially a dielectric filler containing a metal oxide, it is easy for the metal layer to be firmly laminated on the surface of the antenna.

The antenna with a metal layer formed on the surface of the antenna can be further subjected to an etching process to form a transmission circuit on the metal layer, and can also be processed in a soldering process. The metal layer is firmly laminated on the surface of the antenna, and has excellent heat resistance (reflow resistance) and chemical resistance. Therefore, in these treatments, the metal layer and the antenna are not easily peeled off. The peel strength of the metal layer to the surface of the antenna is preferably 3 N/cm or more, more preferably 5 N/cm or more, and still more preferably 10 N/cm or more. Furthermore, the upper limit of peel strength is usually 25 N/cm. Furthermore, peel strength refers to cutting the surface of the antenna on which the metal layer is formed into a rectangular shape (length 100 mm, width 10 mm), and fixing the position 50 mm away from one end of the length direction at a stretching speed of 50 mm/min. The maximum load (N/cm) applied when peeling the surface of the antenna from the metal layer at an angle of 90° relative to the slice from one end of the length direction.

As mentioned above, although the composition of this invention, the manufacturing method of an antenna, and the molded article were demonstrated, this invention is not limited to the structure of the said embodiment. For example, the composition and molded article of the present invention may have other arbitrary configurations in addition to the configurations of the above-mentioned embodiments, or may be replaced with arbitrary configurations that exert the same effect. In addition, the method of manufacturing the antenna of the present invention may have other arbitrary steps added to the configuration of the above-mentioned embodiment, or may be replaced with arbitrary steps that produce the same effect. [Example]

Hereinafter, the present invention will be explained in detail with examples, but the present invention is not limited to these. 1. F polymer F polymer 1: a polymer containing TFE units, PPVE units and NAH units in order of 98.0 mol%, 1.9 mol%, and 0.1 mol%, and has polar functional groups (melting point: 300°C, melt viscosity : 1×10 ³ Pa·s, MFR: 8 g/10 minutes) 2. Dielectric filler Filler 1: Barium titanate fiber (fiber length: 20 μm, fiber diameter 1.5 μm) Filler 2: Glass fiber (cross section Shape: round, fiber length: 3 mm, fiber diameter 11 μm, "CS-3J-256" manufactured by Nitto Textile Co., Ltd.) Filler 3: Boron Nitride filler (scaly, particle size: 35 mm, aspect ratio : 30. "XGP" manufactured by Denka) Filler 4: Polybenzoxazole fiber (fiber length: 1 mm, fiber diameter: 12 μm, "Zylon" manufactured by Toyobo) Filler 5: spherical silica filler (using Surface treatment product obtained by aminosilane coupling agent, average particle size: 0.5 μm, "Admafine SO-C2" manufactured by Admatechs)

3. Composition Composition 1: Using a twin-screw extruder with a cylinder temperature set to 340°C, 66 parts by mass of F polymer 1 and 34 parts by mass of filler 1 were melt-kneaded and passed through a head hole to form filaments, and then After cooling in water, cut into ϕ2×5 mm to obtain pellets Composition 2: Powder obtained by dry blending 66 parts by mass of F polymer 1 powder (average particle size: 20 μm) and 34 parts by mass of filler 1 Composition 3: 70 parts by mass of F polymer 1 powder (average particle size: 50 μm), 10 parts by mass of filler 2 and 20 parts by mass of filler 3 were used, except for this, in the same manner as composition 1 Obtained particles Composition 4: Particles obtained by melt-kneading 90 parts by mass of F polymer 1 powder (average particle size: 50 μm) and 10 parts by mass of filler 4 using a Laboplastomill device Composition 5: particles obtained by melt-kneading 60 parts by mass of F polymer 1 powder (average particle size: 50 μm) and 40 parts by mass of filler 5 using a Laboplastomill device Composition 6: Using 90 parts by mass of F polymer 1 powder (average particle size: 50 μm) and 10 parts by mass of filler 3, except for the particles obtained in the same manner as composition 1

4. Forming examples of the composition Below, the dielectric constant and dielectric loss tangent of the substrate are measured by the cavity resonator perturbation method (measurement frequency: 20 GHz) using a network analyzer as the measuring instrument. 4-1. Injection molding example The composition 3 was put into an injection molding machine, melted at 320°C, and then injection molded into a ϕ3 mm side gate of a metal forming mold to obtain a substrate (dielectric substrate) with a sheet portion. The dielectric constant of the substrate with the metal layer is 3.0, and the dielectric loss tangent is 0.0019. Except for using composition 4 instead of composition 3, the matrix was obtained in the same manner as described above. The dielectric constant is 2.3, the dielectric loss tangent is 0.0016, and the linear expansion coefficient is 79 ppm/°C.

Except for using composition 5 instead of composition 3, the matrix was obtained in the same manner as described above. The dielectric constant is 2.6, the dielectric loss tangent is 0.0010, and the linear expansion coefficient is 134 ppm/°C. Except for using composition 6 instead of composition 3, the matrix was obtained in the same manner as described above. The dielectric constant is 2.3, the dielectric loss tangent is 0.0010, and the linear expansion coefficient is less than 200 ppm/℃.

