JPH04149266A - Non-halogen-based flame retardant resin composition - Google Patents
Non-halogen-based flame retardant resin compositionInfo
- Publication number
- JPH04149266A JPH04149266A JP27337990A JP27337990A JPH04149266A JP H04149266 A JPH04149266 A JP H04149266A JP 27337990 A JP27337990 A JP 27337990A JP 27337990 A JP27337990 A JP 27337990A JP H04149266 A JPH04149266 A JP H04149266A
- Authority
- JP
- Japan
- Prior art keywords
- pts
- weight
- resin
- resin composition
- rubber
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- 239000003063 flame retardant Substances 0.000 title claims abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 26
- 239000002480 mineral oil Substances 0.000 claims abstract description 15
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 abstract description 16
- 239000005060 rubber Substances 0.000 abstract description 13
- -1 poly(2,6- dimethyl-1,4-phenylene ether) Polymers 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 6
- 241001082241 Lythrum hyssopifolia Species 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 15
- 239000002245 particle Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- UQQALTRHPDPRQC-UHFFFAOYSA-N nitrogen tribromide Chemical compound BrN(Br)Br UQQALTRHPDPRQC-UHFFFAOYSA-N 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical class CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野コ 本発明は難燃性に優れた樹脂組成物に関する。[Detailed description of the invention] [Industrial application fields] The present invention relates to a resin composition with excellent flame retardancy.
更に詳しくは、ハロゲン化合物を含まない難燃性スチレ
ン系樹脂組成物に関する。More specifically, the present invention relates to a flame-retardant styrenic resin composition that does not contain a halogen compound.
［従来の技術と発明が解決しようとする課題］ＨＩＰＳ
に代表されるゴム変性ビニル芳香族樹脂は、成形性、寸
法安定性に優れることに加え、耐衝撃性、剛性、電気絶
縁性に優れていることから、家電部品、ＯＡ機器部品を
始めとする多岐の分野で使用されるに至っている。[Problems to be solved by conventional technology and invention] HIPS
Rubber-modified vinyl aromatic resins, represented by , have excellent moldability and dimensional stability, as well as impact resistance, rigidity, and electrical insulation properties, so they are used in home appliance parts, OA equipment parts, and other applications. It has come to be used in a wide variety of fields.
近年かかる分野で使用されるプラスチック材料に対し、
安全上の問題から、難燃性の要求が高まってきており、
種々の難燃性規格が定められている。易燃性のかかる樹
脂に難燃性を付与する方法として、種々の方法が考案さ
れているが、ごく−射的には、難燃効果の高い臭素化合
物などのハロゲン化合物、及び必要に応じ酸化アンチモ
ンを樹脂に添加する方法が採用されている。臭素化合物
としては、デカブロモジフェニルエーテル、テトラブロ
モビスフェノールＡ、ブロム化フタルイミドなどの核臭
素置換芳香族化合物が知られているが、これらの難燃剤
の添加による方法は、優れた難燃性が得られるものの、
衝撃強度や熱変形温度が低下し、場合によっては難燃剤
が樹脂の成形品表面にブリード・アウトして成形品外観
を悪化させたりするなどの問題を有していた。更にまた
樹脂の成形時に、ハロゲン化合物の熱分解により、人体
に有毒なガスを発生したり、金型及びスクリューを腐食
するなどの問題を有していた。For plastic materials used in such fields in recent years,
Due to safety issues, the demand for flame retardant properties is increasing.
Various flame retardant standards have been established. Various methods have been devised to impart flame retardancy to such easily combustible resins, but most commonly, halogen compounds such as bromine compounds, which have a high flame retardant effect, and oxidation as necessary. A method has been adopted in which antimony is added to the resin. Nuclear bromine-substituted aromatic compounds such as decabromodiphenyl ether, tetrabromobisphenol A, and brominated phthalimide are known as bromine compounds, but methods that involve the addition of these flame retardants provide excellent flame retardancy. of things,
There have been problems such as a decrease in impact strength and heat distortion temperature, and in some cases, flame retardant may bleed out onto the surface of the resin molded product, deteriorating the appearance of the molded product. Furthermore, during molding of the resin, thermal decomposition of the halogen compound generates gas toxic to the human body and corrodes the mold and screw.
