WO2007069770A1 - ポリアリーレンサルファイド樹脂組成物 - Google Patents
ポリアリーレンサルファイド樹脂組成物 Download PDFInfo
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- WO2007069770A1 WO2007069770A1 PCT/JP2006/325309 JP2006325309W WO2007069770A1 WO 2007069770 A1 WO2007069770 A1 WO 2007069770A1 JP 2006325309 W JP2006325309 W JP 2006325309W WO 2007069770 A1 WO2007069770 A1 WO 2007069770A1
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- resin composition
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- 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
Definitions
- the present invention relates to a rearylene sulfide resin composition that exhibits a high dielectric constant and a low dielectric loss tangent, is excellent in moldability, and has improved metal corrosivity.
- Polyphenylene sulfide hereinafter may be abbreviated as PPS
- PAS Polyarylene sulfide
- resin has high heat resistance, mechanical properties, chemical resistance, and dimensional stability. Because of its properties and flame retardancy, it is widely used in electrical and electronic equipment component materials.
- PPS Polyphenylene sulfide
- PAS Polyarylene sulfide
- resin has high heat resistance, mechanical properties, chemical resistance, and dimensional stability. Because of its properties and flame retardancy, it is widely used in electrical and electronic equipment component materials.
- remarkable technological developments have been made in the information and communication fields, such as mobile phones, wireless LANs, and ITS technologies such as GPS, VI CS and ETC.
- GPS GPS, VI CS and ETC
- Thermoplastic resins such as PAS resin are widely used for injection molding applications, and due to their easy moldability, it is easy to create parts with relatively complex shapes.
- Metals, thermosetting resins, and ceramics that have been used as a product have the advantage that the degree of design freedom that has been limited becomes much higher. Also, it can be said that it is more advantageous than conventional materials in terms of environment such as recyclability.
- 3-28 1557 has a relatively high dielectric loss tangent, and , JP-A-8-4 1 2 4 7, JP-A 2 0 0 5_ 9 3 0 9 6 and JP-A 2 0 0 5-9 4 0 6 8
- the product has a high melt viscosity and is not necessarily suitable for injection molding.
- no countermeasure has been taken against the generation of corrosive gas resulting from the decomposition of the PAS resin when the resin composition is melt-kneaded. , — .. ⁇ Disclosure of Invention
- An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a PAS resin composition which exhibits a high dielectric constant and a low dielectric loss tangent, is excellent in moldability, and has improved metal corrosiveness.
- the present inventors have formulated a specific alkaline earth metal titanate salt and an alkaline earth metal hydroxide or oxide into the PAS resin.
- the present inventors have found that a high dielectric constant and a low dielectric loss tangent, excellent moldability, and improved metal corrosion properties have been completed.
- the present invention is.
- the resin is mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit.
- the arylene group includes, for example, p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, ⁇ , ⁇ '—diphenylene sulfonate group, ⁇ , ⁇ ' —biphenyl group. Rene group, ⁇ , ⁇ '—diphenylene ether group, ⁇ , ⁇ ' -diphenylene carbonyl group, naphthalene group, etc. can be used.
- a polymer using the same repeating unit that is, the processability of the composition in addition to the homopolymer.
- a copolymer containing different types of repeating units may be preferable.
- a homopolymer having a ⁇ -phenylenanolide group as a repeating unit and having a ⁇ -phenylene group as the arylene group is particularly preferably used.
- the copolymer two or more different combinations of arylene sulfide groups composed of the above-mentioned arylene groups can be used. Among them, a combination including a ⁇ _phenylene sulfide group and an m_phenylene sulfide group. Is particularly preferably used.
- a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used.
- a partially branched or crosslinked structure is formed using a small amount of a monomer such as a polyhaloaromatic compound having three or more haguchigen substituents.
- the polymer can be used, and a relatively low molecular weight linear structure polymer is heated at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking, thereby improving molding processability.
- Polymers or mixtures thereof can also be used.
- the PAS resin of component (A) is mainly composed of the linear PAS resin (viscosity at 310 ° C ′ shear rate OOsecf 1 of 10 to 300 Pa ⁇ s), and a part thereof (1 to 30% by weight, preferably 2 to 25% by weight) force relatively high viscosity (3 00 ⁇ 3000Pa 's, preferably 500 ⁇ 2000Pa ⁇ A mixed system with a branched or cross-linked PAS resin of s) may be used.
- the PAS resin used in the present invention is preferably one obtained by purifying by-product impurities and the like by performing acid washing, hot water washing, organic solvent washing (or a combination thereof) after polymerization.
