WO2004104091A1 - Composition de resine styrene ignifuge - Google Patents

Composition de resine styrene ignifuge Download PDF

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Publication number
WO2004104091A1
WO2004104091A1 PCT/JP2004/006367 JP2004006367W WO2004104091A1 WO 2004104091 A1 WO2004104091 A1 WO 2004104091A1 JP 2004006367 W JP2004006367 W JP 2004006367W WO 2004104091 A1 WO2004104091 A1 WO 2004104091A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
tribromoneopentyl
retardant
phosphate
resin composition
Prior art date
Application number
PCT/JP2004/006367
Other languages
English (en)
Japanese (ja)
Inventor
Takashi Haruna
Original Assignee
Dai-Ichi Kogyo Seiyaku Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai-Ichi Kogyo Seiyaku Co., Ltd. filed Critical Dai-Ichi Kogyo Seiyaku Co., Ltd.
Publication of WO2004104091A1 publication Critical patent/WO2004104091A1/fr

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Classifications

    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K3/2279—Oxides; Hydroxides of metals of antimony

Definitions

  • the present invention relates to a styrenic resin composition having excellent flame retardancy and self-extinguishing by melting and dropping at the time of ignition.
  • the composition includes a plurality of specific flame retardants that exhibit a synergistic effect on flame retardancy when used in combination. These flame retardants exhibit the desired flame retardancy even in small amounts, are highly heat-stable, and do not significantly impair the appearance and strength properties of the resin. Rather, it is possible to economically provide a flame-retardant styrenic resin composition having excellent workability for use in molding a melt-dropping flame-retardant object.
  • Styrene resins are widely used as housings and components for home appliances and OA equipment, taking advantage of their excellent moldability and appearance and physical properties of molded products.
  • it is necessary to provide flame retardancy to avoid danger from fire.
  • a flame-retardant styrene resin in which a halogen-based flame retardant is blended with a styrene resin has been used.
  • improvements in thermal stability, heat resistance, fluidity, impact resistance, and the like have been further demanded for each application.
  • Japanese Patent Application Laid-Open No. 4 325564 discloses a flame-retardant resin by adding tris (tribromophenoxy) triazine, a bromine-containing epoxy resin and antimony trioxide to a thermoplastic resin such as polystyrene in combination. Disclose the technology to perform. However, in this technique, since the total amount of the added flame retardant is large, it adversely affects the physical properties such as heat resistance, strength, and light resistance of the resin molded product. JP-A-64-11164 suggests that various types of thermoplastic and thermosetting resins can be made flame-retardant by using a small amount of a hydroquinone compound in combination with tris (tribromoneopentyl) phosphate.
  • the quinone conjugated compound functions as an antioxidant and improves the thermal stability (prevents discoloration and deterioration) of the flame-retardant resin composition.
  • This technology is applied to polystyrene resin.
  • a relatively large amount of tris (tribromoneopentyl) phosphate is still required, and deterioration of the physical properties of the resin molded product is inevitable.
  • Japanese Patent Application Laid-Open No. 11-323064 discloses that tris (tripromophenoxy) triazine, tris (tribromoneopentyl) phosphate, antimony trioxide, and polytetrafluoroethylene are added to rubber-reinforced polystyrene resin.
  • the present invention provides a good balance between desired flame retardancy and physical properties such as flexural strength, heat stability, heat resistance, and light resistance at a relatively small amount of a bromine-containing flame retardant. It is a main object of the present invention to provide a melt-dropping flame-retardant styrene-based resin composition which can obtain a resin. Other objects and advantages of the present invention will become apparent as the description proceeds.
  • the present invention provides
  • the total amount of the added amount (B) + (C) to 100 parts by weight is 2-10 parts by weight, and the weight ratio of (B) in (B) + (C) is 0.9-0. 2.
  • (c) Compounds include tris (tribromoneopentyl) phosphate, bis (tribromoneopentyl) alkylphosphate, bis (tribromoneopentyl) alkylphenylate, bis (tribromoneopentyl) tribromophenate. Phosphoric acid ester, bis (tribromophenyl) tribromoneopentyl phosphoric acid ester, or a mixture thereof.
  • a styrene-based resin refers to a homo- or copolymer of a styrene monomer.
