WO2001004214A1 - Composition a base de resine de polycetone ignifuge et article moule - Google Patents
Composition a base de resine de polycetone ignifuge et article moule Download PDFInfo
- Publication number
- WO2001004214A1 WO2001004214A1 PCT/JP2000/004402 JP0004402W WO0104214A1 WO 2001004214 A1 WO2001004214 A1 WO 2001004214A1 JP 0004402 W JP0004402 W JP 0004402W WO 0104214 A1 WO0104214 A1 WO 0104214A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- magnesium hydroxide
- composition according
- carbon atoms
- flame
- 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
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
Definitions
- the present invention relates to flame retardancy of polyketone resin useful as OA equipment, electric and electronic parts of home appliances, their housing parts, automobile parts, mechanical parts, and the like. More specifically, the present invention relates to a flame-retardant polyketone resin composition obtained by blending specific magnesium hydroxide particles with a polyketone resin, and a molded product thereof.
- Polyketone resin is a newly developed resin synthesized from carbon monoxide and olefin, and its mechanical properties fall into the category of engineering plastics.
- U.S. Pat. No. 4,843,144 and U.S. Pat. No. 4,880,903 disclose linear alternating ketones synthesized from ethylene and olefins such as propylene and carbon monoxide.
- a method for making a terpolymer is disclosed.
- the polyketone resin thus obtained has excellent impact resistance, high rebound resilience at both room temperature and low temperature, and has excellent creep characteristics. However, it is susceptible to a cross-linking reaction during processing such as extrusion and injection, and has poor melt stability. In addition, there is a problem of discoloration during processing.
- Japanese Patent Application Laid-Open No. 11-116975 describes that an aliphatic ketone polymer synthesized from carbon monoxide and at least one ethylenically unsaturated hydrocarbon contains polyol and aluminum hydroxide. It is disclosed that by adding a stabilizer containing a compound, stabilization and discoloration during melt processing can be reduced. In addition, it describes the addition of impact modifiers, flame retardants, reinforcing fillers, antioxidants, and other polymers. However, there is no specific explanation for flame retardancy of this polymer.
- Japanese Patent Application Laid-Open No. H11-71513 discloses a polyketone resin having a thickness of 100 in order to improve thin-wall fluidity, heat resistance, organic solvent resistance, and moldability useful as housing parts.
- a polyketone resin composition in which 0.01 to 50 parts by weight of a liquid crystalline resin is blended in parts by weight, and 0.01 to 60 parts by weight of a flame retardant is further contained.
- This publication states that organic bromides, organic phosphorus compounds, red phosphorus and the like can be mentioned as flame retardants, and that red phosphorus that is coated with a metal hydroxide coating such as magnesium hydroxide can also be used. I have.
- An object of the present invention is to provide an OA device and an electrical appliance for home appliances that have excellent appearance without adversely affecting the working environment and have good moldability and workability in the flame retardant polyketone resin composition.
- ⁇ To provide a flame-retardant polyketone resin composition useful as electronic parts and their housing parts, automobile parts, mechanical parts and the like.
- the present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, completed the present invention by blending a predetermined amount of specific magnesium hydroxide particles with a polyketone resin.
- the magnesium hydroxide particles used in the present invention are those in which the crystals grow well and have little aggregation, and whose surfaces are coated.
- the method of producing magnesium hydroxide particles as an additive for resins or as a flame retardant is already known.
- Magnesium hydroxide particles with good crystal growth and low agglomeration have good moldability, mechanical strength, and flame retardancy. It can show the nature. It is synthesized by the reaction of a water-soluble magnesium salt such as magnesium salt with an alkali such as caustic soda. Further, magnesium hydroxide particles obtained by rehydrating magnesium oxide or natural magnesium hydroxide can also be used as a flame retardant.
- the object of the present invention is:
- the average secondary particle size is 0.2 to 5 ⁇ m and
- the polyketone resin used in the present invention is generally called an aliphatic polyketone resin.
- the polyketone resin is obtained by reacting an ethylene-based orifice with carbon monoxide.
- the polyketone resin is not limited as long as it can be used for molding, and its production method is not limited.
- a resin obtained by reacting carbon monoxide with an olefin mixture containing a small proportion of ethylene and other olefins is preferable.
