WO2005049732A1 - Polyphenylene sulfide thermoplastic resin composition - Google Patents
Polyphenylene sulfide thermoplastic resin composition Download PDFInfo
- Publication number
- WO2005049732A1 WO2005049732A1 PCT/KR2004/002609 KR2004002609W WO2005049732A1 WO 2005049732 A1 WO2005049732 A1 WO 2005049732A1 KR 2004002609 W KR2004002609 W KR 2004002609W WO 2005049732 A1 WO2005049732 A1 WO 2005049732A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyphenylene sulfide
- weight
- resin composition
- thermoplastic resin
- parts
- Prior art date
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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
Definitions
- the present invention relates to a polyphenylene sulfide thermoplastic resin composition with good impact strength and flame retardancy. More particularly, the present invention relates to a polyphenylene sulfide thermoplastic resin composition having good flame retardancy and mechanical strength, which comprises a polyphenylene sulfide resin, an olefinic graft copolymer and a fluorinated polyolefin resin.
- thermoplastic resins have been applied to the materials for components of electrical or electronic appliances, automobile devices or chemical instruments.
- Al or Zn die casting metals had been conventionally used.
- these metals are now replaced with thermoplastic resins, especially reinforced plastics.
- These thermoplastic resins especially applied to the materials for electrical or electronic parts require high heat resistance and chemical resistance.
- Polyphenylene sulfide is one of the resins satisfying this demand. Polyphenylene sulfide has good heat resistance, dimensional stability, chemical resistance, flame retardancy and processability, so it can be suitably employed to the above uses.
- polyphenylene sulfide has a fundamental disadvantage in that it has poor impact resistance in comparison with other engineering plastics.
- Japanese Patent Laid-Open No. 58-154757 discloses a method of adding an epoxy group-containing olefin copolymer to polyphenylene sulfide resin.
- Japanese Patent Laid-Open No. 1-306467 discloses a polyphenylene sulfide composition prepared by incorporating a polyphenylene sulfide, an epoxy group-containing olefin copolymer and an elastomer free from epoxy and acid anhydride groups.
- Japanese Patent Laid-Open No.62-172056 discloses a polyphenylene sulfide composition obtained by blending a polyphenylene sulfide and an olefin copolymer graft copolymerized with unsaturated carboxylic acid, its anhydride or derivative thereof.
- these compositions thus produced are yet insufficient for some uses requiring mechanical strength and impact resistance and therefore are required to be further improved in many cases.
- the present inventors have developed a polyphenylene sulfide resin composition comprising thermoplastic polyphenylene sulfide resin, olefininc graft copolymer, epoxy compound and inorganic filler, which has improved mechanical strength and izod impact strength, while maintaining processability and dimensional stability.
- a polyphenylene sulfide resin composition comprising thermoplastic polyphenylene sulfide resin, olefininc graft copolymer, epoxy compound and inorganic filler, which has improved mechanical strength and izod impact strength, while maintaining processability and dimensional stability.
- the impact resistance, especially izod impact strength of the above composition has been improved to some extent, the flame resistance of the polyphenylene sulfide is deteriorated.
- the present inventors have developed a polyphenylene sulfide thermoplastic resin composition having good impact resistance and flame retardancy, while maintaining processability, dimensional stability, mechanical strength by adding an olefinic graft copolymer and a fluorinated polyolefin resin to a thermoplastic polyphenylene sulfide.
- the polyphenylene sulfide thermoplastic resin composition may further contain epoxy compound and inorganic filler.
- the polyphenylene sulfide thermoplastic resin composition according to the present invention comprises (A) 20 to 99.4 parts by weight of a polyphenylene sulfide resin; (B) 0.5 to 10 parts by weight of olefinic graft copolymer prepared by graft polymerizing (bi) 40 to 90 parts by weight of a copolymer prepared by polymerizing 60 to 100 % by weight of olefin monomer and 0 to 40 % by weight of vinyl monomer and (b 2 ) 10 to 60 parts by weight of a vinyl polymer; and (C) 0.1 to 10 parts by weight of a fluorinated polyolefin resin.
- the polyphenylene sulfide thermoplastic resin composition of the present invention may further contain (D) 0 to 3 parts by weight of an epoxy compound having two or more epoxy groups in one molecule and (E) 0 to 70 parts by weight of a filler.
