WO2000042108A1 - Composition de resine a base de sulfure de polyarylene - Google Patents
Composition de resine a base de sulfure de polyarylene Download PDFInfo
- Publication number
- WO2000042108A1 WO2000042108A1 PCT/JP2000/000128 JP0000128W WO0042108A1 WO 2000042108 A1 WO2000042108 A1 WO 2000042108A1 JP 0000128 W JP0000128 W JP 0000128W WO 0042108 A1 WO0042108 A1 WO 0042108A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- resin composition
- polyarylene sulfide
- spherical silica
- silica
- Prior art date
Links
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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K7/02—Fibres or whiskers
Definitions
- the present invention relates to a polyarylene sulfide resin composition for molding precision parts. More specifically, the present invention relates to a resin composition for precision component molding suitable for optical communication components such as optical fiber connector ferrules and optical pickup components.
- epoxy-filled silica-filled resin compositions have been used for precision parts such as connector ferrules for optical fibers.
- this epoxy resin composition has a problem peculiar to a thermosetting resin such that a molding cycle is long and recycling is difficult.
- thermoplastic resin polystyrene sulfide (PAS) resin composition has been proposed.
- PAS thermoplastic resin polystyrene sulfide
- JP-A-57-196 '208 discloses a resin composition in which PAS is filled with spherical silica, and is disclosed in JP-A-6-29972.
- a resin composition in which PAS is filled with silica surface-treated with a silane coupling agent has been proposed.
- a re-disclosed patent WO95 / 25770 proposes a resin composition in which PAS is filled with whiskers and spherical silica.
- the present invention has a good balance between physical properties such as dimensional accuracy and mechanical strength, has good moldability, and is suitable for molding precision parts such as a connector fiber for an optical fiber. It is an object of the present invention to provide a resin composition.
- the present inventors have pursued a polylene sulfide resin composition having a good balance of dimensional accuracy, mechanical strength, and moldability, with a particular emphasis on dimensional accuracy.
- a polylene sulfide resin composition having a good balance of dimensional accuracy, mechanical strength, and moldability, with a particular emphasis on dimensional accuracy.
- whiskers whose dimensional accuracy is not sufficient
- the present invention has the following gist.
- the total amount of (B) spherical silica and (C) whiskers is 66 to 80% by weight.
- the total amount of (B) spherical silica and (C) whiskers is 72 to 78% by weight.
- FIG. 1 is a perspective view of a plate-like molded product for measuring roundness.
- the polyarylene sulfide used in the present invention has a repeating unit represented by the structural formula [1 Ar—S—] (where Ar is an arylene group and S is ⁇ ).
- R 1 is an alkyl group having 6 or less carbon atoms, an alkoxy group, a phenyl group, a carboxylic acid or a metal salt thereof, an amino group, a nitro group, and a fluorine, chlorine, bromine, etc.
- a substituent selected from a halogen atom, m is an integer of 0 to 4.
- n represents an average degree of polymerization and is in the range of 1.3 to 30.
- It is a polyarylene sulfide having 0 mol% or more.
- the content of the repeating unit is less than 70 mol%, the original crystalline component, which is a characteristic of the crystalline polymer, is small, and the mechanical strength may be insufficient. You.
- a copolymer may be used in addition to a homopolymer.
- Its copolymerized structural units include methacrylene sulfide unit, orthophenylene sulfide unit, p — P '— diphenylene ketone sulfide unit, p _ p' — Diphenylene sulfone sulfide, p — p '— biphenylene sulfide unit, p — P' — diphenylene methylene sulfide unit, P — P '— diphenylene sulfonyl sulfide And naphthyl sulfide units.
- the molecular structure may be any of a linear structure, a branched structure, and a cross-linked structure, but preferably has a linear structure.
- the polyarylene sulfide of the present invention in addition to a polymer having a substantially linear structure, a branched structure obtained by polymerizing a small amount of a monomer having three or more functional groups as a part of the monomer Alternatively, a polymer having a crosslinked structure can also be used. Further, this may be blended with the above-mentioned polymer having a substantially linear structure and used.
- polyarylene sulfide used in the present invention a polymer obtained by increasing the melt viscosity of a polymer having a substantially linear structure having a relatively low molecular weight by oxidative crosslinking or thermal crosslinking to improve moldability. Can also be used.