- (B) used in the present invention alkaline earth metal titanate as component relative dielectric constant at 1 MH Z is 50 or more, a dielectric loss tangent 0.05 or less, and is extracted with hot water
- the amount of metal ions contained is less than 500 ppm.
- a high dielectric constant metal titanate having a relative dielectric constant of 50 or more at 1 MHz a molded article having a high dielectric constant can be obtained efficiently.
- the relative dielectric constant is less than 50, the dielectric constant does not increase so much and it is not practical.
- the dielectric loss tangent at 1 MHz must be 0.05 or less, and if it is greater than 0.05, the dielectric loss increases, leading to performance degradation as an electronic component.
- Examples of such an alkaline earth metal titanate having a relative permittivity at 1 MHz of 50 or more and a dielectric loss tangent of 0.05 or less include calcium titanate and barium titanate.
- the alkaline earth metal titanate used in the present invention has a metal ion content of less than 500 ⁇ 1 , preferably less than lOOppm , in the alkaline earth metal titanate extracted with hot water. It is necessary to be.
- Such an alkaline titanic acid metal salt is obtained by synthesizing an alkaline earth metal titanate synthesized by a conventionally known method such as a flux method, hot water or hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. It can be obtained by treating with an inorganic acid. If the amount of metal ions extracted with hot water exceeds 500 ppm, the melt viscosity of the resin composition increases and the moldability deteriorates.
- the alkaline earth titanate metal salt as a component has a shape such as a fiber, a plate, or a particle. Depending on the purpose of using this composition, the shape of the alkaline earth titanate metal salt By selecting, it becomes possible to further improve the characteristics.
- a fibrous aluminum titanate earth metal salt from the standpoint of further improving the mechanical strength and thermal properties, it is preferable to use a fibrous aluminum titanate earth metal salt.
- the alkaline earth metal titanate fibrous used in the present invention, the fiber diameter 3 mu [pi less and a fiber length of 5 ⁇ ⁇ above, aspect ratio is 3 or more, Preferably it is 10 or more.
- the plate shape includes shapes such as a flake shape, a flake shape, and a mica shape.
- the plate-like alkaline earth metal titanate used in the present invention usually has an average major axis of about 0.5 to 100 ⁇ , preferably about 1 to 20 ⁇ m.
- the average minor axis is about 0.2 to 100 ⁇ m, preferably about 0.5 to 20 ⁇ m , and the average thickness is about 0:01 to 10 ⁇ , preferably about 0.05 to 5 / zm.
- the ratio (average particle diameter / average thickness) of the average particle diameter measured by the laser diffraction particle size distribution meter and the average thickness measured by the scanning electron microscope is about 3 to 100, preferably 5 to About 50.
- the particulate aluminum titanate alkaline earth metal salt has a median diameter of ⁇ or more, preferably 20 m or more, and more preferably 20 to 500 zm or more. .
- the median diameter can be measured with a laser diffraction particle size distribution analyzer.
- the median diameter is the cumulative diameter at 50% by volume.
- the blended amount of the (B) alkaline earth metal titanate is ⁇ 400 parts by weight with respect to 100 parts by weight of the PAS resin.
- the blending amount is less than 10 parts by weight, the effect of improving the dielectric constant is small.
- the blending amount is more than 400 parts by weight, the workability deteriorates.
- a high dielectric constant, a low dielectric loss tangent, and an excellent compound can be obtained by further blending at least one compound selected from hydroxides and oxides of alkaline earth metal as component (C).
- a PAS resin composition with improved metal corrosion can be obtained while maintaining the moldability.
- the metal of such a compound include calcium, tungsten, barium, and magnesium, preferably calcium.
- the compounding amount of one or more compounds selected from hydroxides and oxides of alkaline earth metal is 0.01 to 15 parts by weight with respect to 100 parts by weight of the PAS resin. If the blending amount is less than 0.01 parts by weight, the effect of improving metal corrosion is small, and if it exceeds 15 parts by weight, the melt viscosity of the resin composition becomes high and the moldability deteriorates.
- the component (D) in order to reduce the temperature change dependency of the relative dielectric constant of the composition, Further, as the component (D), it is preferable to mix the temperature-dependent adjusting material for the relative dielectric constant (D) described below.