このためハロゲン化合物を用いないて難燃化する方法が
検討されている。かかる方法として、樹脂に水酸化アル
ミニウム、水酸化マグネシウムなどの水和金属化合物を
添加する方法が知られているが、充分な難燃性を得るた
めには、上記水和金属化合物を多量に添加する必要があ
り、樹脂本来の特性が失われるという欠点を有していた
。For this reason, methods of making flame retardant without using halogen compounds are being considered. As such a method, a method of adding a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide to the resin is known, but in order to obtain sufficient flame retardancy, it is necessary to add a large amount of the hydrated metal compound. This has the disadvantage that the original properties of the resin are lost.
一方このような水和金属化合物を用いない方法として、
熱可塑性樹脂にフェノール・アルデヒド樹脂、有機窒素
化合物、有機リン化合物を配合してなる難燃性樹脂組成
物（米国特許明細書簡４．６３２．９４６号明細書）
、 ＡＢＳ樹脂に赤リン、メラミン、熱架橋硬化性樹脂
を配合してなる′Ｎ燃性樹脂組成物（特開昭６ｌ−２９
１６４３）が開示されている。しかしながら、かかる方
法では多種多量の添加剤を必要とし、樹脂本来の特性を
損なうという問題があった。On the other hand, as a method that does not use such hydrated metal compounds,
Flame-retardant resin composition formed by blending a thermoplastic resin with a phenol/aldehyde resin, an organic nitrogen compound, and an organic phosphorus compound (U.S. Patent Specification Letter No. 4.632.946)
, 'N flammable resin composition made by blending ABS resin with red phosphorus, melamine, and thermally crosslinked curable resin (Japanese Patent Application Laid-open No. 61-29
1643) has been disclosed. However, this method requires a large amount of various additives, which has the problem of impairing the original properties of the resin.
一方、米国特許第４．４６１．８７４号明細書には、ボ
ッフェニレンエーテル、スチレン系樹脂及び赤リンより
なる難燃性樹脂組成物が開示されている。On the other hand, US Pat. No. 4,461,874 discloses a flame-retardant resin composition comprising bophenylene ether, styrene resin, and red phosphorus.
上記樹脂組成物は、ハロゲン化合物を用いない有用なｎ
Ｐ性耐樹脂材料はあるが、流動性の低いボッフェニレン
エーテルを多量に含んでいるため、樹脂組成物の成形性
が劣るという問題があった。The above resin composition is a useful n
Although P-based resin-resistant materials exist, they contain a large amount of bophenylene ether, which has low fluidity, and therefore have a problem in that the moldability of the resin composition is poor.
［課題を解決するための手段］
本発明者等は、）ＩＮ’ｓに代表されるゴム変性ビニル
芳香族樹脂と、ポリフェニレンエーテル及び赤リンより
なる難燃性樹脂の流動性を改善すべく鋭意検荊した結果
、上記ポリフェニレンエーテル樹脂が特定範囲の還元粘
度を有する場合に、上記問題を効率良く解決することが
出来ることを見出し本発明を完成するに至った。[Means for Solving the Problems] The present inventors have made efforts to improve the fluidity of a flame-retardant resin consisting of a rubber-modified vinyl aromatic resin represented by IN's, polyphenylene ether, and red phosphorus. As a result of investigation, it was found that the above problem can be efficiently solved when the polyphenylene ether resin has a reduced viscosity within a specific range, and the present invention has been completed.
すなわち本発明は、
Ａ）ゴム変性ビニル芳香族樹脂９７〜７５重量部、Ｂ）
ポリフェニレンエーテル３〜２５ｍｔｍの合計１（］（
］重量部に対し
Ｃ）赤リン１〜１５重量部
Ｄ）ミネラルオイル０〜１０重量部
を配合して成る樹脂組成物であって、前記ポリフェニレ
ンエーテルの還元粘度が０．２０〜０．５０ｄｌ／ｇノ
範囲にあることを特徴とする成形性に優れた難燃性樹脂
組成物を提供するものである。That is, the present invention comprises: A) 97 to 75 parts by weight of rubber-modified vinyl aromatic resin; B)
Polyphenylene ether 3-25mtm total 1(](
] C) 1 to 15 parts by weight of red phosphorus D) 0 to 10 parts by weight of mineral oil, wherein the reduced viscosity of the polyphenylene ether is 0.20 to 0.50 dl/ The object of the present invention is to provide a flame-retardant resin composition with excellent moldability, which is characterized by being in the .