- the polyarylene sulfide used in the present invention can be produced by a known method. For example, it can be obtained by subjecting a dihaloaromatic compound and a sulfur source to a polycondensation reaction in an organic polar solvent, washing and drying.
- the polyarylene sulfide used in the present invention has a melt viscosity at a resin temperature of 300 ° C., a shearing speed of 500 sec- 1 and a void viscosity of 150 to 800, preferably 2 or less. It needs to be between 0 and 700 voices, more preferably between 200 and 600 voices. If it is larger than 800 voids, the fluidity during molding will decrease, the dimensional accuracy of the molded product will deteriorate, and granulation will be difficult. In addition, if it is smaller than 150 voices, the mechanical strength is greatly reduced.
- the whiskers constituting the resin composition of the present invention when added, it is preferably 150 to 700 vise, more preferably 150 to 600 vise, and still more preferably. Preferably it is between 200 and 500 voices.
- the spherical silica used in the present invention is a fused silica (amorphous silicon dioxide).
- the average particle size is between 0.3 and 10 ⁇ m , preferably between 0.4 and 8 ⁇ m, more preferably between l and 8 wm. As long as the average particle size is within the above range, two or more types of spherical silicas having different average particle sizes may be used. If the average particle size is smaller than 0.3, the melt viscosity of the resin composition increases, the fluidity during molding decreases, and the dimensional accuracy of the molded product deteriorates. On the other hand, if the average particle size is larger than 10 m, the mechanical strength decreases.
- a surface treatment was carried out with a silane compound such as a coupling agent, preferably amino silane, vinyl silane, phenyl silane, epoxy silane or other silane-based printing agents. Those are preferred. Among them, a vinylsilane coupling agent having excellent moisture resistance is particularly preferable.
- the surface-treated product is expected to have the effect of improving the mechanical strength of the molded product and improving the hygroscopicity, thereby increasing the dimensional stability.
- the whiskers used in the present invention include potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium carbonate whiskers, titanium oxide whiskers, aluminum nawhiskers, silicate whiskers, silicon carbide whiskers, and silicon carbide whiskers. Whisker, aluminum silicate whiskers, magnesium pyroborate whiskers, magnesia whiskers, basic magnesium sulfate whiskers, titanium diboride whiskers, etc. can be used. From the viewpoints of effects and moldability, calcium silicate whiskers, more preferably calcium metasilicate whiskers, can be used.
- the whiskers used in the present invention include those treated with a silane compound such as a coupling agent, preferably an aminosilane, vinylsilane, phenylsilane, epoxysilane or other silane-based coupling agent. preferable.
- the polyylene sulfide resin composition of the present invention comprises (A) 20 to 34% by weight of the above-mentioned poly (arylene sulfide) and (B) 66 to 80% by weight of a spherical silica.
- (C) ⁇ isker 0 to 12% by weight (however, the total amount of (B) spherical silica and (C) ⁇ isker is 66 to 80% by weight), and preferably (A) ) Polyethylene sulfide 22 to 28% by weight, (B) 72 to 78% by weight of spherical silica, (C) 0 to 6% by weight of whisker (However, (B) spherical silica) And (C) the total amount of Iskar is 72 to 78% by weight).
- the above resin composition comprising the components (A), (B) and (C) may further contain a coupling agent, preferably amino silane, vinyl silane, phenyl silane, epoxy silane, and other silane-based resins.
- a silane compound such as a printing agent is used in an amount of preferably from 0.3 to 3.0 parts by weight, per 100 parts by weight of the total of the components (A), (B) and (C). Preferably, 0.5 to 1.5 parts by weight can be added and used.
- the component (B) and the component (C) are not silane-coated in advance, it is significant to add them later.
- the amount of the silane compound is less than 0.3 parts by weight, the mechanical strength of the molded article cannot be expected to be improved, and if it exceeds 3.0 parts by weight, the melt viscosity increases and the moldability decreases. There are cases.
- the polyarylene sulfide resin composition of the present invention may contain, if necessary, other components in addition to the above components, as long as the effects of the present invention are not impaired.
- Other components include, for example, various additives such as antioxidants, weathering agents, lubricants, plasticizers, antistatic agents, coloring agents, polyamides, epoxy resins, silicone resins, silicone oils, and polyester oils.
- Thermoplastic resin and / or thermosetting resin such as olefin, polyether sulphone, poly (vinylene ether), hydrogenated SBS, hydrogenated NBR, silicone rubber, fluorine rubber, etc. List rubbers, pigments, etc. Can be.