- Particularly preferred polyketone resins include the following repeating units (X) and (Y) in the main chain.
- D represents an alkylene chain other than an ethylene chain (—CH 2 —CH 2 —)
- the molar ratio (YZX) is in the range of 0.01 to 0.2, preferably 0.02 to 0.1.
- X is a unit based on ethylene
- Y is a unit based on an olefin other than ethylene.
- D in Y is, specifically, an alkylene chain based on propylene, butylene, pentene or styrene, particularly preferably an alkylene chain based on propylene.
- magnesium hydroxide particles blended in the polyketone resin magnesium hydroxide particles blended in the polyketone resin
- the specific surface area measured by the BET method is 1 to 15 m 2 Zg, preferably 2 to 1 Om 2 Zg.
- the magnesium hydroxide particles have an average secondary particle diameter of 0.2 to 5 m, preferably 0.5 to 3 m, as measured by a laser single light diffraction scattering method. If the magnesium hydroxide particles having the above-mentioned shape are added to the polyketone resin in an amount sufficient to impart flame retardancy, the fluidity will be extremely reduced, the moldability will be poor, and the physical properties will be poor.
- the magnesium hydroxide particles having the above-mentioned shape are used after covering the surface with a surface treating agent.
- the luster composition has improved flowability and excellent moldability, and the resulting molded article has improved physical strength and colorability.
- the flame retardancy is at least V-1 based on the UL94 standard, and in most cases V-0 is achieved.
- surface treatment agents used for surface coating of magnesium hydroxide particles (a) for example, C 14 -C 24 higher aliphatics and alkali metal salts thereof; (b) phosphates, for example; For example, higher alcohol sulfates such as stearyl alcohol and oleyl alcohol; and (d) silane coupling agents such as vinylethoxysilane, methacryloxypropyltrimethoxysilane, and araminopropylmethoxysilane.
- polymers such as styrene-acrylic low molecular weight polymers can be exemplified.
- the phosphoric ester of the above (b) has a more excellent effect, but according to the study of the present inventors, the phosphoric ester represented by the following formula (1) is particularly preferable. There was found.
- R is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms
- A is an alkylene group having 2 to 4 carbon atoms
- n is an integer of 0 to 6
- m is 1 or Represents a cation and M represents a cation
- the cation represents an alkali metal, an alkylamine having 1 to 4 carbon atoms or an alkanolamine cation represented by the following formula.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- B represents carbon It represents an alkylene group having 2 to 4 atoms
- r represents an integer of 1 to 3.
- sodium salt of steryl alcohol phosphate is particularly preferred.
- the surface treatment method is to maintain the temperature of the magnesium hydroxide particles dispersed in water at or above a temperature at which the surface treatment agent dissolves or emulsifies, and gradually pours in an aqueous solution of the surface treatment agent with stirring. Continue stirring for 15 to 30 minutes after completion.
- the obtained slurry of magnesium hydroxide particles after surface treatment is dehydrated, washed with water, and dried according to a conventional method.
- the fatty acid is not soluble in an aqueous solvent like a higher fatty acid
- the one dissolved in heat or an organic solvent can be subjected to a surface treatment in magnesium hydroxide powder by a dry method using a Henschel mixer or the like.
- the treatment amount of the surface treatment agent is in the range of 0.5 to 5% by weight, and preferably in the range of 2 to 4% by weight, based on the magnesium hydroxide particles.
- a polyketone resin composition having suitable resin physical properties and less coloring is obtained. Is obtained.
- the content of the magnesium hydroxide particles is less than the above range, the flame retardancy becomes insufficient, and when the content exceeds the upper limit, the resin fluidity is poor and the moldability and mechanical strength of the resin become insufficient, which is not preferable.
- polymers can be added to the flame-retardant resin composition of the present invention as long as physical properties and appearance are not impaired.
- a polyester resin, a polyamide resin, polyacetal, polyethylene, polypropylene, ABS, polystyrene and the like can be blended.
- a polyketone in which one or more of a hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, and a carboxylic acid anhydride group are added to the molecule or a part of the terminal.
- These other polymers are desirably at most 20% by weight, preferably at most 10% by weight, based on the resin composition of the present invention.
