JPS62263247A - Flame-retarded resin composition - Google Patents
Flame-retarded resin compositionInfo
- Publication number
- JPS62263247A JPS62263247A JP10666286A JP10666286A JPS62263247A JP S62263247 A JPS62263247 A JP S62263247A JP 10666286 A JP10666286 A JP 10666286A JP 10666286 A JP10666286 A JP 10666286A JP S62263247 A JPS62263247 A JP S62263247A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- red phosphorus
- parts
- styrene
- composition
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 17
- 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 claims abstract description 16
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 poly(2,6-dimethyl-1,4-phenylene) Polymers 0.000 claims abstract description 8
- 229920005669 high impact polystyrene Polymers 0.000 claims abstract 2
- 239000004797 high-impact polystyrene Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 31
- 229920001890 Novodur Polymers 0.000 claims description 5
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000005062 Polybutadiene Substances 0.000 abstract description 2
- 229920002857 polybutadiene Polymers 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 241001082241 Lythrum hyssopifolia Species 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000011115 styrene butadiene Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 241000590631 Biblis hyperia Species 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing 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
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、樹脂組成物が本来持つ性質を損なうことなし
に難燃化された樹脂組成物に関する。更に詳しくは、？
リフエニレンエーテル系樹脂とスチレン系樹脂とよシな
る樹脂組成物と架橋−リマーあるいは金属酸化物および
架橋ポリマーで被覆され九赤リンとよシなる加工性、耐
衝撃性、色調等がすぐれ、成形金型を腐蝕しない、経済
性にもすぐれた難燃性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition that has been made flame retardant without impairing its inherent properties. For more details?
It is coated with resin compositions and crosslinked remers or metal oxides and crosslinked polymers such as rifhenylene ether resins and styrene resins, and has excellent processability, impact resistance, color tone, etc., and is moldable. This invention relates to a flame-retardant resin composition that does not corrode molds and is highly economical.
ポリフェニレンエーテル系樹脂トスチレン系樹脂よシな
る樹脂組成物は、機械的物性、熱的物性、電気的物性等
に優れ、家電部品、配電部品、自動車部品等に広く用い
られ、近年その需要の伸びは著しく、有用な材料である
。Resin compositions such as polyphenylene ether resins and styrene resins have excellent mechanical, thermal, and electrical properties, and are widely used in home appliance parts, power distribution parts, automobile parts, etc., and the demand for them has increased in recent years. It is an extremely useful material.
一方、樹脂に対する産業界の要求性能のひとつとして、
難燃化がめげられる。米国のＵＬ規格等に見られる如く
、樹脂の難燃化規制は厳しさを増し、その対応が求めら
れておシ、ポリフェニレンエーテル系樹脂とスチレン系
樹脂の樹脂組成物も例外ではない。On the other hand, as one of the performance requirements of the industry for resins,
Flame retardant efforts are unsuccessful. As seen in the UL standards in the United States, flame retardant regulations for resins are becoming increasingly strict, and compliance with these regulations is required, and resin compositions of polyphenylene ether resins and styrene resins are no exception.
この要求に答えるべく、該樹脂組成物に、芳香族リン酸
エステルを配合させたもの（特公昭５３−４１８号公報
、特開昭５３−７３２４８号公報）や、有機ハロゲン化
物、若しくは、有機ハロゲン化物と三酸化アンチモンを
併用し配合したもの（特開昭４８−７９４５号公報、特
開昭５１−７４０３８号公報、特開昭５２−１２８９４
６号公報）や、元素リンを配合し念もの（米国特許第３
、６６３ 、６５４号明細書）等の技術が公開されて
いるが、いずれも充分とは言えない。即ち芳香族リン酸
エステルを用いた場合の耐熱温度の低下、有機ハロゲン
化物、三酸化アンチそンを用い之場合の耐衝撃性の低下
や成形金型の腐蝕、三酸化アンチモンが医療周外劇物で
ある故の作業性の悪さ、元素リンを用いた場合の耐衝撃
性の低下や、樹脂の暗赤色化等、充分満足のゆく様々難
燃剤は開発されておらず、ポリフェニレンエーテル系樹
脂とスチレン系樹脂との樹脂組成物の優れ良性能を損う
事なく、難燃化する事は強く求められている。In order to meet this demand, resin compositions containing aromatic phosphate esters (Japanese Patent Publication No. 53-418, JP-A-53-73248), organic halides, or organic halogen Compounds of compound and antimony trioxide (JP-A-48-7945, JP-A-51-74038, JP-A-52-12894)
No. 6 Publication), and a medicine containing elemental phosphorus (U.S. Patent No. 3)
, 663 and 654) have been published, but none of them can be said to be sufficient. Namely, there is a decrease in heat resistance when aromatic phosphate esters are used, a decrease in impact resistance and corrosion of molding molds when organic halides and antisodium trioxide are used, and antimony trioxide causes medical problems. Various satisfactory flame retardants have not been developed, such as poor workability due to the use of polyphenylene ether resins, decreased impact resistance when using elemental phosphorus, and dark red coloring of the resin. There is a strong demand for flame retardancy without impairing the excellent performance of resin compositions with styrene resins.