- (D) As a component of the temperature-dependent adjusting material of the relative dielectric constant, for example, A 1 2 0 3 , BN, B a O, B e O, B i 2 0 3 , C a 0, C e 0 2 , C r 2 0, F e 2 0, L a 2 0 3 , N a 2 0, N b 2 0 5 , Nd 2 0 3 , P r 6 O u , S i C, S i 2 N 4 , S i ⁇ 2, S r O, T i 0 2, Y 2 0 3, Z nO, mention may be made of Z r O 2, etc., usually, one configured know of two or more of these are used, oxide Used by mixing raw materials such as products, carbonates, hydroxides, etc., and sintering and calcination (a method of firing once at a temperature slightly below the actual sintering temperature and not completely solidified) .
- oxide Used by mixing raw materials such as products,
- the above compounds are used in combination, or two or more kinds of the above compounds are contained, and these compounds occupy 80% by weight (for example, Otsuka Chemical Co., Ltd .; trade name) BTTE Ba-Nd-Ti-Bi-La system) can be used.
- the particle diameter of the component (D) is preferably 10 m or less, more preferably 2 m or less, from the viewpoint of dispersibility in the resin. '.
- the content of the component (D) is blended in a proportion of 1 to 400 parts by weight with respect to 100 parts by weight of the resin, and more preferably in a proportion of 100 to 300 parts by weight.
- the content is small, the temperature change characteristic of the relative dielectric constant becomes large, and when the content is too large, the moldability becomes poor and becomes brittle.
- component (E) it is preferable to blend the following component (E) for the purpose of improving mechanical strength and thermal characteristics while maintaining the low dielectric loss tangent of the composition.
- the aluminum borate fibers are preferably those represented by the formula 9 ⁇ 1 2 0 3 ⁇ 2 ⁇ 2 0 3 or the formula 2A1 2 0 3 ⁇ B 2 0 3 , and more specifically as the magnesium borate fibers, 2Mg0 'represented by the B 2 0 3, as the boric acid nickel fibers, and more specifically can be exemplified those represented by the formula 3NiO * B 2 0 3.
- Fibrous materials include wollastonite represented by the formula CaO ⁇ Si0 2 , zonotlite represented by 6CaO ⁇ 6Si0 2 ⁇ H 2 0, zinc silicate represented by 2Zn0 ⁇ Si0 2 , 3A 1 2 0 mullite DOO represented by 3 ⁇ 2Si0 2, sepiolite preparative represented by 2Mg0 ⁇ 3Si0 2 ⁇ 3. 5H 2 0, 3Mg0. '2Si0 chrysotile, etc. represented by 2 ⁇ 2H 2 0 and the like.
- Warasutonai preparative represented by the formula CaO 'Si0 2 as, Zono Toraito like represented by 6CaO ⁇ 6Si0 2 ⁇ H 2 0 .
- the component has a weight ratio of 6 or more and is 60% by weight. /. Above, preferably 80 weight. / 0 and contain more, and the fiber diameter 5 m following ingredients 8 0 wt% or more, and it is preferably to use a long fibrous substance finely that contain 9 5% by weight or more.
- the content of the component (E) may be one or more of the above compounds, and is blended at a ratio of 1 to 150 parts by weight with respect to 100 parts by weight of the resin, at a ratio of 10 to 100 parts by weight. More preferably. When the content is small, the mechanical strength and thermal characteristics are lowered, and when the content is too large, the moldability is inferior and brittle.
- fibrous fillers examples include glass fibers, asbestos fibers, bonbon fibers, silica fibers, silica alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, potassium titanate fibers, stainless steel, aluminum, titanium, copper,
- inorganic fibrous materials such as metallic fibers such as brass.
- Particularly typical fibrous fillers are glass fibers or carbon fibers. High melting point organic fiber materials such as polyamide, fluororesin, and acrylic resin can also be used.
- granular fillers include carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate ', kaolin, talc, clay, diatomaceous earth, and wollastonite.
- Metal oxides such as iron oxide, titanium oxide, zinc oxide, and alumina, carbonate carbonate, metal carbonates such as magnesium carbonate, '' metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, Examples include silicon nitride, boron nitride, and various metal powders.
- the plate-like filler include My strength, glass flakes, and various metal foils.
- inorganic fillers can be used alone or in combination of two or more. 'When using these fillers, it is desirable to use sizing agents or surface treatment agents if necessary. Examples of this are functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after surface treatment or convergence treatment in advance, or they may be added at the same time as material preparation.
- the amount of inorganic filler used is not particularly limited, but is generally 10 to 400 parts by weight per 100 parts by weight of component (A) PAS resin. If it is too small, the mechanical strength is slightly inferior. If it is too large, the molding work becomes difficult and there is also a problem in mechanical strength.