以下、本発明の内容を順を追って説明する。Hereinafter, the contents of the present invention will be explained in order.
本発明の樹脂組成物は、前記Ａ成分に言うゴム変性ビニ
ル芳香族樹脂及び前記Ｂ成分に言うポリフェニレンエー
テルより構成される樹脂成分と難燃性付与成分である赤
リン及び必要に応じて加えられる流動性促進剤のミネラ
ルオイルよりなるが、上記樹脂成分に占めるＢ成分の割
合は、３〜２５重量％の範囲である。Ｂ成分の割合が３
重量％に満だないものは、難燃性が十分でなく、２５重
置型を越えるものは、成形加工性が著しく劣ったものと
なり、本発明の範囲に属さない６Ｂ成分のより好ましい
範囲は、５〜１５重量％である。The resin composition of the present invention comprises a resin component consisting of a rubber-modified vinyl aromatic resin referred to as component A and a polyphenylene ether referred to as component B, red phosphorus as a flame retardant imparting component, and optionally added. It consists of mineral oil as a fluidity promoter, and the proportion of component B in the resin component is in the range of 3 to 25% by weight. The proportion of B component is 3
If the amount is less than 25% by weight, the flame retardance will be insufficient, and if it exceeds 25% by weight, the molding processability will be extremely poor. , 5 to 15% by weight.
つぎに、本発明のＢ成分に言うポリフェニレンエーテル
（以下ＰＰＥと略称する６）とは、下記−数式で示され
る結合単位からなるホモ重合体及び／または共重合体で
ある；
（ここに、Ｒ，、Ｒ，、Ｒ，、Ｒ，は、それぞれ水素、
炭化水素、または置換炭化水素基からなる群から選択さ
れるものであり、互いに同一でも異なっていてもよい。Next, polyphenylene ether (hereinafter abbreviated as PPE 6) referred to as component B of the present invention is a homopolymer and/or copolymer consisting of bonding units represented by the following formula; ,,R,,R,,R,respectively represent hydrogen,
They are selected from the group consisting of hydrocarbons or substituted hydrocarbon groups, and may be the same or different from each other.
）
このＰＰＥの具体的な例としては、ポリ（２，６ジメチ
ルー１．４−フェニレンエーテル） 、 ２．６−シメ
チルフエノールと２．３．６− トリメチルフェノール
との共重合体等が好ましく、中でも、ポリ（２゜６−シ
メチルー１．４−フェニレンエーテル）が好ましい。) Specific examples of this PPE include poly(2,6 dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, etc. Among these, poly(2°6-dimethyl-1,4-phenylene ether) is preferred.
かかるＰＰＨの製造方法は公知の方法で得られるもので
あれば特に限定されるものではなく、例えば、米国特許
第３．３０６．８７４号明細書記載の方法による第一銅
塩とアミンのコンプレ・ンクスを触媒として用い、例え
ば２．６キシレノールを酸化重合することにより容易に
製造出来、そのほかにも米国特許第３．３０６．８７５
号明細書、米国特許第３．２５７．３５７号明細書、米
国特許第３．２５７．３５８号明細書及び特公昭５２−
１７８８０号公報、特開昭５０−５１１９７号公報に記
載された方法で容易に製造出来る。The method for producing PPH is not particularly limited as long as it can be obtained by a known method. For example, a complex of a cuprous salt and an amine may be produced by the method described in U.S. Pat. No. 3,306,874. It can be easily produced by oxidative polymerization of, for example, 2.6-xylenol using Nx as a catalyst.
specification, U.S. Patent No. 3.257.357, U.S. Patent No. 3.257.358, and Japanese Patent Publication No. 1973-
It can be easily produced by the method described in JP-A No. 17880 and JP-A-50-51197.