- the polyphenylene sulfide used in the present invention is a polymer comprising at least 70 molar % of recurring units of the following structural formula.
- the polyphenylene sulfide comprising at least 70 molar % of recurring units has high degree of crystallization and sufficient heat- and chemical- resistance, and good impact strength.
- the polyphenylene sulfide of the present invention may be a linear, branched or cross-linked polymer or mixtures of the same.
- a method of preparing cross-linked polyphenylene sulfide resin is disclosed in Japanese publication No. 45-3368, and a method of preparing linear polyphenylene sulfide resin is disclosed in Japanese publication No. 52-12240, which are incorporated by reference herein.
- the polyphenylene sulfide of the present invention may contain less than 50 molar %, preferably less than 30 molar % of other recurring units of the following structural formulae:
- the melt index of polyphenylene sulfide is in the range of 10 to 300 g/10 min under 2.16 kg load at 316 °C , considering heat-stability or processability of the resin composition. If the melt index is more than 300 g/lOmin, the strength is reduced, and if it is less than 10 g/lOmin, the melt blendability and processability during melt blending and injection molding process will be lowered.
- the olefinic graft copolymer of the present invention is a coplymer prepared by graft polymerizing (bi) 40 to 90 parts by weight of a copolymer prepared by polymerizing 60 to 100 % by weight of olefin monomer and 0 to 40 % by weight of vinyl monomer and (b 2 ) 10 to 60 parts by weight of a vinyl polymer.
- the olefin monomer usable in the present invention are ethylene, propylene and butylene and so forth. These olefin monomers may be used in single or in combination as a mixture.
- vinyl monomer examples include methyl(meta)acrylate, ethyl(meta)acrylate, butyl(meta)acrylate, and a mixture thereof with maleic anhydride; vinyl acetate; vinyl monomer containing epoxy group such as glycidyl methacrylate, glycidyl acrylate, glycidyl ethacrylate and etc.
- vinyl monomer containing epoxy group such as glycidyl methacrylate, glycidyl acrylate, glycidyl ethacrylate and etc.
- methyl acrylate, ethyl acrylate/maleic anhydride, vinyl acetate, glycidyl methacrylate and a mixture thereof are preferred.
- the vinyl polymer (b 2 ) examples are polymethyl methacrylate, polystyrene, copolymer of styrene and cyanided vinyl monomer such as styrene-acrylonitrile copolymer(SAN) and a mixture thereof.
- the olefinic graft copolymer is used in an amount of 0.5 to 10 parts by weight. If the amount is less than 0.5 parts, impact modification effect cannot be obtained. If the amount exceeds 10 parts, flame-resistance of the V-0 grade at 0.8 mm cannot be fulfilled.
- the examples of the fluorinated polyolefin resin of the present invention are polytetrafluoroethylene, polyvinylidenefluori.de, tetrafluoroethylene/vinylidenefluoride copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, and ethylene/tetrafluoroethylene copolymer.
- the fluorinated polyolefin resin may be used in single or in combination as a mixture.
- the fluorinated polyolefin resin functions to form a fibrillar network when the resin composition containing the fluorinated polyolefin resin is extruded, resulting to decrease a flow viscosity and to increase the shrinkage during combustion so as to prevent the dripping phenomena.
- the fluorinated polyolefin resin (E) according to the present invention is prepared by a conventional process, for example, the resin is prepared in an aqueous solvent at 7 to 71 kg/cm 2 and 0 to 200 " C , preferably 20- 100 ° C , in the presence of a free radical forming catalyst such as sodium-, potassium-, or ammonium-peroxydisulphate.
- the fluorinated polyolefin resin is used in emulsion state or in powder state. In case using in emulsion state, dispersion of the fluorinated polyolefin resin is good, but the process will be somewhat complicated. Accordingly, if the fluorinated polyolefin resin could be uniformly dispersed in the entire resin composition to form the fibrillar network structure, it is preferable to use the fluorinated polyolefin resin in powder state.
- the preferable fluorinated polyolefin resin of the present invention is a polytetrafluoroethylene having an average particle size of 0.05 to 1,000 m and density of 1.2 to 2.3 g/cm 3 .