- the flame-retardant polyketone resin composition of the present invention may contain, if necessary, an antioxidant, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, a release agent, a colorant, a pigment, Other flame retardants such as crystallization nucleating agents, plasticizers and organophosphorus compounds, antimony trioxide It can also be added.
- the flame-retardant polyketone resin composition of the present invention is produced by a generally known method.
- a polyketone resin, surface-treated magnesium hydroxide particles, and other necessary additives are mixed, or each is separately supplied to an extruder and melt-kneaded at 150 to 350 ° C in a temperature range of 150 to 350 ° C. It can be obtained by:
- the kneading machine may be a single-screw extruder or a twin-screw extruder having a mixing section, or a double kneader may be used.
- the tensile strength, elongation, Dupont falling ball impact test, colorability (Y.1), and flame retardancy test were measured on specimens after injection molding.
- sample for evaluation of magnesium hydroxide particles 10 L of 100 g / L aqueous slurry of magnesium hydroxide particles synthesized by the reaction of magnesium chloride and sodium hydroxide was prepared, heated and aged at 17 Ot: for 5 hours with stirring, and cooled. After removal, the mixture was again heated to 80 ° C, 35 g of sodium stearate previously dissolved in warm water was gradually added to the magnesium hydroxide particle slurry with stirring, and stirring was continued for 30 minutes. After cooling, solid-liquid separation, washing, drying at 120, and pulverized by a hammer mill for testing, had a BET specific surface area of 6 m 2 Zg and an average secondary particle diameter of 0.9 ⁇ m. The coverage of sodium stearate was 3.1% by weight based on the magnesium hydroxide particles.
- Sample 2 Samples were prepared in the same manner as in Sample 1, except that sodium stearate was replaced with sodium salt of stearyl alcohol phosphate.
- the BET specific surface area was 5.8 m 2 Zg, and the average secondary particle size was 0.9 ⁇ m.
- the coating amount of the phosphate was 3.0% by weight based on the weight of the magnesium hydroxide particles.
- sample 3 The surface area of sample 1 before surface treatment was used.
- Sample 2 was synthesized using magnesium hydroxide having a BET specific surface area of 35 m 2 Z g and an average secondary particle diameter of 0.5 ⁇ m, which was synthesized by the reaction of magnesium salt and calcium hydroxide. The same treatment was performed. The amount of the phosphoric ester covered was 3.0% by weight based on the magnesium hydroxide particles.
- each sample of the above magnesium hydroxide was powder-mixed according to the formulation shown in the table, and pellets were formed with a twin-screw extruder adjusted to 220 to 240 ° C. 60 pellet resulting et a, 16 hr and vacuum dried, cylinders some 220 ° C ⁇ 245 ° C, mold temperature of 60 ° C, each test at injection pressure 6 OKg / cm 2 to adjust the injection molding machine A sample was obtained. The results are shown in the table below.
- the resin composition of the present invention has high flame retardancy and good fluidity, so that a molded article having good moldability and high impact resistance can be obtained. Accordingly, flame-retardant polyketone resin molded articles useful as OA equipment “electricity of home appliances” electronic parts and housing parts, automobile parts, machine parts, and the like can be obtained.