  • Comonomers that can be copolymerized with styrene include styrene derivatives such as a small proportion of ⁇ -methylstyrene, butadiene, methyl methacrylate, acrylonitrile, maleic anhydride or its derivatives, itaconic acid, and the like.
  • the impact-resistant styrene resin ( ⁇ ) is a polymer alloy or a polymer blend of a styrene resin containing a rubber component, and a polystyrene, a styrene-butadiene copolymer, a polyisoprene, Butadiene isoprene copolymer, natural rubber, rubber-like polymer such as ethylene propylene copolymer.
  • S-dispersed, rubber-reinforced styrene resin (known as HI-PS), and acryl-toluene. Contains butadiene styrene copolymer (known as ABS).
  • the compound (B) is typically tris (tribromophenoxy) triazine and tris (dibromophenoxy) triazine, but may be a mixture of bis (tribromophenoxy) dibromophenoxy.
  • Their melting points are above 170 ° C. However, they usually melt at the processing temperature of styrene resins between 180 ° C and 260 ° C.
  • the compound (C) is a phosphate ester having a melting point of 170 ° C. or higher and at least one of the ester residues is a tribromoneopentyl group.
  • a typical example of the corresponding phosphoric acid ester is tris (tribromoneopentyl) phosphate (melting point: 181 ° C), but bis (tribromoneopentyl) alkyl phosphate and bis (tribromoneopentyl) Melting point of 170 among alkyl phenyl ester, bis (tribromoneopentyl) tribromophenyl phosphate, bis (tribromophenoxy) tribromoneopentyl phosphate and the like. C's can be used as well.
  • These phosphate esters with a melting point of 170 ° C or higher are styrene It melts at the processing temperature of the resin.
  • Antimony trioxide (D) is widely used as a flame retardant aid that enhances the flame retardant effect of halogen-containing flame retardants. Those having an average particle size of 0.4-1.5 / z m are easily dispersed uniformly in the resin.
  • the amount of the compound (B) and the compound (C) added is 2.0-10.0 parts by weight based on 100 parts by weight of the styrene resin (A). If the amount is less than 2.0 parts by weight, sufficient flame retardancy cannot be obtained. If the amount exceeds 10.0 parts by weight, the heat resistance, impact resistance and thermal stability of the flame-retardant resin composition are reduced. It is also disadvantageous for economy.
  • the amount of antimony trioxide is 0.2-3.0 parts by weight, preferably 0.3-3.0 parts by weight. However, if it is less than 0.2 parts by weight, the flame retardancy is insufficient, and 3.0 parts by weight. If the ratio exceeds the above range, the fluidity will decrease, impairing the melt dripping property and adversely affecting the flame retardancy.
  • the processing temperature for kneading the flame-retardant styrenic resin composition of the present invention is suitably in the range of 180 ° C and 260 ° C.
  • the flame-retardant styrenic resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired. Examples are a melt dripping accelerator, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a colorant, a lubricant, a release agent, an antistatic agent, etc.
  • melt-dropping flame-retardant styrene-based resin yarn composition of the present invention will be specifically described based on Examples and Comparative Examples. It is not intended to be limiting.
  • HI-PS 100 parts by weight, compound (B), compound (C), antimony trioxide (D), and antioxidant are uniformly mixed by a speed mixer.
  • the mixture was kneaded with an extruder with an inner diameter of 20 mm ⁇ adjusted to 230 ° C, extruded from a die with a diameter of 3 mm ⁇ , immersed in water and cooled, and then pelletized to obtain a flame-retardant resin composition of the test compound. Obtained.
  • the obtained flame-retardant resin composition was injection-molded using an injection molding machine adjusted to 200 ° C. It was created. Flame retardancy, flexural modulus, heat distortion temperature, thermal stability, and light resistance were examined according to the following test methods. The results are shown in Tables 1 and 2.
  • Flame retardancy Performed according to UL-94 vertical test method. The thickness of the test piece was 3.2 mm. Flexural strength: The test piece was 3.2 mm thick, 12.7 mm wide and 127 mm long according to JI SK-7203-1982. The distance between supporting points is 68mm.
  • Heat deformation temperature The test piece was used in accordance with JIS K-7207-1983 using a thickness of 3.2 mm, a width of 12.7 mm and a length of 127 mm. The distance between the fulcrums was 100 mm, the load was 18.5 kg, and the temperature when the deformation reached 0.26 mm was set.
  • Test pieces were 3.2 mm wide and 40 mm square, heated by a hot press at 230 ° C for 30 minutes, and represented by the color difference before and after the test.
  • the symbols in the table are as follows.
  • Antioxidant Irganox B225 (manufactured by Ciba Specialty Chemicals)

