CN114341257A - Composition, method for producing antenna, and molded article - Google Patents
Composition, method for producing antenna, and molded article Download PDFInfo
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- CN114341257A CN114341257A CN202080060409.6A CN202080060409A CN114341257A CN 114341257 A CN114341257 A CN 114341257A CN 202080060409 A CN202080060409 A CN 202080060409A CN 114341257 A CN114341257 A CN 114341257A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P11/00—Apparatus or processes specially adapted for manufacturing waveguides or resonators, lines, or other devices of the waveguide type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3456—Antennas, e.g. radomes
Abstract
The invention provides a composition capable of forming a substrate with excellent dielectric property and adhesiveness by injection molding or compression molding, a method for manufacturing a high-performance antenna with a substrate formed by the composition, and a molded article formed by the molded article. The composition of the present invention comprises a hot-melt polymer containing a tetrafluoroethylene-based unit for forming a matrix having a dielectric loss tangent of 0.05 or less by injection molding or compression molding. The method for manufacturing an antenna of the present invention is a method for manufacturing an antenna using the above composition, the antenna including a molding portion formed by injection molding and holding an antenna pattern, or an antenna including an integration layer formed by compression molding and covering an antenna pattern.
Description
Technical Field
The present invention relates to a composition containing a predetermined hot-melt polymer, and a method for producing an antenna and a molded article using the same.
Background
With the miniaturization of mobile communication devices such as mobile phones and smartphones, antennas (chip antennas) mounted thereon have also been miniaturized.
Such a small antenna generally includes an antenna pattern made of a conductor and a base (dielectric base) made of a dielectric such as a resin for holding the antenna pattern (see patent document 1).
In patent document 1, a small antenna in which an antenna pattern and a base are integrated is manufactured by forming a base by injection molding of a dielectric material using the antenna pattern as an insert member.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2013/137404
Disclosure of Invention
Technical problem to be solved by the invention
From the viewpoint of further improvement in performance of an antenna (improvement in antenna gain), a dielectric having excellent dielectric characteristics is required. However, according to the studies of the present inventors, the dielectric (dielectric substrate) of patent document 1 has disadvantages. In patent document 1, the antenna pattern and the dielectric substrate are integrated, but the adhesiveness therebetween is not sufficient.
The present inventors have earnestly studied in order to improve these points. As a result, they have found that a composition suitable for injection molding or compression molding, which is excellent in electrical characteristics and adhesion, can be prepared by including a predetermined hot-melt polymer.
An object of the present invention is to provide a composition capable of forming a substrate having excellent adhesiveness and a low dielectric loss tangent by injection molding or compression molding, a method for producing a high-performance antenna provided with a substrate formed from the composition, and a molded article formed from the molded article.
Technical scheme for solving technical problem
The present invention has the following technical contents.
< 1 > a composition comprising a hot-melt polymer containing a tetrafluoroethylene-based unit for forming a matrix having a dielectric loss tangent of 0.05 or less by injection molding or compression molding.
< 2 > the composition as stated in above < 1 >, wherein said substrate is a shaped part or an integrated layer of an antenna.
< 3 > the composition as defined above < 1 > or < 2 >, wherein the substrate is a shaped part or an integrated layer of the antenna, and the thickness of the shaped part or the integrated layer is 1cm or less.
< 4 > the composition as defined in any one of the above < 1 > to < 3 >, further comprising a dielectric filler having a dielectric constant of 1.5 or more, the matrix having a dielectric constant of more than 1.5.
< 5 > the composition as described in < 4 > above, 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 as stated above < 4 > or < 5 >, wherein the mass ratio of the dielectric filler to the hot-melt polymer in the composition is 1/10 to 1/1.
< 7 > the composition as defined in any one of above < 1 > -6 >, wherein said hot-melt polymer contains units based on perfluoro (alkyl vinyl ether), hexafluoropropylene or fluoroalkyl vinyl.
< 8 > the composition as defined in any one of the above < 1 > to < 7 >, further comprising polytetrafluoroethylene.
< 9 > the composition as defined in any one of above < 1 > -to < 8 >, further comprising polytetrafluoroethylene, wherein a mass ratio of a proportion of the polytetrafluoroethylene to a proportion of the hot-melt polymer in the composition is 1 or less, for forming the substrate by injection molding.
< 10 > the composition as defined in any one of the above < 1 > -to < 9 >, further comprising polytetrafluoroethylene, wherein a mass ratio of a proportion of the polytetrafluoroethylene to a proportion of the hot-melt polymer in the composition is 1 or more, and the composition is used for forming the matrix by compression molding.
< 11 > a method for manufacturing an antenna comprising an antenna pattern and a molded part holding the antenna pattern and having a dielectric tangent of 0.05 or less, wherein the antenna pattern is placed in a mold or the molded part and the antenna pattern are assembled after the molded part is formed, when the molded part is formed by injecting the composition of any one of < 1 > -to < 10 > into the mold having a shape corresponding to the molded part.