- the polyarylene sulfide resin composition of the present invention comprises the above component (A),
- silane compound and various additives are blended with component (B) and component (C), and melted at 280-350 ° C with Henschel mixer, twin screw extruder, etc. It can be obtained by kneading.
- the polyarylene sulfide resin composition of the present invention has extremely high dimensional accuracy and mechanical strength.
- the method of measuring the dimensional accuracy will be described later, but assuming that it is applied to an optical connector ferrule for optical communication, the roundness of the through-hole when a plate-shaped molded product having a through-hole in the cross section is evaluated. Therefore, it is less than 1.8.
- the mechanical strength the bending strength is 12 OMPa or more.
- the polyarylene sulfide resin composition of the present invention has extremely high dimensional accuracy and mechanical strength, it is suitably used for various precision machine parts, and especially in the optical communication field.
- test methods used in the examples are as follows.
- test pieces (12.7 X 12.7 X 3.2 mmt) at a resin temperature of 330 ° C and a mold temperature of 135 ° C ), And Measure according to ASTM.
- a flat plate (80 X 80 X 3.2 mm t) is injection molded, and a 12 X 8 X 3.2 mm t sample piece is flowed from the center of the flat plate into the flow direction (MD) and its perpendicular direction (TD). each cut-out, measuring the TMA method (TMA 1 2 0 C Se I code electronic Industries Ltd.) by the measurement using temperature 0 5 0 linear expansion coefficient ° C (1 0 _ 5 / K) to.
- TMA 1 2 0 C Se I code electronic Industries Ltd. measuring the TMA method (TMA 1 2 0 C Se I code electronic Industries Ltd.) by the measurement using temperature 0 5 0 linear expansion coefficient ° C (1 0 _ 5 / K) to.
- the plate-shaped molded product shown in Fig. 1 (8 X 7 X 2 mm t, through-hole diameter 0.7 mm ⁇ )! : Injection molding at a fat temperature of 330 and a mold temperature of 135. After leaving at room temperature for 24 hours, the roundness (; um) of the through hole is measured with an optical length measuring machine (IDM-30 ) And calculate by image processing.
- IDDM-30 optical length measuring machine
- PPS—1 Polyphenylene sulfide (Linear type, melt viscosity of 100 Voids, manufactured by Idemitsu Petrochemical Co., Ltd.)
- PPS—2 Polyphenylene sulfide (Linear type, melt viscosity 170 Voids, manufactured by Idemitsu Petrochemical Co., Ltd.)
- PPS-3 Polyphenylene sulfide (Linear type, melt viscosity 250 boise, manufactured by Idemitsu Petrochemical Co., Ltd.)
- PPS-4 Polyphenylene sulfide (Toprene, T-1, Semi-Liner type, melt viscosity 290 Boys)
- PPS—5 Polyvinyl sulfide (Linear type, melt viscosity of 450 Boys, manufactured by Idemitsu Petrochemical Co., Ltd.)
- PPS-6 Polyphenylene sulfide (Linear type, melt viscosity of 600 Vise, manufactured by Idemitsu Petrochemical Co., Ltd.)