- a silane compound can be blended.
- the silane compounds include various types such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, mercapto silane, etc., for example, vinyltrichlorosilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysila. , ⁇ -aminopropyltriethoxysilane, ⁇ -mercaptopropyl trimethoxysilane and the like, but are not limited thereto.
- thermoplastic resin any thermoplastic resin that is stable at a high temperature may be used.
- aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate and diols or oxycarboxylic acids, polyamides, polycarbonates, ABS, polyphenylene oxide, polyalkylacrylates, polysulfone Polyether sulfone, polyether imide, polyether ketone, fluorine resin, polyrelate, etc.
- thermoplastic resins may be used in combination of two or more.
- the resin composition of the present invention includes known substances generally added to thermoplastic resins, that is, stabilizers such as antioxidants, colorants such as flame retardants, dyes and pigments, lubricants, and crystallization accelerators. Crystal nucleating agents and the like can be added as appropriate according to required performance.
- the resin composition of the present invention can be prepared by facilities and methods generally used for preparing a synthetic resin composition.
- necessary components can be mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form pellets for molding. It is also a preferable method to melt-extrude the resin component and add and mix an inorganic component such as glass fiber in the middle.
- the material pellets thus obtained can be molded using generally known thermoplastic resin molding methods such as injection molding, extrusion molding, vacuum molding, compression molding, etc. The most preferred is injection molding. is there. Example
- Preparation method A titanic acid-strength fiber was synthesized by a flux method, and then calcium carbonate was deposited using a titanate fiber that had been dealt with a de-altering force as a raw material, and then heat-treated to synthesize a calcium titanate fiber. Thereafter, the mixture was put into a 90 ° C pure eternity, stirred for 2 hours, and dried at 110 ° C for 2 hours after filtration.
- the amount of metal ions that can be extracted from the obtained calcium titanate with hot water is determined by dispersing calcium titanate in pure water at 80 ° C at a slurry concentration of 1% and stirring for 2 hours.
- the amount of metal ions contained in calcium titanate was determined by quantification by the absorption method.
- Filler dielectric constant Using Toyo Seiki's Labo Plus mill, blending filler into polyethylene and mixing the filler, kneading, pulverizing the resulting sample, molding a test piece for dielectric property measurement, impedance Using an analyzer, measure the relative permittivity (r) and dielectric loss tangent (tanS) at 1MHz by the capacitance method using Agilent Technologies' dielectric test fixture, and use the obtained data in relation to the filling rate of the filler. The values at which the ratio of this boiler is 100 vol% were taken as the relative dielectric constant ( ⁇ r) and dielectric loss tangent (tan ⁇ ) of the filler, respectively.
- Preparation method Lithium potassium titanate plate-like particles were synthesized by a calcination method, and the obtained plate-like particles and a ruthenium raw material were mixed and subjected to heat treatment to synthesize calcium titanate plate-like particles. Thereafter, the mixture was poured into pure water at 90 ° C, stirred for 2 hours, and then filtered and dried at 110 ° C for 2 hours.
- the amount of metal ions contained in hot water extraction was determined by the same method as (B-1).
- Preparation method A scale-like lithium potassium titanate was synthesized by a melting method, and the obtained scale-like material was pulverized to obtain particulate lithium potassium titanate. The obtained particulate matter and calcium raw material were mixed and subjected to heat treatment to synthesize particulate calcium titanate. Thereafter, the mixture was poured into pure water at 90 ° C, stirred for 2 hours, filtered and dried at 110 ° C for 2 hours.
- the amount of metal ions contained in hot water extraction was determined in the same manner as (B-1).
- Preparation method Titanium oxide and calcium raw materials were mixed in a pulverizing mixer such as a ball mill, and then heat-treated to synthesize calcium titanate particles. Thereafter, the mixture was poured into pure water at 90 ° C, stirred for 2 hours, filtered and dried at 110 ° C for 2 hours. The amount of metal ions contained in hot water extraction was determined by the same method as (B-1).
- Preparation method The constituent raw materials were mixed in a pulverizing mixer such as a ball mill, and the uniformly mixed raw materials were heat-treated to obtain a sintered body.
- the obtained sintered body was pulverized with a pulverizer and adjusted to the target particle size.
- melt viscosity at a barrel temperature of 310 ° C and a shear rate of lOOOsec- 1 was measured using a ⁇ ⁇ ⁇ ⁇ 20 ⁇ L / flat die as the carrier.