< 12 > a method for manufacturing an antenna comprising an antenna pattern and an integration layer covering the antenna pattern and having a dielectric tangent of 0.05 or less, wherein the integration layer is formed by supplying and compressing the composition described in any one of the above < 1 > -to < 8 > and < 10 > into a mold having a shape corresponding to the integration layer, and then the integration layer and the antenna pattern are assembled.
< 13 > the manufacturing method as stated above < 12 >, further forming a metal layer on a face of the integration layer on a side opposite to the antenna pattern.
< 14 > a molded article formed by injection molding or compression molding of the composition as defined in any one of the above < 1 > to < 10 >.
< 15 > the molded article of < 14 > above, wherein the molded article is an antenna.
Effects of the invention
According to the present invention, a composition for injection molding or compression molding suitable for molding a substrate having excellent adhesiveness and a low dielectric loss tangent, and a high-performance antenna can be obtained.
Detailed Description
The following terms have the following meanings.
The "hot-melt polymer" is a polymer exhibiting melt fluidity, and is a polymer having a melt flow rate of 0.1 to 1000g/10 min at a temperature higher by at least 20 ℃ than the melting temperature of the polymer under a load of 49N.
"Melt Flow Rate (MFR)" means JIS K7210: 1999(ISO 1133: 1997) the melt flow rate of the polymer.
"melting temperature (melting point) of a polymer" means a temperature corresponding to the maximum value of the melting peak of a polymer measured by a Differential Scanning Calorimetry (DSC) method.
"melt viscosity of the composition" means a viscosity in accordance with JIS K7199: 1999(ISO 11443: 1995) determined shear rate at 1000/sec.
The "average particle diameter" is obtained by dispersing the target particles (powder, filler, etc.) in water and analyzing the dispersion by a laser diffraction/scattering particle size distribution measuring device (LA-920 measuring device manufactured by horiba corporation) (horiba corporation). That is, the particle size distribution of the particles was measured by a laser diffraction scattering method, and a cumulative curve was obtained with the total volume of the particle group as 100%, and the point on the cumulative curve where the cumulative volume reached 50% was defined as the average particle diameter (D50). Further, a cumulative curve was obtained with the total volume of the particle clusters taken as 100%, and the point on the cumulative curve at which the cumulative volume reached 10% was D10.
"ten-point average roughness (Rzjis)" is JIS B0601: 2013, attached JA.
The "dielectric constant" in the present invention is also referred to as a specific dielectric constant, and means a relative dielectric constant with respect to a dielectric constant in a vacuum.
The "unit" in the polymer may be a radical formed directly from a monomer by polymerization, or a radical obtained by treating a polymer obtained by polymerization by a predetermined method to convert a part of the structure. The unit based on the monomer a contained in the polymer is also referred to simply as "monomer a unit".
The composition of the present invention comprises a hot-melt polymer (hereinafter also referred to as "F polymer") containing a Tetrafluoroethylene (TFE) -based unit for forming a matrix (dielectric matrix) having a dielectric loss tangent of 0.05 or less by injection molding or compression molding.
The F polymer of the present invention exhibits good heat fusibility, and the melt viscosity thereof falls within a predetermined range, so that it can be easily subjected to high-density filling molding in injection molding or compression molding. As a result, it is considered that bubbles (air layer) are less likely to be generated in the formed matrix, and the deterioration of the dielectric properties due to the presence of the bubbles is suppressed. In addition, when the composition contains a filler such as a dielectric filler, the filler is easily uniformly and stably dispersed. As a result, it is presumed that a substrate exhibiting a low dielectric loss tangent can be formed.
The dielectric loss tangent of the substrate of the present invention is 0.05 or less. The dielectric loss tangent of the matrix is preferably 0.04 or less, more preferably 0.03 or less. The lower limit is usually 0.001.
The dielectric constant of the matrix of the present invention is preferably greater than 1.5, and more preferably 2 or more. More preferably 3 or more, and particularly preferably 4 or more. Its upper limit is typically 10. The substrate of the present invention preferably has a dielectric constant of more than 1.5 and a dielectric loss tangent of 0.05 or less, and more preferably has a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less. The dielectric constant and the dielectric loss tangent in the present specification are values measured at 20GHz, respectively.
The substrate of the invention can be particularly suitably used as a forming part or an integration layer of an antenna to improve the performance of the antenna. Such an antenna tends to exhibit high performance (antenna gain).
Here, the shaped portion of the antenna is preferably a member (holding member) that holds an antenna pattern made of a conductor. The integration layer of the antenna is a layer provided so as to cover the antenna pattern in order to suppress attenuation of a current flowing through the antenna pattern.
The thickness of the antenna molding portion and the thickness of the conforming layer are preferably 1cm or less, more preferably 0.5mm or less, and still more preferably 0.01mm or less, respectively. The composition of the present invention is excellent in moldability, and can form a molded part or a conforming layer having such a small thickness as to be excellent in dielectric properties.