本発明にて用いる上記ＰＰＥの還元粘度（０，５ｇ／ｄ
Ｉ、クロロフォルム溶液、３０℃測定）は、常用の変
性ポリフェニレンエーテル樹脂におけるＰＰＥの最適還
元粘度範囲と異なり、０．２０〜０．５０ｄｌ／ｇの範
囲にあることが必要であり、０．３０〜ｏ、４５ｄ、ｌ
／ｇの範囲にあることがより好ましい。還元粘度が０２
０ｄｌ／ｇに満たない場合には、最終的に得られる樹脂
組成物の衝撃強度が劣り、０．５０ｄｌ／ｇを越える場
合には、流動性が劣ったものとなる。Reduced viscosity of the above PPE used in the present invention (0.5 g/d
I, chloroform solution, measured at 30°C) is different from the optimum reduced viscosity range of PPE in commonly used modified polyphenylene ether resins, and needs to be in the range of 0.20 to 0.50 dl/g, and 0.30 to 0.50 dl/g. o, 45d, l
It is more preferable to be in the range of /g. Reduced viscosity is 02
If it is less than 0 dl/g, the final resin composition will have poor impact strength, and if it exceeds 0.50 dl/g, it will have poor fluidity.
ＰＰＥの還元粘度に関する上記要件を満たすための手段
としては、前記ＰＰＥの製造の際の触媒量の調整などを
挙げることが出来る。As a means for satisfying the above-mentioned requirements regarding the reduced viscosity of PPE, there may be mentioned adjustment of the amount of catalyst during the production of the PPE.
次に上記Ａ成分のゴム変性ビニル芳香族樹脂とは、ビニ
ル芳香族重合体よりなるマトリックス中にゴム状重合体
が粒子状に分散して成る重合体を言い、−射的にはゴム
状重合体をビニル芳香族単量体（及び不活性溶媒を加え
た液）に溶解し、撹拌下に塊状重合、塊状懸濁重合、ま
たは溶液重合を行ない、ゴム状重合体を析出、粒子化す
ることにより得られる。Next, the rubber-modified vinyl aromatic resin of component A refers to a polymer in which a rubber-like polymer is dispersed in the form of particles in a matrix made of a vinyl aromatic polymer. Dissolving the polymer in a vinyl aromatic monomer (and a liquid containing an inert solvent) and performing bulk polymerization, bulk suspension polymerization, or solution polymerization while stirring to precipitate and form a rubber-like polymer into particles. It is obtained by
上記のビニル芳香族単量体としては、又チレンのほか、
０−メチルスチレン、ｐ−メチルスチレン、ｍ−メチル
スチレン、２．４ジメチルスチレン、エチルスチレン、
ｐ−ターシャリ−ブチルスチレン等の核アルキル置換ス
チレン、α−メチルスチレン、α−メチル−ｐ−メチル
スチレン等のα−アルキル置換スチレン等を挙げること
ができるが、代表的なものはスチレンである。これらは
その２種以上を併用してもよい。In addition to tyrene, the above-mentioned vinyl aromatic monomers include
0-methylstyrene, p-methylstyrene, m-methylstyrene, 2.4 dimethylstyrene, ethylstyrene,
Nuclear alkyl-substituted styrenes such as p-tert-butylstyrene, α-alkyl-substituted styrenes such as α-methylstyrene, and α-methyl-p-methylstyrene can be mentioned, with styrene being a typical example. Two or more of these may be used in combination.
また前記ゴム状重合体としては、ポリブタジェン、スチ
レン−ブタジェン共重合体、ポリイソプレン、ブタジェ
ン・イソプレン共重合体、天然ゴム、エチレン・プロピ
レン共重合体等を挙げることができるが、−Ｍ的には、
ポリブタジェン、スチレン・ブタジェン共重合体が好ま
しい。Examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, ethylene-propylene copolymer, etc. ,
Polybutadiene and styrene-butadiene copolymers are preferred.
上言己ゴム変性ビニル芳香族樹脂中のゴム状重合体含量
について特に制約はないが一般的には４〜１５重歌％、
より好ましくは６〜ｌＯ重量％である。As stated above, there are no particular restrictions on the content of the rubbery polymer in the rubber-modified vinyl aromatic resin, but it is generally 4 to 15%,
More preferably, it is 6 to 10% by weight.
またゴム変性ビニル芳香族樹脂中のゴム状重合体部分を
除いたマトリックス部分の還元粘度は常用の０゜４０〜
１．２０ｄｌ／ｇの範囲に制御されるが、好ましくは０
−５０〜０．８０ｄｌ／ｇの範囲である。In addition, the reduced viscosity of the matrix part excluding the rubbery polymer part in the rubber-modified vinyl aromatic resin is the usual 0°40~
Controlled within the range of 1.20 dl/g, preferably 0
-50 to 0.80 dl/g.
