WO1999047607A1 - Composition de resine - Google Patents
Composition de resine Download PDFInfo
- Publication number
- WO1999047607A1 WO1999047607A1 PCT/JP1999/001323 JP9901323W WO9947607A1 WO 1999047607 A1 WO1999047607 A1 WO 1999047607A1 JP 9901323 W JP9901323 W JP 9901323W WO 9947607 A1 WO9947607 A1 WO 9947607A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- resin composition
- parts
- fluororesin
- following
- 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
- 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
-
- 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
-
- 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 resin composition containing polyphenylene sulfide (hereinafter, referred to as PPS) and a fluororesin. More specifically, the dimensional accuracy of a molded article having a three-dimensional shape obtained by an injection molding method is significantly improved.
- a resin composition containing polyphenylene sulfide (hereinafter, referred to as PPS) and a fluororesin. More specifically, the dimensional accuracy of a molded article having a three-dimensional shape obtained by an injection molding method is significantly improved.
- PPS polyphenylene sulfide
- PPS is known as a resin with excellent heat resistance, solvent resistance, electrical properties, mechanical strength, dimensional stability, flame retardancy, etc.It is used for electric and electronic equipment parts and automotive parts materials. , Chemical equipment parts materials, other functional parts materials and so on.
- PPS has a low degree of polymerization and has the property of being compounded with fiber reinforcing agents such as glass fiber and carbon fiber and inorganic fillers, etc., and can be used as engineering plastics. This is because a phenomenon occurs in which the dimensions of the molded product differ depending on the orientation direction and it is difficult to obtain a predetermined dimensional accuracy.
- An object of the present invention is to provide a resin composition containing PPS, a fluororesin, and a filler, from which a three-dimensional molded article having high dimensional accuracy can be obtained by injection molding.
- the present inventors have found that the above object can be achieved by blending a specific amount of a fluororesin having a higher solidification temperature than PPS into PPS, and have accomplished the present invention.
- the present invention relates to the following (a) and (b): (a) 50 to 99.5% by weight, (b) 0.5 to 50 in the total amount of (a) and (b).
- a resin composition containing the resin composition in a percentage by weight.
- the present invention provides the above resin composition containing the following (c) in a total amount of more than 0 to 250 parts by weight based on 100 parts by weight of the total of (a) and (b).
- PPS (a) used in the present invention is substantially a repetition of the structure represented by Formula 1. It is a random copolymer or block copolymer containing at least 70 mol%, preferably at least 90 mol%, of these repeating units. If this repeating unit is less than 70 mol%, it is difficult to obtain a composition that achieves the object of the present invention.
- the copolymer units other than the repeating unit having the structure represented by the formula 1 are present in the PPS (a) in a proportion of less than 30 mol%, preferably less than 10 mol%, and do not lower the crystallinity of the polymer. It may contain an arylene sulfide structure unit represented by the following structure within the range.
- R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group, or a carboxylic acid metal base.
- PP S (a) can be obtained by various known polymerization methods.
- a preferred method is to react sodium sulfide with p-dichlorobenzene in an amide-based solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone-based solvent such as sulfolane.
- an amide-based solvent such as N-methylpyrrolidone or dimethylacetamide
- a sulfone-based solvent such as sulfolane.
- PP S (a) can be used after washing after polymerization.However, for example, it may be used after treatment with an aqueous solution containing an acid such as hydrochloric acid or acetic acid or a mixed solution of water and an organic solvent, or with a salt solution such as ammonium chloride. Even processed ones can be used.
- the melt index of P PS (a) is measured at a cylinder temperature of 300 ° C, a load of 5 kg, an orifice diameter of 2.095 mm and a length of 8 mm, and is preferably 0.1 to 500, particularly preferably. Is 1 to 300. If the melt index is less than 0.1, the fluidity during injection molding is poor, and if it exceeds 500, the mechanical strength of the molded product is low, making it unsuitable for industrial parts.