The F polymer of the present invention is a hot-melt polymer containing TFE-based units (TFE units). The F polymer may be a homopolymer of TFE or a copolymer of TFE and another monomer (comonomer) copolymerizable with TFE. That is, if exhibiting hot melt properties, the F polymer may also be Polytetrafluoroethylene (PTFE).
The F polymer preferably has a TFE unit in an amount of 90 to 100 mol% based on the total units constituting the polymer.
The fluorine content of the F polymer is preferably 70 to 76 mass%, more preferably 72 to 76 mass%. When the F polymer having a fluorine content within the above range is used, improvement of the dielectric characteristics of the matrix (in particular, reduction of the dielectric loss tangent) is expected.
Examples of the F polymer include a copolymer of TFE and ethylene (ETFE), a copolymer of TFE and propylene, a copolymer of TFE and perfluoro (alkyl vinyl ether) (PAVE) (PFA), a copolymer of TFE and Hexafluoropropylene (HFP) (FEP), a copolymer of TFE and Fluorinated Alkyl Ethylene (FAE), and a copolymer of TFE and Chlorotrifluoroethylene (CTFE). These copolymers may also contain units based on other comonomers.
The F polymer preferably contains TFE units, and PAVE units or HFP units or FAE units.
As PAVE, CF is mentioned2＝CFOCF3、CF2＝CFOCF2CF3、CF2＝CFOCF2CF2CF3(PPVE)、CF2＝CFOCF2CF2CF2CF3、CF2＝CFO(CF2)8F。
As FAE, CH may be mentioned2＝CH(CF2)2F、CH2＝CH(CF2)3F、CH2＝CH(CF2)4F、CH2＝CF(CF2)3H、CH2＝CF(CF2)4H。
The melt viscosity of the F polymer is preferably 1X 10 at 380 ℃2～1×106Pa · s, more preferably 1X 10 at 300 ℃2～1×106Pa · s. In this case, the molding of the molding base body at a lower temperature is easy.
The melting temperature of the F polymer is preferably 260-320 ℃, and more preferably 285-320 ℃. In this case, the dielectric filler can be favorably prevented from being deteriorated or deteriorated.
The MFR of the F polymer is preferably 20g/10 min or less, more preferably 10g/10 min or less. In this case, a complex-shaped substrate can be more easily formed.
The melt viscosity of the composition is preferably 50 to 1000 pas, more preferably 75 to 750 pas at a shear rate of 1000/sec. In this case, too, a substrate having a complicated shape can be more easily formed.
Suitable specific examples of the F polymer include modified PTFE, FEP, and PFA. The modified PTFE refers to a copolymer of TFE and a very small amount of comonomer (HFP, PAVE, FAE, etc.), and is PTFE exhibiting thermal fusion properties.
As the F polymer, an F polymer having a polar functional group is preferable. The polar functional group may be included in the monomer unit in the F polymer, or may be included in the terminal group of the main chain of the polymer. The latter polymer may be a polymer having a polar functional group as an end group derived from a polymerization initiator, a chain transfer agent, or the like. Further, as the F polymer, there can be mentioned an F polymer having a polar functional group obtained by plasma treatment or ionizing radiation treatment.
The F polymer having a polar functional group is preferably an F polymer having a polar functional group-containing monomer unit (hereinafter also referred to as "polar unit"). The monomer having a polar functional group which becomes a polar unit by polymerization is hereinafter also referred to as "polar monomer".
As the polar functional group, a hydroxyl-containing group, a carbonyl-containing group, an acetal group and a phosphoryl group (-OP (O) OH) are preferable2) The carbonyl group-containing group is more preferable from the viewpoint of further improving the adhesiveness to other members (such as an antenna pattern).
As the hydroxyl group-containing group, preferred is an alcoholic hydroxyl group, more preferred is-CF2CH2OH、-C(CF3)2OH and 1, 2-diol group (-CH (OH) CH2OH)。
The carbonyl group-containing group is a group containing a carbonyl group (> C (O)), and the carbonyl group-containing group is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH)2) Anhydride (-), anhydride (-C (O) OC (O) -), imide (-C (O) NHC (O) -, etc.) and carbonate (-OC (O) O-).
As the monomer having a carbonyl group, further preferred are itaconic anhydride, citraconic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride (alias: nadic anhydride; hereinafter also referred to as "NAH") and maleic anhydride.
Preferred specific examples of the F polymer having a polar functional group include F polymers containing TFE units, HFP units, PAVE units, FAE units, and units 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, FAE units, and 0.01 to 3 mol% of polar units, respectively, based on all units constituting the polymer. Specific examples of the F polymer include polymers described in International publication No. 2018/16644.
When the F polymer has a polar functional group (particularly, a carbonyl group-containing group), the adhesiveness of the substrate to other members (such as an antenna pattern) is further improved.