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00942448A EP1122283B1 (en) | 1999-07-09 | 2000-07-03 | Flame-retardant polyketone resin composition and molded article |
US09/786,429 US6372835B1 (en) | 1999-07-09 | 2000-07-03 | Flame-retardant polyketone resin composition and molded article |
DE60006639T DE60006639T2 (de) | 1999-07-09 | 2000-07-03 | Flammgeschützte polyketonmischung und formteil |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19625399 | 1999-07-09 | ||
JP11/196253 | 1999-07-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001004214A1 true WO2001004214A1 (fr) | 2001-01-18 |
Family
ID=16354744
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/004402 WO2001004214A1 (fr) | 1999-07-09 | 2000-07-03 | Composition a base de resine de polycetone ignifuge et article moule |
Country Status (4)
Country | Link |
---|---|
US (1) | US6372835B1 (ja) |
EP (1) | EP1122283B1 (ja) |
DE (1) | DE60006639T2 (ja) |
WO (1) | WO2001004214A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0402627D0 (en) * | 2004-02-06 | 2004-03-10 | Imerys Minerals Ltd | Ultrafine Ground Natural Brucite |
GB0622106D0 (en) * | 2006-11-06 | 2006-12-20 | Imerys Minerals Ltd | Grinding and beneficiation of brucite |
US8933334B2 (en) * | 2006-11-21 | 2015-01-13 | Autonetworks Technologies, Ltd. | Flame retardant, a flame-retardant composition, an insulated wire, a wiring harness, and a method for manufacturing the flame-retardant composition |
US20170158851A1 (en) * | 2014-07-18 | 2017-06-08 | Hyosung Corporation | Polyketone resin composition having outstanding water resistance |
EP3168252B1 (de) * | 2015-11-13 | 2019-01-09 | Ems-Patent Ag | Polyketon-formmassen mit verbesserten eigenschaften, hieraus hergestellter formkörper sowie verfahren zu dessen herstellung |
EP3168253B1 (de) * | 2015-11-13 | 2018-04-11 | Ems-Patent Ag | Flammgeschützte, aliphatische polyketonmassen, hieraus hergestellte formkörper sowie verfahren zu deren herstellung |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02274767A (ja) * | 1989-03-31 | 1990-11-08 | Shell Internatl Res Maatschappij Bv | 難燃性組成物 |
US5286785A (en) * | 1991-06-25 | 1994-02-15 | Dsm N.V. | Thermostable ethylene-carbon monoxide copolymer containing Al-Mg-CO3 or CaO |
US5684117A (en) * | 1995-10-16 | 1997-11-04 | Shell Oil Company | Flame retardant polyketone polymer blend |
JP2000007883A (ja) * | 1998-05-29 | 2000-01-11 | Siecor Operations Llc | 難燃性ポリマ―組成物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IN166314B (ja) | 1985-08-29 | 1990-04-07 | Shell Int Research | |
NL8602164A (nl) | 1986-08-26 | 1988-03-16 | Shell Int Research | Katalysatorcomposities. |
US4885328A (en) * | 1989-03-31 | 1989-12-05 | Shell Oil Company | Flame retardant compositions |
JP2805329B2 (ja) | 1989-04-07 | 1998-09-30 | 協和化学工業株式会社 | 難燃性樹脂組成物および難燃剤 |
JPH1171513A (ja) | 1997-06-25 | 1999-03-16 | Toray Ind Inc | ポリケトン樹脂組成物 |
US5973048A (en) | 1997-08-08 | 1999-10-26 | General Electric Company | Melt and color stabilization of aliphatic polyketones |
JP3299921B2 (ja) * | 1997-10-17 | 2002-07-08 | 協和化学工業株式会社 | 水酸化マグネシウムを含有する耐酸性熱可塑性樹脂組成物 |
-
2000
- 2000-07-03 US US09/786,429 patent/US6372835B1/en not_active Expired - Fee Related
- 2000-07-03 EP EP00942448A patent/EP1122283B1/en not_active Expired - Lifetime
- 2000-07-03 DE DE60006639T patent/DE60006639T2/de not_active Expired - Fee Related
- 2000-07-03 WO PCT/JP2000/004402 patent/WO2001004214A1/ja active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02274767A (ja) * | 1989-03-31 | 1990-11-08 | Shell Internatl Res Maatschappij Bv | 難燃性組成物 |
US5286785A (en) * | 1991-06-25 | 1994-02-15 | Dsm N.V. | Thermostable ethylene-carbon monoxide copolymer containing Al-Mg-CO3 or CaO |
US5684117A (en) * | 1995-10-16 | 1997-11-04 | Shell Oil Company | Flame retardant polyketone polymer blend |
JP2000007883A (ja) * | 1998-05-29 | 2000-01-11 | Siecor Operations Llc | 難燃性ポリマ―組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1122283A4 * |
Also Published As
Publication number | Publication date |
---|---|
DE60006639T2 (de) | 2004-09-16 |
DE60006639D1 (de) | 2003-12-24 |
EP1122283A4 (en) | 2002-01-30 |
EP1122283B1 (en) | 2003-11-19 |
US6372835B1 (en) | 2002-04-16 |
EP1122283A1 (en) | 2001-08-08 |
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