- the fluororesin (b) is a fluororesin having a solidification temperature (T mc ) of 237 ° C or higher when cooled at a cooling rate of 10 ° CZ after being melted in a nitrogen atmosphere of 330 ° C.
- HFP TF EZ hexafluoropropylene copolymer
- PFA is preferably commercially available, in which the number of carbon atoms in the alkyl group of PAVE of the polymerization component is 1 to 6 and the polymerization unit based on PAVE is 1 to 5 mol%.
- PAVE perfluro (propyl vinyl ether), perfluor (ethyl vinyl ether), perfluoro (methyl vinyl ether) are preferable, and particularly perfluoro (propyl vinyl ether) is preferable.
- the PF A may contain polymerized units based on two or more of these.
- the FEP preferably has a polymerization unit of 1 to 20 mol% based on HFP and is commercially available.
- a PAVEZHFP / TFE copolymer a polymerization component Z (PAVE and / or HFP) ZTFE copolymer other than PAVE and HFP, and the like may be used.
- the polymerized units based on PAVE are 0 to 5 mol%
- the polymerized units based on HFP are 0 to 20 mol%
- the total of the polymerized units based on PAVE and HFP is 1 to 20 mol%. % Is preferred.
- a copolymer containing 0.5 mol% of a polymerization unit based on perfluoro (propylbutyl ether) and 7.0 mol% of a polymerization unit based on HFP is used.
- the melt index of these fluororesins (b) is not particularly limited, it is measured under the conditions of 330 ° C, 5 kg load, orifice diameter 2.095 mm and length 8 mm. It is preferable for dispersion. Melt index measurement conditions are specified in ASTM D1238.
- fluororesins (b) can be produced by conventionally known various polymerization methods such as suspension polymerization, emulsion polymerization and solution polymerization.
- the mixing ratio (a) / (b) of PPS (a) and fluororesin (b) in the composition of the present invention is 5050 to 99.5 / 0.5 by weight. Particularly, T O / S O S SZ 5 (weight ratio) is preferable. If the weight ratio of PPS is less than 50Z50, the fluororesin cannot clearly form islands, and if it exceeds 99.5 / 0.5, the amount of fluororesin will be small, and the effects of the present invention cannot be expected.
- the sea portion is preferably PPS
- the island portion is preferably formed of a fluororesin.
- Fig. 1 shows a schematic cross-sectional view of the mold. 1 is a sprue, 2 is a runner, 3 is a pin gate, and 4 is a molded product.
- the molded product obtained by injection molding the composition of the present invention at a cylinder temperature of 330 ° C. and a mold temperature of 150 ° C. is a molded product A shown in FIG. It has excellent dimensional accuracy, with the dimensional difference of the B part and the difference between the maximum and minimum dimensions of the B part when formed by 100 shots are about 10 times smaller than before.
- Figure 2 is a cross-sectional view of the molded product. Indicates the dimensions and shape. The unit of the dimensions in Fig. 2 is mm, D 1 is 25.0 in diameter, D 2 is 19.0 in diameter, D 3 is 35.0 in diameter, D 4 is 24.6 in diameter, and D 5 is 22. 8, D6 is diameter 19.6, L1 is 35.0, L2 is 20.0, L3 is 5.4, L4 is 3.0, L5 is 8.0, L6 is 2.0 is there.
- composition of the present invention contains (c) an organic reinforcing material, an inorganic reinforcing material, or a filler in addition to (a) and (b), but based on 100 parts by weight of the total of (a) and (b).
- C) May contain up to 250 parts by weight of organic reinforcement, inorganic reinforcement or filler.
- A) If the component exceeds 250 parts by weight, injection molding is difficult. Also, injection molding can be performed without the component (c).
- components include organic fillers of thermosetting resin powder, fly, mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, graphite, titanium oxide, zinc oxide, riichi
- examples include inorganic fillers such as bon black, glass fiber, bonbon fiber, inorganic reinforcing material with a weak force such as potassium titanate and aluminum borate, and organic reinforcing materials such as polyimide fiber.
- These components (c) may be used as they are, but it is preferable to use those that have been surface-treated with a silane coupling agent or the like before blending.