The composition of the present invention preferably further comprises Polytetrafluoroethylene (PTFE) in addition to the F polymer. As PTFE other than F polymer, non-heat-fusible PTFE is preferable. The PTFE is preferably low molecular weight PTFE, electron-ray-treated PTFE, or gamma-ray-treated PTFE.
The mass ratio of PTFE to the F polymer in the composition for forming a 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 ratio is usually 0.1 or more. In this case, the F polymer is contained in a sufficient amount relative to PTFE, and a matrix highly filled with the F polymer is easily formed by injection molding.
The mass ratio of PTFE to the F polymer in the composition for forming a 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, the PTFE is contained in a sufficient amount relative to the F polymer, and not only physical properties of PTFE excellent in compression moldability are easily exhibited, but also a substrate excellent in adhesion and adhesiveness is easily formed.
The shape of the F polymer of the composition of the invention is preferably granular.
The shape of the F polymer in the composition for forming a substrate by injection molding is preferably a granular shape, and more preferably a block shape of 3 to 5 mm. In this case, the injection moldability is not easily impaired, and a highly filled matrix of the F polymer is easily formed.
The shape of the F polymer of the composition for forming a matrix by compression molding is preferably a powder. When the powder is used, the volume-based cumulative 10% diameter is preferably 0.1 to 10 μm, and the volume-based cumulative 50% diameter is preferably 0.3 to 50 μm. In this case, a substrate having excellent adhesion and adhesiveness can be easily formed.
The composition of the present invention preferably further comprises a dielectric filler.
The dielectric constant at 25 ℃ of the dielectric filler is preferably 1.5 or more, more preferably 6 or more. More preferably 18 or more, and particularly preferably 25 or more. The upper limit of the dielectric constant is usually 1000. When the dielectric filler having a dielectric constant within the above range is used, excellent dielectric characteristics (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 having a dielectric constant of 1.5 or more for forming a matrix having a dielectric constant of more than 1.5 and a dielectric loss tangent of 0.05 or less by injection molding or compression molding. The composition of the present invention more preferably contains a dielectric filler having a dielectric constant of 6 or more for forming a matrix having a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less by injection molding or compression molding.
Such a dielectric filler may use either an organic dielectric filler or an inorganic dielectric filler.
Examples of the organic dielectric filler include fillers composed of a cured product of a curable resin or a non-curable resin. Examples of the curable resin or the non-curable resin include epoxy resins, polyimide resins, polyamic acids which are precursors of polyimides, acrylic resins, phenol resins, liquid crystalline polyester resins, polyolefin resins, modified polyphenylene ether resins, polyfunctional cyanate ester resins, polyfunctional maleimide-cyanate ester resins, polyfunctional maleimide resins, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea copolycondensation resins, styrene resins, polycarbonate resins, polyarylate resins, polysulfones, polyarylsulfones, aromatic polyamide resins, aromatic polyetheramides, polyphenylene sulfides, polyaryl ether ketones, polyamideimides, polyphenylene ethers, polybenzoxazoles, aromatic polyamides, and polyethylenes.
As the inorganic dielectric, a metal oxide containing at least 1 metal element selected from magnesium, silicon, titanium, zinc, calcium, strontium, zirconium, barium, tin, neodymium, samarium, bismuth, lead, lanthanum, lithium, and tantalum, and glass are preferable.
Specific examples of the inorganic dielectric include barium titanate, lead zirconate titanate, lead titanate, zirconium oxide, titanium oxide, strontium bismuth tantalate, strontium bismuth niobate, and bismuth titanate.
The dielectric filler may be a composite filler in which an inorganic dielectric filler is coated with an organic dielectric coating layer, or a composite filler in which inorganic dielectric fine particles are dispersed in an organic dielectric filler.
The dielectric filler may be an inorganic dielectric ceramic (sintered body).
The low dielectric constant ceramic filler having a dielectric constant of 1.5 to 18 includes powders of sintered bodies of alumina, calcium carbonate and forsterite.
The high dielectric constant ceramic filler having a dielectric constant of 100 to 200 includes a sintered powder of rutile titanium oxide or calcium titanate.
When the ceramic filler is used, it is preferable to use a powder of a low dielectric constant ceramic together with a powder of a high dielectric constant ceramic from the viewpoint of suppressing dielectric constant anisotropy of the obtained matrix by injection molding. In this case, the ratio of the latter powder in the ceramic powder is preferably 50% by volume or less. Further, from the viewpoint of arrangement of the ceramic filler in the obtained matrix, it is preferable that the particle diameter of the former powder is 1 to 7 μm and the particle diameter of the latter powder is 0.1 to 2 μm, and it is preferable that the particle diameter of the former powder is larger than the particle diameter of the latter powder.
The shape of the dielectric filler may be particulate, non-particulate (scaly, lamellar), or fibrous.