次ぎにゴム変性ビニル芳香族樹脂中のゴム粒子の平均粒
子径は、０．５〜６０ミクロンの範囲に制御される。上
記ゴム粒子径は、ゴム変性ビニル芳香族樹脂の超薄切片
法による透過型電子顕微鏡写真を撮影し、１．０００個
のゴム粒子についでその直径を求め、次式に従って求め
る。Next, the average particle diameter of the rubber particles in the rubber-modified vinyl aromatic resin is controlled within the range of 0.5 to 60 microns. The rubber particle diameter is determined by taking a transmission electron micrograph of the rubber-modified vinyl aromatic resin using an ultra-thin section method, determining the diameter of 1,000 rubber particles, and determining the diameter according to the following formula.
Σｎ、Ｄ ゴム粒子径： Σ ｎ＋Ｄ＋ 但し Ｄ、 分散ゴム粒子の直径６ ｎ１：直径り、のゴム粒子の個数。Σn,D Rubber particle size: Σ n+D+ However, D, diameter of dispersed rubber particles 6 n1: Number of rubber particles with diameter.
また前記ゴム変性ビニル芳香族樹脂中のゲル含量（トル
エン不溶分）は、常法の１５〜４０重量％に調整される
が、より好ましくは２０〜３５重量％である。Further, the gel content (toluene-insoluble content) in the rubber-modified vinyl aromatic resin is adjusted to 15 to 40% by weight by a conventional method, and more preferably 20 to 35% by weight.
次に本発明では、第三の成分として赤リンを用いる６赤
リンとしては、微粒子状のものであれば良いが、取り扱
いの上からは、表面を樹脂、ミネラルオイル、または金
属水和物にてコーティングしたものが好ましい６
上記赤リンの配合量としては、前記Ａ成分及びＢ成分よ
りなる樹脂成分１００重量部に対し、１〜１５重皿部で
あることが必要である。配合量が１重量部に濯だない場
合には、充分な難燃性が得られない。また配合量が１５
重量部を越える場合には、最終的に得られる組成物の衝
撃強度、成形性及び外観が劣ったものとなる。より好ま
しい配合量は３〜８重量部である。Next, in the present invention, red phosphorus is used as the third component.6 Red phosphorus may be in the form of fine particles, but from the viewpoint of handling, it is necessary to coat the surface with resin, mineral oil, or metal hydrate. Preferably, the amount of the red phosphorus is 1 to 15 parts by weight per 100 parts by weight of the resin component consisting of the A component and the B component. If the amount is less than 1 part by weight, sufficient flame retardancy cannot be obtained. Also, the blending amount is 15
If the amount exceeds 1 part by weight, the impact strength, moldability, and appearance of the final composition will be poor. A more preferable amount is 3 to 8 parts by weight.
本発明においては上記Ａ１．Ｂ１．Ｃ）成分に、必要に
応し、Ｄ）ミネラルオイルを、Ａ、１．Ｂ１１成分の合
計１００重量部に対し、１０重量部を上限に加えること
ができる。ミネラルオイルの添加量が１０重量部を越え
ると、最終的に得られる樹脂組成物の熱変形温度が低下
し、また成形加工時に金型表面に油状の物質が蓄積する
ようになり好ましくない、ミネラルオイルのより好まし
い添加量は、３〜６重量部である。ミネラルオイルとし
ては常用のものを使用することができるが、ｉ ０ｍ＋
ｎＨｇにおける初留点が２１０℃以上のものがより好ま
しい、このような条件を満たすミネラルオイルとしては
、例えばエッソ石油■製のミネラルオイルであるクリス
トール３５２などを挙げることが出来る。また上記ミネ
ラルオイルの全量もしくはその一部を前記Ｂ成分のゴム
変性ビニル芳香族樹脂を重合する際に、その重合液中に
投入して、ミネラルオイル含有のゴム変性ビニル芳香族
樹脂を調整し、最終的に得られる樹脂組成物中のミネラ
ルオイルの含有量を調整することもてきる。In the present invention, the above A1. B1. C) Ingredients, if necessary, add D) mineral oil to A.1. Up to 10 parts by weight can be added to a total of 100 parts by weight of the B11 component. If the amount of mineral oil added exceeds 10 parts by weight, the heat distortion temperature of the final resin composition will decrease, and oily substances will accumulate on the mold surface during molding, which is undesirable. A more preferable amount of oil added is 3 to 6 parts by weight. You can use commonly used mineral oil, but i 0m+
It is more preferable to have an initial boiling point of 210° C. or higher in nHg. Examples of mineral oils that meet these conditions include Crystoll 352, a mineral oil manufactured by Esso Oil ■. Further, when polymerizing the rubber-modified vinyl aromatic resin of the component B, the entire amount or a part of the mineral oil is added to the polymerization solution to prepare a mineral oil-containing rubber-modified vinyl aromatic resin, It is also possible to adjust the content of mineral oil in the resin composition finally obtained.