5. Antenna manufacturing example 5-1. Manufacturing example of antenna by injection molding The composition 1 was put into an injection molding machine, melted at 320°C, and then injection molded into a ϕ3 mm side gate of a metal forming mold embedded with an antenna pattern made of copper foil to obtain an antenna pattern and hold the antenna The pattern base (dielectric base) antenna. The dielectric constant of the substrate is 4.0, and the dielectric loss tangent is 0.03. In addition, in the antenna, the interface between the antenna pattern and the substrate has high adhesion, and it is firmly bonded.

5-2. Manufacturing example of antenna using compression molding Put the composition 2 into a compression molding machine, and perform compression molding under the conditions of a temperature of 380°C and a compression pressure of 17 MPa to form an integrated layer with a shape covering the antenna pattern (a lozenge shape with a thickness of 0.03 cm, dielectric constant: 4.0. Dielectric loss tangent: 0.03). The integration layer is embedded in the antenna pattern to obtain an antenna with the integration layer. 5-3. Examples of metal layer formation Use a vacuum sputtering device to form a nickel-chromium alloy layer (thickness: 20 nm, nickel content 80%, chromium Content 20%) and copper layer (thickness: 100 nm). Furthermore, a copper layer (thickness: 16 μm) was formed on the seed copper layer by copper sulfate plating to form a metal layer on the surface of the antenna. The metal layer is firmly adhered to the surface of the antenna, and has excellent heat resistance (reflow resistance) when a transmission circuit is formed thereon. [Industrial availability]

The composition of the present invention is excellent in injection moldability or compression moldability, and can be well used for the manufacture of various parts (components) represented by electrical and electronic parts, especially antenna substrates. In addition, all of the specification, scope and abstract of Japanese Patent Application No. 2019-157041 filed on August 29, 2019 and Japanese Patent Application No. 2019-187947 filed on October 11, 2019 are cited in this specification. The content is incorporated in the form of the disclosure content of the specification of the present invention.

Claims (15)

A composition containing a hot-melt polymer containing tetrafluoroethylene-based units and used for forming a matrix with a dielectric loss tangent of 0.05 or less by injection molding or compression molding. The composition of claim 1, wherein the above-mentioned substrate is a formed part or an integrated layer of an antenna. The composition of claim 1 or 2, wherein the substrate is a molded part or an integrated layer of an antenna, and the thickness of the molded part or the integrated layer is 1 cm or less. The composition according to any one of claims 1 to 3, which further contains a dielectric filler having a dielectric constant of 1.5 or more, and the dielectric constant of the above-mentioned matrix exceeds 1.5. The composition of claim 4, wherein the above-mentioned dielectric filler is a spherical filler having an average particle diameter of 2 μm or less, or a fibrous filler having a length of 30 μm or less and a diameter of 2 μm or less. The composition of claim 4 or 5, wherein the ratio by mass of the ratio of the above-mentioned dielectric filler in the above-mentioned composition to the ratio of the above-mentioned hot-melt polymer in the above-mentioned composition is 1 /10～1/1. The composition according to any one of claims 1 to 6, wherein the hot melt polymer contains units based on perfluoro(alkyl vinyl ether), hexafluoropropylene or fluoroalkyl ethylene. The composition according to any one of claims 1 to 7, which further contains polytetrafluoroethylene. The composition according to any one of claims 1 to 8, which further contains polytetrafluoroethylene, and the ratio of the polytetrafluoroethylene in the composition is relative to the ratio of the hot melt polymer in the composition The ratio of the ratio by mass is 1 or less, and the composition is used to form the above-mentioned matrix by injection molding. The composition according to any one of claims 1 to 9, which further contains polytetrafluoroethylene, and the ratio of the polytetrafluoroethylene in the composition relative to the ratio of the hot melt polymer in the composition The ratio of the ratio by mass is 1 or more, and the composition is used to form the above-mentioned matrix by compression molding. An antenna manufacturing method, which is a method of manufacturing an antenna having an antenna pattern and a dielectric loss tangent of 0.05 or less and maintaining the above-mentioned antenna pattern forming part, and it is set to any one of claims 1 to 9 When the composition of the item is injected into a mold having a shape corresponding to the molded part to form the molded part, the antenna pattern is already arranged in the molded mold, or the molded part and the antenna are formed after the molded part is formed. Pattern to be assembled. An antenna manufacturing method, which is a method of manufacturing an antenna having an antenna pattern and a dielectric loss tangent of 0.05 or less and covering an integrated layer of the antenna pattern, and it is based on any one of claims 1 to 8 and 10 After the composition of the item is supplied into a mold having a shape corresponding to the integration layer and compressed to form an integration layer, the integration layer and the antenna pattern are assembled. According to the manufacturing method of claim 12, a metal layer is further formed on the surface of the integration layer opposite to the antenna pattern. A molded product formed from the composition according to any one of claims 1 to 10 by injection molding or compression molding. The molded product of claim 14, wherein the molded product is an antenna.