Examples of the particulate dielectric filler include a spherical inorganic oxide filler, and specific examples thereof include a silica filler having an average particle diameter of 1 μm or less (such as "admafin (アドマファイン)" series manufactured by yadama corporation (アドマテックス)) surface-treated with a silane coupling agent, a zinc oxide having an average particle diameter of 0.1 μm or less (such as "FINEX" series manufactured by sakakai chemical industry corporation (sakai ), a spherical fused silica having an average particle diameter of 0.5 μm or less and a maximum particle diameter of less than 1 μm (such as "SFP grade" manufactured by electrical corporation) (デンカ)), a rutile titanium oxide having an average particle diameter of 0.5 μm or less (such as "tipaeque (タイペーク)" series manufactured by stone origin ) coated with a polyhydric alcohol and an inorganic substance, and the like, Rutile titanium oxide having an average particle diameter of 0.1 μm or less (JMT series, manufactured by electrochemical Co., Ltd.) having been surface-treated with an alkylsilane.
Specific examples of the scaly dielectric filler include scaly boron nitride fillers. The particle size is preferably 30 to 100 μm, and the aspect ratio is preferably 10 to 100.
When the fibrous filler is an organic dielectric, the fibrous filler preferably has a fiber length of 0.5 to 10mm and a fiber diameter of 5 to 20 μm.
Specific examples of such fibrous fillers include polybenzazole fibers, para-aramid fibers, polyacrylate fibers, and high molecular weight polyethylene.
When the fibrous filler is a glass fiber, the fiber length is preferably 10 μm to 5 mm. The cross-sectional shape may be any of a perfect circle, an eyebrow shape, an ellipse, a semicircle, a polygon, and a star shape, and a perfect circle is preferable. Further, the aspect ratio (the ratio of the fiber length to the diameter of a cross section perpendicular to the longitudinal direction of the fiber) is preferably 10 to 600.
From the viewpoint of obtaining a matrix having more excellent dielectric characteristics in which the dielectric filler is densely and uniformly dispersed, it is preferable to use a dielectric filler having a fine structure as the dielectric filler.
Suitable forms of the inorganic filler having such a fine structure include spherical fillers having an average particle diameter of 2 μm or less and fibrous fillers having a length of 30 μm or less and a diameter of 2 μm or less.
The former dielectric filler preferably has an average particle diameter of 0.05 to 5 μm, more preferably 0.1 to 3 μm. In this case, the dielectric filler is more easily uniformly dispersed in the injection molding material and the matrix in a molten state.
The latter dielectric filler has a length of the fiber length and a diameter of the fiber diameter. The fiber length is preferably 1 to 30 μm, more preferably 10 to 20 μm. The fiber diameter is preferably 0.1 to 1 μm, more preferably 0.3 to 0.6. mu.m.
The mass ratio of the dielectric filler to the F polymer in the composition 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 characteristics of the substrate are more easily improved.
The specific proportion of the F polymer in the composition is preferably 10 to 80% by mass, more preferably 25 to 75% by mass, and further preferably 50 to 70% by mass.
The specific proportion 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.
Further, the composition of the present invention may further contain a thixotropy-imparting agent, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weather-resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a mold release agent, a surface treatment agent, a viscosity modifier, a flame retardant, within a range not to impair the effects of the present invention.
Examples of uses of the substrate produced from the composition of the present invention include: electric and electronic parts such as antenna, connector, socket, relay part, bobbin, optical pickup, oscillator, printed wiring board, computer-related part, etc., parts related to semiconductor manufacturing process such as IC tray, wafer carrier, etc., parts for household electric products such as VTR, television, electric iron, air conditioner, audio, dust collector, refrigerator, electric rice cooker, lighting equipment, etc., parts for lighting equipment such as lamp reflector, lamp holder, etc., parts for audio products such as compact disc, laser disc (registered trademark), speaker, etc., parts for communication equipment such as ferrule for optical cable, telephone, facsimile, modem, etc., parts related to copying machine such as separation claw, heater holder, etc., mechanical parts such as impeller, fan gear, bearing, motor part, and housing, structural parts for automobile, engine part, inner part cover, part, etc., parts for automobile, Automotive parts such as interior parts, cooking devices such as microwave cooking pots and heat-resistant tableware, heat and sound insulating members such as bed materials and wall materials, supporting members such as beams and columns, building materials such as roof materials, civil engineering and construction members, radiation facility members such as airplanes, spacecrafts, space equipment, nuclear reactors, marine facility members, cleaning jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts, sensor parts, sanitary equipment, and the like.
Among them, an antenna (particularly, a small antenna) is suitable for use as the substrate of the present invention. Specific examples of such an antenna include I: an antenna (former antenna) provided with an antenna pattern and a molded part holding the antenna pattern and having a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less, and II: an antenna (the latter antenna) comprising an antenna pattern and an integrated layer covering the antenna pattern and having a dielectric constant of 2 or more and a dielectric loss tangent of 0.05 or less.
The former antenna is preferably manufactured by injection molding the composition of the present invention into a mold having a shape corresponding to the molded portion to form the molded portion.