以上のＡ−Ｃ（またはＡ−Ｃ及びＤ）の各成分の配合方
法に特に制約は無く、押出し機、ニーダ、バンバリーミ
キサ−等の常用の混合機により、上記成分を溶融混合す
ればよいにの際、出来得れば、Ｃ成分の混合に先立ち、
予めＡ成分及びＢ成分の混線りを実施し、然るのちＣ成
分を加えて？ｌＩＩりを実施するほうがＢ成分が均一に
分散し好ましい。There are no particular restrictions on the method of blending each component of the above A-C (or A-C and D), and the above components may be melt-mixed using a commonly used mixer such as an extruder, kneader, or Banbury mixer. If possible, prior to mixing component C,
Mix A component and B component in advance, then add C component? It is preferable to carry out the second process because the B component is uniformly dispersed.
以下実施例により本発明を更に詳しく説明する６［実施
例１
以下の実施例、比較例では、下記の試料を用いた。The present invention will be explained in more detail with reference to Examples below.6 [Example 1] In the following Examples and Comparative Examples, the following samples were used.
［参考例：ゴム変性ビニル芳香族樹脂の調整］［参考例
１−ゴム変性ビニル芳香族樹脂、ＳＩＪ下記組成の重合
原液を調整した。[Reference Example: Preparation of Rubber Modified Vinyl Aromatic Resin] [Reference Example 1 - Rubber Modified Vinyl Aromatic Resin, SIJ A polymerization stock solution having the following composition was prepared.
・ポリブタジェンゴム１８．０重量部
（旭化成工業株ＮＦ−３５Ａ）
・スチレン ： ７７．０重量部・エチルベン
ゼン ：１５．ｏｉｉｔ部・ ａ −メチルスチレン
タイマー ：ｏ、０６重量部・ ステアリル３〜
（３，５−ジターシャリブチル−４−ヒドロキシフェニ
ル）−
プロピオ半一） ： ０．１
５重量部次いで上記重合原液を攪拌棒を備えた多段式反
応機に連続的に送液し、重合を行った。ゴム粒子の平均
粒子径が２．５ミ９０ン、最終反応掻出の固形分濃度が
８０重量％となるように、重合温度及び撹拌数を調節し
た。引き続き重合液を脱揮装置に導き、ゴム含量１０重
量％のゴム変性ビニル芳香族樹脂を得た。得られたゴム
変性ビニル芳香族樹脂を分析した結果、マトリックスの
還元粘度ｏ、 ７２ｄｌ／ｇ、ゲル含量は２８重量％で
あった。・Polybutadiene rubber 18.0 parts by weight (Asahi Kasei Kogyo NF-35A) ・Styrene: 77.0 parts by weight ・Ethylbenzene: 15. oiit part・a-methylstyrene timer: o, 06 parts by weight・stearyl 3～
(3,5-ditertiarybutyl-4-hydroxyphenyl)-propio-1): 0.1
5 parts by weight of the above polymerization stock solution was then continuously fed into a multistage reactor equipped with a stirring bar to carry out polymerization. The polymerization temperature and the number of stirring were adjusted so that the average particle diameter of the rubber particles was 2.5 mm and the solid content concentration of the final reaction scrape was 80% by weight. Subsequently, the polymerization liquid was led to a devolatilization device to obtain a rubber-modified vinyl aromatic resin with a rubber content of 10% by weight. Analysis of the obtained rubber-modified vinyl aromatic resin revealed that the reduced viscosity of the matrix was 72 dl/g and the gel content was 28% by weight.