- lubricants such as sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite
- Adjustment of the resin composition of the present invention can be performed by charging the extruder into the hopper using a number of metering feeders, or by premixing using a tumbler, V mixer, hensile mixer, etc.
- a method of selecting a screw with a bidding function with a kneading machine, melting and kneading to make a pellet is used.
- the sample was heated from normal temperature to 330 ° C at a rate of 10 ° C / minute under a nitrogen atmosphere, and maintained at 330 ° C for 5 minutes. The temperature was lowered from 10 ° C. to 100 ° C. in 10 ° C.Z for measurement.
- PTFE Asahi Glass Co., Ltd., full-on PTFE L-150 J (no coagulation temperature).
- PF A manufactured by Asahi Glass Co., Ltd., Aflon PF A P-61 (with a solidification temperature of 271).
- FEP Aflon FEP (solidification temperature 241) manufactured by Asahi Glass Co., Ltd.
- ETFE Asahi Glass Co., Ltd., Aflon COPC88AX (coagulation temperature 230 ° C).
- Low melting point ETF E hereinafter referred to as LM-ETFE
- Aflon LM 740 solidification temperature 206 ° C, manufactured by Asahi Glass Co., Ltd.
- PVdF NEOFLON VP 800 (coagulation temperature: 150 ° C), manufactured by Daikin.
- Glass fiber 03MAFT 562, manufactured by Asahi Fiber One Glass Co., Ltd.
- No surface treatment was performed with a silane coupling agent before blending glass fiber, spherical silica, or calcium carbonate.
- Table 1 shows the PPS and filler in the hopper of the first feeder and the fluororesin in the hopper of the second feeder of the same-direction twin-screw extruder with a kneading section having two kneading points.
- a cylinder temperature of 320 ° C a screw rotation speed of lOO rpm, the raw materials are kneaded while sucking with a vacuum pump from the vent, and the discharged strand is gradually cooled and then 3 mm long with a beretizer.
- the cylinder temperature of a molding machine of 30 tons for electric type mold clamping, which was cut into pieces to prepare a composition was set to 330.
- the outer diameter of points A and B in Fig. 2 was measured using a laser scan micrometer (manufactured by Mitutoyo Corporation) for the obtained molded article.
- the dimensional difference between parts A and B (wm) (hereinafter referred to as AZB dimensional difference) and the difference between the maximum and minimum dimensions of part B of a 100 shot molded product (wm) (hereinafter referred to as B dimensional difference) are shown. Shown in 1. [table 1 ]
- the resin composition of the present invention has extremely high dimensional accuracy of a molded article having a three-dimensional shape obtained by injection molding the resin composition, and is useful for structural materials and various parts in the fields of automobiles, home appliances, and electronics.
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/623,486 US6780944B1 (en) | 1998-03-19 | 1999-03-17 | Resin composition |
DE69938340T DE69938340T2 (de) | 1998-03-19 | 1999-03-17 | Harzzusammensetzung |
EP99909203A EP1065247B1 (en) | 1998-03-19 | 1999-03-17 | Resin composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10/70848 | 1998-03-19 | ||
JP07084898A JP4223089B2 (ja) | 1998-03-19 | 1998-03-19 | 樹脂組成物 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999047607A1 true WO1999047607A1 (fr) | 1999-09-23 |
Family
ID=13443408
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/001323 WO1999047607A1 (fr) | 1998-03-19 | 1999-03-17 | Composition de resine |