In this case, the antenna may be manufactured by external molding (アウター molding) in which the substrate and the antenna pattern are separately produced and then assembled (embedded), or may be manufactured by insert molding (インサート molding) in which a material for molding is injection-molded in a molding die with the antenna pattern arranged in the molding die, and preferably by the latter insert molding.
By the insert molding, an antenna in which the antenna pattern and the base are highly bonded can be obtained. The antenna has excellent performance and good durability.
The heating temperature during injection molding may be set to a temperature equal to or higher than the melting point of the F polymer, and specifically, is preferably 300 to 400 ℃, and more preferably 320 to 380 ℃.
Further, the antenna may have only 1 antenna pattern, or may have 2 or more antenna patterns.
The latter antenna is preferably manufactured by external forming, that is, after the composition of the present invention is supplied into a mold having a shape corresponding to the integration layer and is compressed to form the integration layer, the integration layer and the antenna pattern are assembled (embedded).
As described above, a molded article formed by injection molding or compression molding of the composition of the present invention has excellent dielectric properties and can be used as an antenna.
A metal layer may be further formed on the surface of the antenna obtained according to 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 may be formed by a vapor deposition method or a metal plating method.
Examples of the metal constituting the metal layer include copper, copper alloy, stainless steel, nickel alloy (including 42 alloy), aluminum, and aluminum alloy.
The thickness of the metal layer is preferably 1 to 50 μm, more preferably 10 to 25 μm. The metal layer having such a thickness can be easily used for various purposes while suppressing the warpage of the entire antenna.
In addition, by the former method, a metal layer which is uniform and excellent in adhesion to the antenna surface is easily formed. The vapor-phase film formation method includes a sputtering method, a vacuum deposition method, an ion plating method, and a laser ablation method, and the sputtering method is preferable.
The portion (1 st portion) of the metal layer on the polymer layer side may be formed by a vapor deposition method, and the remaining portion (2 nd portion) may be formed by plating or the like.
In particular, the metal layer is preferably formed by a vapor deposition method (particularly, a sputtering method) for the 1 st portion and by an electroplating method for the 2 nd portion.
Specifically, the metal layer is preferably formed by sputtering to form a 1 st portion on the order of nm, and then grown by electroplating to the order of μm with the 1 st portion as a seed layer.
In addition, in part 1, the crystalline structure of the metal preferably 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 such a surface roughness, the laminated metal layer can be easily firmly bonded to the surface of the antenna. Since the substrate forming the surface of the antenna in the present invention is formed from the composition of the present invention by injection molding or compression molding, the surface roughness thereof can be easily controlled within such a desired range.
Further, when the composition of the present invention contains a dielectric filler, particularly a dielectric filler containing a metal oxide, it is easy to strongly adhere the laminated metal layer to the surface of the antenna.
The antenna having the metal layer formed on the surface thereof may be further subjected to etching treatment to form a transmission circuit on the metal layer, or may be subjected to soldering treatment for processing. Since the metal layer on the surface of the antenna is firmly adhered and laminated and is excellent in heat resistance (solder reflow) and chemical resistance, the metal layer and the antenna are not easily peeled off in these treatments.
The peel strength of the metal layer from the antenna surface is preferably 3N/cm or more, more preferably 5N/cm or more, and still more preferably 10N/cm or more. In addition, the upper limit of the peel strength is usually 25N/cm.
The peel strength is the maximum load (N/cm) applied when the antenna surface on which the metal layer is formed is cut into a rectangular shape (100 mm long and 10mm wide), the position 50mm away from one end in the longitudinal direction is fixed, and the antenna surface and the metal layer are peeled from each other at 90 ° from the cut piece from the other end in the longitudinal direction at a drawing speed of 50 mm/min.
The composition, the method for producing an antenna, and the molded article of the present invention have been described above, but the present invention is not limited to the configuration of the above embodiment.
For example, the composition and the molded article of the present invention may be configured in any other way, or may be configured in any way to exhibit the same function, in addition to the configuration of the above embodiment.
In the antenna manufacturing method according to the present invention, in the configuration of the above embodiment, any other steps may be added, or any other steps that perform the same function may be substituted.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
Polymers of formula (I) F
F, polymer 1: polymer having polar functional group comprising TFE unit, PPVE unit and NAH unit in this order in 98.0 mol%, 1.9 mol% and 0.1 mol% (melting point: 300 ℃ C., melt viscosity: 1X 10)3Pa · s, MFR: 8g/10 min)
2. Dielectric filler
Packing 1: barium titanate fiber (fiber length: 20 μm, fiber diameter 1.5 μm)
And (3) filler 2: glass fiber (circular cross section, fiber length: 3mm, fiber diameter: 11 μm, "CS-3J-256" manufactured by Ridong textile Co., Ltd. (Ridoodun Co., Ltd.))