Landscapes

  • 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

L'invention concerne une composition de plastique ignifuge. Cette composition contient (A) une matière plastique de styrène résistant aux chocs, (B) un composé tris(di- ou tri-bromophénoxy)triazine présentant un point de fusion supérieur ou égal à 170°C, (C) un ester phosphorique présentant un point de fusion supérieur ou égal à 170°C et dont l'un au moins des résidus d'ester est un groupe tribromonéopentyle, et (D) un trioxyde d'antimoine.
PCT/JP2004/006367 2003-05-20 2004-05-12 Composition de resine styrene ignifuge WO2004104091A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-141546 2003-05-20
JP2003141546A JP2004346105A (ja) 2003-05-20 2003-05-20 溶融滴下性難燃スチレン系樹脂組成物

Publications (1)

Publication Number Publication Date
WO2004104091A1 true WO2004104091A1 (fr) 2004-12-02

Family

ID=33475028

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/006367 WO2004104091A1 (fr) 2003-05-20 2004-05-12 Composition de resine styrene ignifuge

Country Status (3)

Country Link
JP (1) JP2004346105A (fr)
TW (1) TW200502293A (fr)
WO (1) WO2004104091A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2657288B1 (fr) * 2010-12-24 2015-08-26 Toyo Styrene Co., Ltd. Composition ignifuge de résine de styrène et récipient de cartouche de toner produit à partir de celle-ci

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1112416A (ja) * 1997-06-23 1999-01-19 Asahi Chem Ind Co Ltd スチレン系樹脂組成物を射出成形して成るｔｖハウジング
JPH11323064A (ja) * 1998-05-14 1999-11-26 Mitsubishi Chemical Corp 難燃性スチレン系樹脂組成物
JP2002003688A (ja) * 2000-06-22 2002-01-09 A & M Styrene Co Ltd 難燃性透明ゴム変性スチレン系樹脂組成物
JP2002097336A (ja) * 2000-09-26 2002-04-02 A & M Styrene Co Ltd 電子機器筐体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1112416A (ja) * 1997-06-23 1999-01-19 Asahi Chem Ind Co Ltd スチレン系樹脂組成物を射出成形して成るｔｖハウジング
JPH11323064A (ja) * 1998-05-14 1999-11-26 Mitsubishi Chemical Corp 難燃性スチレン系樹脂組成物
JP2002003688A (ja) * 2000-06-22 2002-01-09 A & M Styrene Co Ltd 難燃性透明ゴム変性スチレン系樹脂組成物
JP2002097336A (ja) * 2000-09-26 2002-04-02 A & M Styrene Co Ltd 電子機器筐体

Also Published As

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JP2004346105A (ja) 2004-12-09
TW200502293A (en) 2005-01-16

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