- the fluorinated polyolefin resin is used in an amount of 0.1 to 10 parts by weight. If the fluorinated polyolefin resin is used more than 10 parts by weight, the fluorinated resin cannot be dispersed in the resin composition, which makes the extrusion difficult.
- Epoxy compound having two or more epoxy groups The epoxy compound according to the present invention which contains two or more epoxy groups in one molecule is represented by the following general formula I :
- Ri and R 2 independently of one another are C 6-8 aryl group, n is 0 or natural number, preferably 0 or 1.
- the resin composition cannot obtain sufficient mechanical strength and impact resistance. And if an epoxy compound having four or more epoxy groups is used, the resin composition has poor flowability due to abrupt reaction.
- the epoxy compound having two or more epoxy groups are polyglycidyl ether compounds, polyglycidyl amine epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, resorcinol type epoxy compounds, tetrahydoxy bisphenol F type epoxy compounds, cresol novolak type epoxy compounds, phenol novolak type epoxy compounds, cycloaliphatic epoxy compounds, and so on.
- bisphenol A type epoxy compounds is preferred in view of impact resistance or extrusion workability of the resin composition
- the epoxy compound having two or more epoxy groups of the present invention is used in an amount of 0 to 3 parts by weight.
- the filler used in the present invention includes fibrous fillers, powdery filler and a mixture thereof.
- the fibrous fillers include glass fiber, carbon fiber, aramid fiber, potassium titanate fiber, silicon carbide fiber, wollastonite and so on.
- the powdery filler include calcium carbonate, silica, titanium oxide, carbon black, alumina, litium carbonate, iron oxide, molybdenum disulfide, graphite, glass beads, talc, clay mica, zirconium oxide, calcium silicate, boron nitride and so on.
- the filler of the present invention is used in an amount of 0 to 70 parts by weight.
- the polyphenylene sulfide thermoplastic resin composition of the present invention may further contain other additives such as antioxidants, release agents, flame retardants, lubricants, colorants such as dyes and pigments, and small amounts of various polymers according to purposes.
- the resin compositions of the present invention can be prepared by any known method. For example, all the components and additives are mixed together and extruded through an extruder and are prepared in the form of pellets.
- the resin compositions of the present invention of the present invention can be applied to various processes for molding and formed into various molded articles. Especially the compositions are suitably applied to substitute materials for Mg or Al die casting, electric or electronic parts, precision parts which require good mechanical strength, processability and impact resistance.
- A Polyphenylene sulfide resin
- PPS polyphenylene sulfide resin
- MI melt index
- Comparative Examples 1-4 were conducted in the same manner as in the Example 1 ⁇ 4 except that the amount of each component was altered.
- Flame retardancy the flame retardancy was measured in accordance with UL94 VB with a thickness of 0.8 mm.
- Flexural strength the flexural strength was measured in accordance with ASTM D790.
- Impact strength The notch Izod impact strength was measured in accordance with ASTM D256 (1/8" notched).
- Example 1 employing polyphenylene sulfide, olefinic graft copolymer and fluorinated polyolefin resin shows good flame retardancy compared to comparative Example 1.
- the resin compositions of Examples 2-4 which further contain epoxy compound and filler show improved mechanical properties.
- the present invention can be easily carried out by an ordinary skilled person in the art. Many modifications and changes may be deemed to be with the scope of the present invention as defined in the following claims.