And (3) filler: boron nitride Filler (scaly, particle diameter: 35mm, aspect ratio: 30, "XGP" available from electrochemical Co., Ltd.)
And (4) filler: polybenzazole fiber (fiber length: 1mm, fiber diameter: 12 μm, "ZYLON (ザイロン)" made by Toyo Boseki Kabushiki Kaisha (Bao imperial Co., Ltd.))
And (5) filler: spherical silica Filler (surface-treated product surface-treated with aminosilane coupling agent, average particle diameter: 0.5 μm, "admafin SO-C2" manufactured by Yadmama Co.)
3. Composition comprising a metal oxide and a metal oxide
Composition 1: melt-kneading 66 parts by mass of the F polymer 1 and 34 parts by mass of the filler 1 in a twin-screw extruder with the barrel temperature set at 340 ℃, shaping the mixture into filaments through a head hole, further cooling the filaments in water, and cutting the filaments into pieces
Left and right of the obtained granules
Composition 2: a powder obtained by dry blending 66 parts by mass of a powder (average particle diameter: 20 μm) of F polymer 1 and 34 parts by mass of filler 1
Composition 3: pellets obtained in the same manner as in composition 1 except that 70 parts by mass of the powder of F polymer 1 (average particle diameter: 50 μm) and 10 parts by mass of filler 2 and 20 parts by mass of filler 3 were used
Composition 4: a powder obtained by melt-kneading 90 parts by mass of a powder (average particle diameter: 50 μm) of F polymer 1 and 10 parts by mass of a filler 4 with a LABO PLASTOMILL apparatus
Composition 5: 60 parts by mass of a powder of F polymer 1 (average particle diameter: 50 μm) and 40 parts by mass of filler 5 were melt-kneaded by a LABO PLASTOMILL apparatus to obtain a powder
Composition 6: pellets obtained in the same manner as in composition 1 except that 90 parts by mass of the powder of F polymer 1 (average particle diameter: 50 μm) and 10 parts by mass of filler 3 were used
4. Examples of the formation of the composition
The dielectric constant and the dielectric loss tangent of the substrate were measured by a resonance cavity perturbation method (measurement frequency: 20GHz) using a network analyzer as a measuring instrument.
4-1 injection Molding example
The composition 3 was charged into an injection molding machine, melted at 320 ℃ and then introduced into a metal mold
The side door was injection molded to obtain a substrate (dielectric substrate) having a thin sheet portion. The dielectric constant of the substrate having the metal layer was 3.0, and the dielectric loss tangent was 0.0019.
A substrate was obtained in the same manner as described above except that composition 4 was used instead of composition 3. The dielectric constant was 2.3, the dielectric loss tangent was 0.0016, and the linear expansion coefficient was 79 ppm/deg.C.
A substrate was obtained in the same manner as described above except that composition 5 was used instead of composition 3. The dielectric constant was 2.6, the dielectric loss tangent was 0.0010, and the linear expansion coefficient was 134 ppm/deg.C.
A substrate was obtained in the same manner as described above except that composition 6 was used instead of composition 3. The dielectric constant is 2.3, the dielectric loss tangent is 0.0010, and the linear expansion coefficient is 200 ppm/DEG C or less.
5. Example of manufacturing an antenna
5-1 production example of antenna by injection Molding
The composition 1 was charged into an injection molding machine, melted at 320 ℃ and then introduced into a metal mold having an antenna pattern made of copper foil inserted therein
The side door was injection-molded to obtain an antenna including an antenna pattern and a base (dielectric base) for holding the antenna pattern.
The dielectric constant of the substrate was 4.0 and the dielectric loss tangent was 0.03. The antenna pattern of the antenna has high interface adhesion with the substrate, and is firmly bonded.
5-2 production example of antenna by compression Molding
The composition 2 was charged into a compression molding machine, and compression-molded at a temperature of 380 ℃ and a compression pressure of 17MPa to form an integrated layer (tablet shape having a thickness of 0.03cm, dielectric constant: 4.0, dielectric loss tangent: 0.03) having a shape covering the antenna pattern. Embedding the integration layer into an antenna pattern to obtain an antenna with the integration layer.
5-3 examples of Forming Metal layer
On the surface of the base (the surface opposite to the antenna pattern) of the antenna obtained in the above-mentioned "5-1", a nichrome layer (thickness: 20nm, nickel content 80%, chromium content 20%) and a copper layer (thickness: 100nm) were formed in this order by using a vacuum sputtering apparatus. Further, a copper layer (thickness: 16 μm) was formed on the seed copper layer by copper sulfate electroplating, thereby forming a metal layer on the antenna surface. The metal layer is firmly adhered to the surface of the antenna, and is excellent in heat resistance (solder reflow) when a transmission circuit is formed thereon.
Possibility of industrial utilization
The composition of the present invention is excellent in injection moldability and compression moldability, and can be suitably used for the production of various parts (members) including electric and electronic parts, particularly, substrates for antennas.