- PPS-7 Polystyrene sulfide (Linear type, manufactured by Idemitsu Petrochemical Co., Ltd., melt viscosity: 730 Boys)
- PPS—8 Polyphenylene sulfide (Topren, LN—2, linear type, melt viscosity 900 Boys)
- Silica 1 Spherical silica (S0—C2, average particle size 0.5 m, manufactured by Admatechs)
- Silicon 2 Surface-treated spherical silica (manufactured by Admatechs Co., Ltd., S0-C2 vinyl silane (Toray's Dow Corning 'Silicon Co., SZ630) treated product, average (Particle size 0.5 ⁇ m)
- Silicon 3 Surface treated spherical silica (S0-C3 vinyl silane manufactured by Admatechs Co., Ltd. (Toray Dow Corning SZ630) manufactured by Silicon Co., Ltd.), average particle size 1.0; um)
- Silicon 4 Spherical silica force (Tatsumori, TSS-6, average particle diameter 5 m)
- Silicon 5 Surface-treated spherical silica (Tatsumori, TSS-6 vinylsilane) Toray Dow Corning Silicone Co., Ltd.SZ 6300) Treated product, average particle size 5.0 ⁇ m)
- Silicon 6 Surface-treated spherical silica (FB-6D epoxy silane manufactured by Denki Kagaku Kogyo Co., Ltd. (SH6404 manufactured by Toray's “Dawko Oneng” Silicone)) (Average particle size 6.0 ⁇ m)
- Silicon 7 Surface-treated spherical silicon (FB_35 epoxy silane manufactured by Denki Kagaku Kogyo Co., Ltd. (Toray 'Dawko Ningu' SH 640 manufactured by Silicone Co., Ltd.)) Diameter 12.0 ⁇ )
- Silicon 8 Surface treated crushed amorphous silicon (FS-74C epoxy silane manufactured by Denki Kagaku Kogyo Co., Ltd. (S ⁇ 6400 manufactured by Dow Corning Toray Silicone Co., Ltd.)) Diameter 15.0 u rn)
- Silicon 9 Surface-treated spherical silica (manufactured by Admatechs, S0_C1 vinyl silane (Toray's Dow Corning 'SZ630 3 manufactured by Silicon), average particle size 0.2 m)
- Silicon 10 Surface-treated spherical silica (FB-74 vinyl silane manufactured by Denki Kagaku Kogyo Co., Ltd. (Toray 'Dow Corning' Silicon Silicon SZ 6300)) treated product, average particle size 3 1.5 u rn)
- Whiskers 1 Calcium metasilicate Whiskers (NY CO, NY
- Whisker 2 Carrier titanic acid Whisker (Osuka Chemical Co., Ltd.
- Whisker 3 Aluminum borate ⁇ Isker (Alporex YS 2A manufactured by Shikoku Chemicals Co., Ltd.) Fiber diameter 0.5 to 1.0 ⁇ um, L // D 10 to 60, specific gravity 3.0)
- Whisker 4 Zinc Oxide Force (Panatetra fiber diameter 0.1-10.0 ⁇ , L / D 5: 100, specific gravity 5.8, manufactured by Matsushita Amtech) [Examples] 1]
- the above components (a), (b) and (c) are mixed at the compounding ratio shown in Table 1, that is, PPS-5 is 28% by weight as component (a), and After uniformly mixing silica 1 with 72% by weight and a Henschel mixer without the component (c), the resin temperature was adjusted to 300 to 3 with a twin-screw extruder (TEM 35B). The mixture was melt-kneaded at 50 ° C to obtain a pellet. Spiral flow length, mechanical strength, coefficient of linear expansion, dimensional accuracy and overall evaluation were evaluated using the obtained pellets. The evaluation results are shown in Table 1.
- the resin composition of the present invention has good moldability, high dimensional accuracy, small linear expansion coefficient and small anisotropy, and also has excellent mechanical strength. Has excellent physical properties.
- addition of a whisker exceeding a predetermined amount is not suitable because the bending strength is large but the dimensional accuracy (roundness) is reduced.
- the blending of PPS with a specific viscosity and granular silica maintained other properties while maintaining almost the same flexural strength. Is excellent.
- the molded article obtained by using the resin composition of the present invention has high dimensional accuracy, particularly the through-hole shown in FIG. 1, which is an important factor for the bonding of the optical fiber. It is suitable for precision molding of optical parts such as ferrules for optical connectors.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Mechanical Coupling Of Light Guides (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00900368A EP1065246B1 (en) | 1999-01-14 | 2000-01-13 | Polyarylene sulfide resin composition |