Country Status (5)
Country | Link |
---|---|
US (1) | US6780944B1 (ja) |
EP (1) | EP1065247B1 (ja) |
JP (1) | JP4223089B2 (ja) |
DE (1) | DE69938340T2 (ja) |
WO (1) | WO1999047607A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8357739B2 (en) * | 2006-12-11 | 2013-01-22 | Sabic Innovative Plastics Ip B.V. | Low fluoride thermoplastic composition, method of manufacture and product made therefrom |
US9243784B2 (en) | 2012-12-20 | 2016-01-26 | International Business Machines Corporation | Semiconductor photonic package |
US9400356B2 (en) | 2013-03-14 | 2016-07-26 | International Business Machines Corporation | Fiber pigtail with integrated lid |
US8923665B2 (en) | 2013-03-15 | 2014-12-30 | International Business Machines Corporation | Material structures for front-end of the line integration of optical polarization splitters and rotators |
US9360635B2 (en) | 2014-07-09 | 2016-06-07 | International Business Machines Corporation | Dual-polymer fiber optic interface with melt-bond adhesive |
JP6405787B2 (ja) * | 2014-08-18 | 2018-10-17 | 株式会社デンソー | 液体ポンプ用ロータ構造 |
US20200055234A1 (en) * | 2016-10-21 | 2020-02-20 | Toray Industries, Inc. | Polyarylene sulfide resin powder granular article mixture and method for producing three-dimensional molded article |
US20210206970A1 (en) | 2018-05-25 | 2021-07-08 | Daikin Industries, Ltd. | Resin composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03292366A (ja) * | 1990-04-10 | 1991-12-24 | Nippon Seiko Kk | 耐摩耗性樹脂組成物 |
JPH09132691A (ja) * | 1995-11-08 | 1997-05-20 | Daikin Ind Ltd | 摺動部品用非付着性成形材料、分離爪及び排紙コロ |
JPH09286916A (ja) * | 1995-12-28 | 1997-11-04 | Ntn Corp | 水中摺動性樹脂組成物および水栓用ディスクバルブ |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2535332B1 (fr) * | 1982-11-03 | 1986-09-26 | Electricite De France | Alliage de polymeres, sa preparation et son application a la fabrication d'elements de reacteurs electrochimiques |
US4749752A (en) | 1985-04-01 | 1988-06-07 | Shanghai Institute Of Organic Chemistry Academia Sinica | Fluoropolymer alloys |
JP3052338B2 (ja) * | 1990-06-08 | 2000-06-12 | ダイキン工業株式会社 | 摺動材組成物およびその製造方法 |
JP2802418B2 (ja) * | 1994-08-04 | 1998-09-24 | 大同メタル工業株式会社 | 摺動用樹脂組成物 |
JP3292366B2 (ja) | 1996-09-09 | 2002-06-17 | ダイワ精工株式会社 | 魚釣用スピニングリール |
-
1998
- 1998-03-19 JP JP07084898A patent/JP4223089B2/ja not_active Expired - Fee Related
-
1999
- 1999-03-17 DE DE69938340T patent/DE69938340T2/de not_active Expired - Lifetime
- 1999-03-17 US US09/623,486 patent/US6780944B1/en not_active Expired - Fee Related
- 1999-03-17 EP EP99909203A patent/EP1065247B1/en not_active Expired - Lifetime
- 1999-03-17 WO PCT/JP1999/001323 patent/WO1999047607A1/ja active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03292366A (ja) * | 1990-04-10 | 1991-12-24 | Nippon Seiko Kk | 耐摩耗性樹脂組成物 |
JPH09132691A (ja) * | 1995-11-08 | 1997-05-20 | Daikin Ind Ltd | 摺動部品用非付着性成形材料、分離爪及び排紙コロ |
JPH09286916A (ja) * | 1995-12-28 | 1997-11-04 | Ntn Corp | 水中摺動性樹脂組成物および水栓用ディスクバルブ |
Non-Patent Citations (1)
Title |
---|
See also references of EP1065247A4 * |
Also Published As
Publication number | Publication date |
---|---|
US6780944B1 (en) | 2004-08-24 |
DE69938340T2 (de) | 2009-03-26 |
DE69938340D1 (de) | 2008-04-24 |
EP1065247A1 (en) | 2001-01-03 |
JP4223089B2 (ja) | 2009-02-12 |
EP1065247A4 (en) | 2001-07-04 |
EP1065247B1 (en) | 2008-03-12 |
JPH11269383A (ja) | 1999-10-05 |
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