In addition, the entire contents of the specification, claims and abstract of japanese patent application No. 2019-157041 filed on 29/8/2019 and japanese patent application No. 2019-187947 filed on 11/10/2019 are cited herein as disclosures of the description of the present invention.
Claims (15)
1. A composition comprising a hot-melt polymer containing a tetrafluoroethylene-based unit for forming a matrix having a dielectric loss tangent of 0.05 or less by injection molding or compression molding.
2. The composition of claim 1, wherein the substrate is a formed part or an integral layer of an antenna.
3. The composition of claim 1 or 2, wherein the substrate is a shaped part or an integral layer of the antenna, the shaped part or the integral layer having a thickness of 1cm or less.
4. The composition of any of claims 1-3, further comprising a dielectric filler having a dielectric constant of 1.5 or greater, the matrix having a dielectric constant greater than 1.5.
5. The composition according to claim 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 according to claim 4 or 5, wherein the mass ratio of the proportion of the dielectric filler to the proportion of the hot-melt polymer in the composition is 1/10 to 1/1.
7. The composition according to any one of claims 1 to 6, wherein the hot-melt polymer comprises units based on perfluoro (alkyl vinyl ether), hexafluoropropylene or fluoroalkyl ethylene.
8. The composition of any one of claims 1 to 7, further comprising polytetrafluoroethylene.
9. The composition according to any one of claims 1 to 8, further comprising polytetrafluoroethylene, wherein the mass ratio of the proportion of the polytetrafluoroethylene to the proportion of the hot-melt polymer in the composition is 1 or less, and the composition is used for forming the matrix by injection molding.
10. The composition according to any one of claims 1 to 9, further comprising polytetrafluoroethylene, the mass ratio of the proportion of the polytetrafluoroethylene in the composition relative to the proportion of the hot-melt polymer being 1 or more, for forming the matrix by compression molding.
11. A method for manufacturing an antenna comprising an antenna pattern and a molded part holding the antenna pattern and having a dielectric tangent of 0.05 or less, wherein the antenna pattern is placed in a mold when the molded part is formed by injecting the composition according to any one of claims 1 to 9 into the mold having a shape corresponding to the molded part, or the molded part and the antenna pattern are assembled after the molded part is formed.
12. A method for manufacturing an antenna comprising an antenna pattern and an integration layer covering the antenna pattern and having a dielectric tangent of 0.05 or less, wherein the integration layer is formed by supplying the composition according to any one of claims 1 to 8 and 10 into a mold having a shape corresponding to the integration layer and compressing the composition, and then the integration layer and the antenna pattern are assembled.
13. The manufacturing method according to claim 12, further forming a metal layer on a face of the integration layer on a side opposite to the antenna pattern.
14. A molded article formed by injection molding or compression molding of the composition according to any one of claims 1 to 10.
15. The molded article of claim 14, wherein the molded article is an antenna.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019157041 | 2019-08-29 | ||
| JP2019-157041 | 2019-08-29 | ||
| JP2019-187947 | 2019-10-11 | ||
| JP2019187947 | 2019-10-11 | ||
| PCT/JP2020/031495 WO2021039596A1 (en) | 2019-08-29 | 2020-08-20 | Composition, method for producing antenna, and molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114341257A true CN114341257A (en) | 2022-04-12 |
Family
ID=74685470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080060409.6A Pending CN114341257A (en) | 2019-08-29 | 2020-08-20 | Composition, method for producing antenna, and molded article |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7468535B2 (en) |
| KR (1) | KR20220051304A (en) |
| CN (1) | CN114341257A (en) |
| TW (1) | TW202126461A (en) |
| WO (1) | WO2021039596A1 (en) |
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| KR20130137404A (en) | 2012-06-07 | 2013-12-17 | 삼성디스플레이 주식회사 | Liquid crsytal composition, method for forming optical isotropic phase of liqui cyrstal and liquid crystal display device |
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2020
- 2020-08-20 KR KR1020217037185A patent/KR20220051304A/en unknown
- 2020-08-20 WO PCT/JP2020/031495 patent/WO2021039596A1/en active Application Filing
- 2020-08-20 CN CN202080060409.6A patent/CN114341257A/en active Pending
- 2020-08-20 JP JP2021542819A patent/JP7468535B2/en active Active
- 2020-08-24 TW TW109128772A patent/TW202126461A/en unknown
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| JPS63234606A (en) * | 1987-03-23 | 1988-09-29 | Fujitsu Ten Ltd | Manufacture of body integrating type antenna |
| JPH11228824A (en) * | 1998-02-10 | 1999-08-24 | Cosmo Sogo Kenkyusho Kk | Resin composition, molded product and production of the resin composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2021039596A1 (en) | 2021-03-04 |
| JP7468535B2 (en) | 2024-04-16 |
| JPWO2021039596A1 (en) | 2021-03-04 |
| TW202126461A (en) | 2021-07-16 |
| KR20220051304A (en) | 2022-04-26 |
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