［参考例２−ＰＰＥ （Ｐｉ）の調整］酸素吹き込み口
を反応種底部に有し、内部に冷却用コイル、撹拌羽根を
有するステンレス製反応機の内部を窒素で十分置換した
のち、臭化第２銅３２．６ｇ 、ジ−ｎ−ブチルアミン
９１５ｇ 、及びトルエン２０Ｉ２、ｎ−ブクノール１
１、メタノール４Ｉ２の混合溶媒に２．６−キシレノー
ル８．７５ｋｇを溶解して反応機に仕込んだ、撹拌しな
がら反応機内部に酸素を吹き込み続け、内温を３０℃に
制御しながら１８０分間重合を行なった０重合終了後、
析出したポリマーを口割しメタノール／塩酸混合液を添
加し、ポリマー中の残存触媒を分解し、さらにメタノー
ルを用いて十分洗浄した後乾燥し、粉末状のＰＰＥを得
た。還元粘度は０．４５ｄｌ／ｇであった６［参考例３
−ＰＰＥ （Ｐ２）の調整］参考例２において、触媒量
及び酸素吹き込み皿を変えた他は同様にしてＰＰＥを得
た。還元粘度は０．３５ｄｌ／ｇであった。[Reference Example 2 - Preparation of PPE (Pi)] After sufficiently purging the inside of a stainless steel reactor with an oxygen inlet at the bottom of the reactant, a cooling coil, and a stirring blade inside, nitrogen bromide was added. 2 copper 32.6 g, di-n-butylamine 915 g, and toluene 20I2, n-buknol 1
1. 8.75 kg of 2.6-xylenol was dissolved in a mixed solvent of methanol 4I2 and charged into the reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was carried out for 180 minutes while controlling the internal temperature at 30°C. After the completion of 0 polymerization,
The precipitated polymer was divided into portions, a methanol/hydrochloric acid mixture was added to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and then dried to obtain powdered PPE. The reduced viscosity was 0.45 dl/g6 [Reference Example 3
- Preparation of PPE (P2)] PPE was obtained in the same manner as in Reference Example 2, except that the amount of catalyst and the oxygen blowing pan were changed. The reduced viscosity was 0.35 dl/g.
［参考例４−ＰＰＥ （Ｐ３）の調整］参考例２におい
て、触媒量及び酸素吹き込み量を変えた他は同様にして
ＰＰＥを得た。還元粘度は０．５５ｄｌ／ｇであった。[Reference Example 4 - Preparation of PPE (P3)] PPE was obtained in the same manner as in Reference Example 2 except that the amount of catalyst and the amount of oxygen blown were changed. The reduced viscosity was 0.55 dl/g.
［参考例５−ＰＰＥ （Ｐ４）の調整］参考例２におい
て、触媒量及び酸素吹き込み量を変えた他は同様にして
ＰＰＥを得た。還元粘度は０．１５ｄｌ／ｇであった。[Reference Example 5 - Preparation of PPE (P4)] PPE was obtained in the same manner as in Reference Example 2, except that the amount of catalyst and the amount of oxygen blown were changed. The reduced viscosity was 0.15 dl/g.
［実施例１〜５、比較例１〜６］
参考例にて調整したゴム変性ビニル芳香族樹脂ＰＰＥ、
赤リン（＃ｌ化学工業■製、ノーバレット＃ １２０．
赤リン含量８５重量％）及びミネラルオイル（エッソ石
油■製のミネラルオイル、クリストール３５２ 、ｌＯ
＋＋ｍＨｇにおける初留点２３７°Ｃ）を表１の割合に
て配合し、２軸押出機にて混練りし、樹脂組成物のベレ
ットを得た１次いで、射出成形機にて、試験片を作成し
、機械的物性及び燃焼性試験を行なった。なお物性、燃
焼性試験は下記方法に従った。[Examples 1 to 5, Comparative Examples 1 to 6] Rubber modified vinyl aromatic resin PPE prepared in Reference Example,
Red phosphorus (manufactured by #l Kagaku Kogyo ■, No Bullet #120.
red phosphorus content 85% by weight) and mineral oil (mineral oil manufactured by Esso Oil, Crystoll 352, lO
++ initial boiling point 237°C at mHg) were blended in the proportions shown in Table 1 and kneaded in a twin-screw extruder to obtain pellets of the resin composition.Next, test pieces were created in an injection molding machine. Then, mechanical properties and flammability tests were conducted. The physical properties and flammability tests were conducted according to the following methods.