DE60012633T DE60012633T2 (de) | 1999-01-14 | 2000-01-13 | Polyarylensulfid-harzzusammensetzung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00782299A JP4209025B2 (ja) | 1999-01-14 | 1999-01-14 | ポリアリーレンスルフィド樹脂組成物 |
JP11/7822 | 1999-01-14 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US62292000A A-371-Of-International | 1999-01-14 | 2000-09-07 | |
US09/986,879 Division US6469091B2 (en) | 1999-01-14 | 2001-11-13 | Polyarylene sulfide resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000042108A1 true WO2000042108A1 (fr) | 2000-07-20 |
Family
ID=11676300
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/000128 WO2000042108A1 (fr) | 1999-01-14 | 2000-01-13 | Composition de resine a base de sulfure de polyarylene |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1065246B1 (ja) |
JP (1) | JP4209025B2 (ja) |
DE (1) | DE60012633T2 (ja) |
WO (1) | WO2000042108A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6534124B2 (en) | 1999-02-22 | 2003-03-18 | Idemitsu Petrochemical Co., Ltd. | Method of producing the plated molded articles by non-electrode plating, and the resin compositions for that use |
CN116601222A (zh) * | 2020-12-25 | 2023-08-15 | 宝理塑料株式会社 | 聚芳硫醚树脂组合物、成型品、及光学套管 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4928660B2 (ja) * | 1999-03-23 | 2012-05-09 | 出光興産株式会社 | 光通信部品用ポリアリーレンスルフィド樹脂組成物 |
US20040116586A1 (en) * | 2001-04-13 | 2004-06-17 | Tomoyoshi Murakami | Polyarylene sulfide resin composition for optical communication part |
JP4919542B2 (ja) * | 2001-05-29 | 2012-04-18 | 出光興産株式会社 | 光学部品用樹脂組成物および光学部品 |
JP6137406B2 (ja) * | 2015-02-25 | 2017-05-31 | 東レ株式会社 | ポリフェニレンスルフィド樹脂組成物、それからなる成形品および半導体パッケージの製造方法 |
WO2021192419A1 (ja) * | 2020-03-25 | 2021-09-30 | 株式会社フジクラ | 光コネクタ部品、光通信部品用樹脂組成物及び光通信部品 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4749598A (en) * | 1987-02-19 | 1988-06-07 | Phillips Petroleum Company | Poly(arylene sulfide) composition and process |
JPH01248546A (ja) * | 1988-03-30 | 1989-10-04 | Toshiba Corp | 電子部品及びその製造方法 |
JP2000001615A (ja) * | 1998-06-15 | 2000-01-07 | Idemitsu Petrochem Co Ltd | ポリアリーレンスルフィド樹脂組成物 |
JP2000007923A (ja) * | 1997-06-10 | 2000-01-11 | Toshiba Corp | 半導体封止用樹脂組成物及び半導体装置とその製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1095918A (ja) * | 1996-09-25 | 1998-04-14 | Idemitsu Petrochem Co Ltd | ポリアリーレンスルフィド樹脂組成物 |
JP3588539B2 (ja) * | 1996-09-30 | 2004-11-10 | 株式会社東芝 | ポリフェニレンサルファイド樹脂組成物、およびこれを用いた樹脂封止型半導体装置 |
-
1999
- 1999-01-14 JP JP00782299A patent/JP4209025B2/ja not_active Expired - Lifetime
-
2000
- 2000-01-13 WO PCT/JP2000/000128 patent/WO2000042108A1/ja active IP Right Grant
- 2000-01-13 DE DE60012633T patent/DE60012633T2/de not_active Expired - Lifetime
- 2000-01-13 EP EP00900368A patent/EP1065246B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4749598A (en) * | 1987-02-19 | 1988-06-07 | Phillips Petroleum Company | Poly(arylene sulfide) composition and process |
JPH01248546A (ja) * | 1988-03-30 | 1989-10-04 | Toshiba Corp | 電子部品及びその製造方法 |
JP2000007923A (ja) * | 1997-06-10 | 2000-01-11 | Toshiba Corp | 半導体封止用樹脂組成物及び半導体装置とその製造方法 |
JP2000001615A (ja) * | 1998-06-15 | 2000-01-07 | Idemitsu Petrochem Co Ltd | ポリアリーレンスルフィド樹脂組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1065246A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6534124B2 (en) | 1999-02-22 | 2003-03-18 | Idemitsu Petrochemical Co., Ltd. | Method of producing the plated molded articles by non-electrode plating, and the resin compositions for that use |
CN116601222A (zh) * | 2020-12-25 | 2023-08-15 | 宝理塑料株式会社 | 聚芳硫醚树脂组合物、成型品、及光学套管 |
CN116601222B (zh) * | 2020-12-25 | 2023-12-01 | 宝理塑料株式会社 | 聚芳硫醚树脂组合物、成型品、及光学套管 |
Also Published As
Publication number | Publication date |
---|---|
JP2000204252A (ja) | 2000-07-25 |
EP1065246A4 (en) | 2003-04-16 |
DE60012633T2 (de) | 2004-12-16 |
EP1065246A1 (en) | 2001-01-03 |
EP1065246B1 (en) | 2004-08-04 |
DE60012633D1 (de) | 2004-09-09 |
JP4209025B2 (ja) | 2009-01-14 |
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