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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)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006541022A JP4511553B2 (en) | 2003-11-21 | 2004-10-13 | Polyphenylene sulfide thermoplastic resin composition |
DE602004019250T DE602004019250D1 (en) | 2003-11-21 | 2004-10-13 | Thermoplastic Polyphenylene Sulfur Resin Composition |
EP04793471A EP1702008B1 (en) | 2003-11-21 | 2004-10-13 | Polyphenylene sulfide thermoplastic resin composition |
CN2004800340987A CN1882658B (en) | 2003-11-21 | 2004-10-13 | Polyphenylene sulfide thermoplastic resin composition |
US11/438,592 US7910655B2 (en) | 2003-11-21 | 2006-05-22 | Polyarylene sulfide thermoplastic resin composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020030083009A KR100566507B1 (en) | 2003-11-21 | 2003-11-21 | Polyphenylene Sulfide Thermoplastic Resin Composition |
KR10-2003-0083009 | 2003-11-21 | ||
KR10-2004-0023108 | 2004-04-02 | ||
KR1020040023108A KR100567401B1 (en) | 2004-04-02 | 2004-04-02 | Polyphenylene Sulfide Thermoplastic Resin Composition |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/438,592 Continuation-In-Part US7910655B2 (en) | 2003-11-21 | 2006-05-22 | Polyarylene sulfide thermoplastic resin composition |
Publications (1)
Publication Number | Publication Date |
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WO2005049732A1 true WO2005049732A1 (en) | 2005-06-02 |
Family
ID=36809330
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2004/002609 WO2005049732A1 (en) | 2003-11-21 | 2004-10-13 | Polyphenylene sulfide thermoplastic resin composition |
Country Status (6)
Country | Link |
---|---|
US (1) | US7910655B2 (en) |
EP (1) | EP1702008B1 (en) |
JP (1) | JP4511553B2 (en) |
DE (1) | DE602004019250D1 (en) |
TW (1) | TWI272290B (en) |
WO (1) | WO2005049732A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130081850A1 (en) | 2011-09-30 | 2013-04-04 | Ticona Llc | Fire-Resisting Thermoplastic Composition for Plenum Raceways and Other Conduits |
MX356435B (en) * | 2012-03-23 | 2018-05-22 | Dainippon Ink & Chemicals | Polyarylene sulfide resin composition and molded body. |
EP3392311A1 (en) * | 2017-04-21 | 2018-10-24 | Solvay Specialty Polymers Italy S.p.A. | Polymer alloy comprising a sulphur-containing aromatic polymer and a thermoplastic vulcanizate |
WO2019225694A1 (en) * | 2018-05-25 | 2019-11-28 | ダイキン工業株式会社 | Resin composition |
US20220002544A1 (en) * | 2019-10-25 | 2022-01-06 | Lg Chem, Ltd. | Polyarylene sulfide resin composition, method of preparing polyarylene sulfide resin composition, and heat insulating material manufactured using polyarylene sulfide resin composition |
WO2024132849A1 (en) * | 2022-12-23 | 2024-06-27 | Dsm Ip Assets B.V. | Pps composition, process for preparation, process for producing an article, and article made of the composition |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59207921A (en) * | 1983-05-13 | 1984-11-26 | Dainippon Ink & Chem Inc | Thermoplastic resin composition |
US4985175A (en) * | 1988-08-24 | 1991-01-15 | Bayer Aktiengesellschaft | Elastomer-modified carbon-containing polyarylene sulfide blends |
EP0431470A2 (en) * | 1989-11-30 | 1991-06-12 | Daikin Industries, Limited | Crosslinkable polyphenylene sulfide resin composition and process for preparing the same |
KR930008195B1 (en) * | 1990-02-14 | 1993-08-26 | 제일합섬 주식회사 | Polyphenylene sulfide resin composition |
JPH05295260A (en) * | 1992-04-16 | 1993-11-09 | Tonen Chem Corp | Thermoplastic resin composition |
JPH09263676A (en) * | 1996-03-28 | 1997-10-07 | Asahi Glass Co Ltd | Impact-resistant polyphenylene sulfide composition and its production |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58154757A (en) | 1982-03-10 | 1983-09-14 | Toray Ind Inc | Polyarylene sulfide resin composition |
JPH0653848B2 (en) | 1986-01-23 | 1994-07-20 | 東レ株式会社 | Polyphenylene sulfide composition |
JP2524593B2 (en) * | 1987-05-19 | 1996-08-14 | エヌティエヌ株式会社 | Polyphenylene sulfide resin composition |