- Measurement was performed according to IS0-527-1 using an autograph manufactured by Shimadzu Corporation.
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2006800473795A CN101331191B (zh) | 2005-12-16 | 2006-12-13 | 聚亚芳基硫醚树脂组合物 |
EP06834979A EP1970412A4 (en) | 2005-12-16 | 2006-12-13 | polyarylene sulfide resin |
JP2007550265A JP5342144B2 (ja) | 2005-12-16 | 2006-12-13 | ポリアリーレンサルファイド樹脂組成物 |
KR1020087014462A KR101287305B1 (ko) | 2005-12-16 | 2006-12-13 | 폴리아릴렌 설파이드 수지 조성물 |
US12/085,912 US7705079B2 (en) | 2005-12-16 | 2006-12-13 | Polyarylene sulfide resin composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005362684 | 2005-12-16 | ||
JP2005-362684 | 2005-12-16 |
Publications (1)
Publication Number | Publication Date |
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WO2007069770A1 true WO2007069770A1 (ja) | 2007-06-21 |
Family
ID=38163072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/325309 WO2007069770A1 (ja) | 2005-12-16 | 2006-12-13 | ポリアリーレンサルファイド樹脂組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US7705079B2 (ja) |
EP (1) | EP1970412A4 (ja) |
JP (1) | JP5342144B2 (ja) |
KR (1) | KR101287305B1 (ja) |
CN (1) | CN101331191B (ja) |
WO (1) | WO2007069770A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011116870A (ja) * | 2009-12-04 | 2011-06-16 | Mitsubishi Engineering Plastics Corp | 誘電体用樹脂組成物及び誘電体アンテナ部品 |
CN113754295A (zh) * | 2021-07-31 | 2021-12-07 | 广东金发科技有限公司 | 一种低介电改性玻璃纤维及其制备方法和应用 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5374994B2 (ja) * | 2008-09-25 | 2013-12-25 | ソニー株式会社 | ミリ波誘電体内伝送装置 |
CN103436016B (zh) * | 2013-09-20 | 2016-01-20 | 云南银峰新材料有限公司 | 一种钛酸钙改性聚苯硫醚介电复合材料的制备方法 |
US20150166731A1 (en) * | 2013-12-16 | 2015-06-18 | Chevron Phillips Chemical Company Lp | Reinforced Poly(Arylene Sulfide) Polymer Compositions |
CN111925651A (zh) * | 2020-08-07 | 2020-11-13 | 安特普工程塑料(苏州)有限公司 | 高频电场下具有高介电常数的改性聚苯硫醚材料、制备方法及其应用 |
CN112080071A (zh) * | 2020-09-07 | 2020-12-15 | 湖南捷立康科技有限公司 | 一种具有低介电性能的聚丙烯透波母料、制备方法及用其制成的聚丙烯制品 |
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2006
- 2006-12-13 KR KR1020087014462A patent/KR101287305B1/ko not_active IP Right Cessation
- 2006-12-13 US US12/085,912 patent/US7705079B2/en not_active Expired - Fee Related
- 2006-12-13 CN CN2006800473795A patent/CN101331191B/zh not_active Expired - Fee Related
- 2006-12-13 JP JP2007550265A patent/JP5342144B2/ja active Active
- 2006-12-13 EP EP06834979A patent/EP1970412A4/en not_active Withdrawn
- 2006-12-13 WO PCT/JP2006/325309 patent/WO2007069770A1/ja active Application Filing
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JP2011116870A (ja) * | 2009-12-04 | 2011-06-16 | Mitsubishi Engineering Plastics Corp | 誘電体用樹脂組成物及び誘電体アンテナ部品 |
CN113754295A (zh) * | 2021-07-31 | 2021-12-07 | 广东金发科技有限公司 | 一种低介电改性玻璃纤维及其制备方法和应用 |
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Publication number | Publication date |
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JP5342144B2 (ja) | 2013-11-13 |
CN101331191A (zh) | 2008-12-24 |
US7705079B2 (en) | 2010-04-27 |
KR20080079653A (ko) | 2008-09-01 |
JPWO2007069770A1 (ja) | 2009-05-28 |
KR101287305B1 (ko) | 2013-07-17 |
EP1970412A4 (en) | 2009-09-16 |
CN101331191B (zh) | 2011-03-30 |
US20090253843A1 (en) | 2009-10-08 |
EP1970412A1 (en) | 2008-09-17 |
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