・アイゾツト衝撃強度： ＡＳＴＭ Ｄ−２５６（／ブ
チ付き）・曲げ弾性率 ： ＡＳＴＭ Ｄ−７９
０・メルトフローレート： ｌ５Ｏ−Ｒ１１３３（２０
０℃、 ５ｋｇ荷重）
： ＵＬ−９４（１／１２インチ）
・燃焼性
結果を表１に示す。・Izotsu impact strength: ASTM D-256 (with /button) ・Flexural modulus: ASTM D-79
0. Melt flow rate: l5O-R1133 (20
0°C, 5kg load): UL-94 (1/12 inch) - Flammability results are shown in Table 1.
（以下余白）
［実施例６］
実施例１の樹脂組成物を用いて、射出成形機東芝機械■
製Ｉ ３８００Ｂ−７５）にて、シリンダー温度２４０
℃、金型温度４５℃の条件で、平均「厚３ＩＩＩ！Ｉの
、テレビ受像機外殻部品の成形体を得ｌ［比較例７コ
実施例６において、実施例１の樹脂組成物にＸえて、比
較例１の樹脂組成物を用いる他は、同旧の操作を行った
が、樹脂の流動性が悪く、成形しを得ることが出来なか
った。(Left below) [Example 6] Using the resin composition of Example 1, injection molding machine Toshiba Machine ■
I 3800B-75), cylinder temperature 240
℃ and a mold temperature of 45℃, a molded body of a television receiver outer shell part having an average thickness of 3III!I was obtained. In addition, the same and old operations were carried out except that the resin composition of Comparative Example 1 was used, but the fluidity of the resin was poor and it was not possible to obtain a molded product.
［実施例７］
実施例６において、実施例１の樹脂組成物に協えて、実
施例５の樹脂組成物を用い、シリンダー温度を２３０℃
とする他は、同様の操作を行ない、良好な成形体を得た
。[Example 7] In Example 6, the resin composition of Example 5 was used in addition to the resin composition of Example 1, and the cylinder temperature was set at 230°C.
A good molded product was obtained by performing the same operation except for the following.
（以下余白）
［発明の効果］
表１に明らかなよう１４二本発明の樹脂組成物は衝撃強
度、ｎ燃性及び流動性に優れたものであり、射出成形用
素材として有用である。また本発明の樹脂組成物は、特
に流動性に優れているのでテレビ受像機の外殻などの大
型成形品を得るのに適しでいる。(The following is a blank space) [Effects of the Invention] As is clear from Table 1, the resin composition of the present invention has excellent impact strength, flammability, and fluidity, and is useful as a material for injection molding. Furthermore, the resin composition of the present invention has particularly excellent fluidity and is therefore suitable for producing large molded products such as the outer shell of a television receiver.
特許出願入 旭化成Ｔ業株式会社Patent application filed Asahi Kasei T-gyo Co., Ltd.
Claims (1)
０重量部に対し Ｃ）赤リン１〜１５重量部 Ｄ）ミネラルオイル０〜１０重量部 を配合して成る樹脂組成物において、前記ポリフェニレ
ンエーテルの還元粘度が０．２０〜０．５０ｄｌ／ｇの
範囲にあることを特徴とする難燃性樹脂組成物。[Claims] 1) A) 97 to 75 parts by weight of a rubber-modified vinyl aromatic resin, B) 3 to 25 parts by weight of polyphenylene ether, a total of 10 parts by weight.
0 parts by weight of C) 1 to 15 parts by weight of red phosphorus D) 0 to 10 parts by weight of mineral oil, wherein the polyphenylene ether has a reduced viscosity of 0.20 to 0.50 dl/g. A flame-retardant resin composition characterized in that it is within the range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27337990A JPH0689207B2 (en) | 1990-10-15 | 1990-10-15 | Non-halogen flame retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27337990A JPH0689207B2 (en) | 1990-10-15 | 1990-10-15 | Non-halogen flame retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04149266A true JPH04149266A (en) | 1992-05-22 |
| JPH0689207B2 JPH0689207B2 (en) | 1994-11-09 |
Family
ID=17527080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27337990A Expired - Fee Related JPH0689207B2 (en) | 1990-10-15 | 1990-10-15 | Non-halogen flame retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689207B2 (en) |
-
1990
- 1990-10-15 JP JP27337990A patent/JPH0689207B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689207B2 (en) | 1994-11-09 |
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