JPH0662849B2 (en) * | 1988-02-03 | 1994-08-17 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition |
JPH01306467A (en) | 1988-06-02 | 1989-12-11 | Toray Ind Inc | Polyphenylene sulfide composition |
JP3133784B2 (en) * | 1991-06-21 | 2001-02-13 | 東燃化学株式会社 | Thermoplastic resin composition |
JP3105035B2 (en) * | 1991-08-30 | 2000-10-30 | 理研ビニル工業株式会社 | Polyarylene sulfide resin composition |
JP2726580B2 (en) * | 1991-09-25 | 1998-03-11 | ポリプラスチックス株式会社 | Sliding property improved polyarylene sulfide resin composition |
JPH05202291A (en) * | 1992-01-28 | 1993-08-10 | Dainippon Ink & Chem Inc | Polyarylene sulfide resin composition |
US5684088A (en) * | 1992-11-05 | 1997-11-04 | Daikin Industries, Ltd. | Polyphenylene sulfide resin compositions and process for preparation of same |
JPH06248160A (en) * | 1993-02-26 | 1994-09-06 | Japan Synthetic Rubber Co Ltd | Flame-retardant desin composition |
JP3560048B2 (en) * | 1994-11-04 | 2004-09-02 | 出光石油化学株式会社 | Polyarylene sulfide resin composition |
US5990225A (en) * | 1995-05-17 | 1999-11-23 | Mitsubishi Chemical Corporation | Resin of polyphenylene sulfide, polyethylene graft and TFE for sliding member |
JP3903505B2 (en) * | 1996-09-25 | 2007-04-11 | ダイキン工業株式会社 | Resin composition |
US6040370A (en) * | 1997-04-17 | 2000-03-21 | General Electric Company | Aqueous fluoropolymer dispersion and method for making fluoropolymer-containing thermoplastic resin composition |
JPH11124480A (en) * | 1997-10-24 | 1999-05-11 | Matsushita Electric Works Ltd | Resin composition for sealing semiconductor and its production, and semiconductor system using the resin composition for sealing semiconductor |
JP2001247751A (en) * | 1999-12-28 | 2001-09-11 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
US6916527B2 (en) * | 2001-01-18 | 2005-07-12 | Matsushita Electric Works, Ltd. | Resin moldings |
JP4307908B2 (en) * | 2003-06-05 | 2009-08-05 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition and coated molded article |
KR100938195B1 (en) | 2008-07-28 | 2010-01-21 | 재단법인대구경북과학기술원 | Method for distance estimation and apparatus for the same using a stereo matching |
-
2004
- 2004-10-13 JP JP2006541022A patent/JP4511553B2/en not_active Expired - Fee Related
- 2004-10-13 EP EP04793471A patent/EP1702008B1/en not_active Ceased
- 2004-10-13 WO PCT/KR2004/002609 patent/WO2005049732A1/en active Application Filing
- 2004-10-13 DE DE602004019250T patent/DE602004019250D1/en active Active
- 2004-10-22 TW TW093132187A patent/TWI272290B/en not_active IP Right Cessation
-
2006
- 2006-05-22 US US11/438,592 patent/US7910655B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59207921A (en) * | 1983-05-13 | 1984-11-26 | Dainippon Ink & Chem Inc | Thermoplastic resin composition |
US4985175A (en) * | 1988-08-24 | 1991-01-15 | Bayer Aktiengesellschaft | Elastomer-modified carbon-containing polyarylene sulfide blends |
EP0431470A2 (en) * | 1989-11-30 | 1991-06-12 | Daikin Industries, Limited | Crosslinkable polyphenylene sulfide resin composition and process for preparing the same |
KR930008195B1 (en) * | 1990-02-14 | 1993-08-26 | 제일합섬 주식회사 | Polyphenylene sulfide resin composition |
JPH05295260A (en) * | 1992-04-16 | 1993-11-09 | Tonen Chem Corp | Thermoplastic resin composition |
JPH09263676A (en) * | 1996-03-28 | 1997-10-07 | Asahi Glass Co Ltd | Impact-resistant polyphenylene sulfide composition and its production |
Non-Patent Citations (1)
Title |
---|
See also references of EP1702008A4 * |
Also Published As
Publication number | Publication date |
---|---|
US7910655B2 (en) | 2011-03-22 |
JP4511553B2 (en) | 2010-07-28 |
EP1702008A1 (en) | 2006-09-20 |
US20070123627A1 (en) | 2007-05-31 |
TW200521185A (en) | 2005-07-01 |
TWI272290B (en) | 2007-02-01 |
DE602004019250D1 (en) | 2009-03-12 |
EP1702008A4 (en) | 2007-01-24 |
JP2007512406A (en) | 2007-05-17 |
EP1702008B1 (en) | 2009-01-21 |
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