〔問題点を解決するための手段および作用〕本発明は、
ポリフェニレンエーテル系樹脂とスチレン系樹脂との樹
脂組成物を難燃化するにあたシ、赤リンの優れた難燃付
与性に着目し、赤リン単独で使用した場合の耐衝撃性の
低下や、樹脂の暗赤色化、取扱い上の不安全性を回避す
る手段を鋭意検討し念結果、架橋ポリマーで被覆した赤
リンあるいは金属酸化物および架橋−リマーで被覆した
赤リンを配合することで、目的に合致した樹脂組成物が
得られることを見出し、本発明を完成した。[Means and effects for solving the problems] The present invention has the following features:
In order to make a resin composition of polyphenylene ether resin and styrene resin flame retardant, we focused on the excellent flame retardant properties of red phosphorus, and investigated the effects of reducing impact resistance when using red phosphorus alone. After careful consideration of methods to avoid the dark red coloring of the resin and unsafe handling, we have developed red phosphorus coated with a cross-linked polymer or red phosphorus coated with a metal oxide and a cross-linked rimer. The present invention was completed based on the discovery that a resin composition meeting the purpose could be obtained.
本発明によれば、ポリフェニレンエーテル系樹脂とスチ
レン系樹脂とよりなる樹脂組成物を赤リンで難燃化する
に際し、架橋−リマーで被覆した赤リンを配合すること
Ｋよって、樹脂組成物の耐熱温度および耐衝撃性を低下
する事なしに、難燃化することが出来る。かかる難燃化
された組成物は、暗赤色に着色しているため濃色系の着
色用に向いている。該樹脂組成物を難燃化するに際し、
金属酸化物および架橋ポリマーで被覆された赤リンを配
合することで、暗赤色に着色せず、明彩色等任意の色調
に着色可能な樹脂組成物を得る事が出来る。架橋ポリマ
ーで被覆した赤リンあるいは金属酸化物及び架橋ポリマ
ーで被覆された赤リンは、発火点が高く赤リンを単独で
扱う場合に起こる発火はなく取扱いが容易である。本発
明の技術は、従来技術で起こる、耐熱温度の低下、耐衝
撃性の低下や成形金型の腐蝕等のない難燃化された樹脂
組成物を安全に、しかも安価に提供するものである。According to the present invention, when flame retardant a resin composition made of a polyphenylene ether resin and a styrene resin with red phosphorus, the heat resistance of the resin composition is Flame retardant can be achieved without reducing temperature and impact resistance. This flame-retardant composition is colored dark red and is therefore suitable for deep coloring. When making the resin composition flame retardant,
By blending red phosphorus coated with a metal oxide and a crosslinked polymer, it is possible to obtain a resin composition that is not colored dark red but can be colored in any desired color tone such as bright color. Red phosphorus coated with a crosslinked polymer or red phosphorus coated with a metal oxide and a crosslinked polymer has a high ignition point and is easy to handle without causing the ignition that occurs when red phosphorus is handled alone. The technology of the present invention safely and inexpensively provides a flame-retardant resin composition that does not cause a decrease in heat resistance, a decrease in impact resistance, or corrosion of a molding die that occurs with conventional techniques. .
本発明にいうポリフェニレンエーテル系樹脂とは、一般
式
（式中、現、Ｒ鵞＊ ”３＊ Ｒ４１”５＋ Ｒ＝は炭
素数１〜４のアルキル基、アリール基、）・ログン、水
素等の一価の残基であシ、Ｒ１ｔ＊ ”＊は同時に水素
ではない。）を繰返し単位とし、構成単位が〔Ｃ〕又は
、〔Ｃ〕および〔Ｄ〕からなる単独重合体、あるいは共
重合体が使用できる。The polyphenylene ether resin referred to in the present invention refers to a polyphenylene ether resin having a general formula (wherein, R= "3* R41"5+ R= is an alkyl group having 1 to 4 carbon atoms, an aryl group, etc.), rogone, hydrogen, etc. A homopolymer or copolymer consisting of [C] or [C] and [D] as a repeating unit and the constituent units are [C] or [C] and [D]. can be used.
ポリフェニレンエーテル樹脂の単独重合体の代表例とし
ては、ポリ（２，６−−、７メチルー１．４−）ユニレ
ン）エーテル、ポＩＪ（２−メチル−６−エチル−１，
４−フエニレン）エーテル、ポリ（２，６−ジニチルー
１．４−）ユニレン）エーテル、ポリ（２−エチル−６
−ｎプロピル−１，４−フェニレン）エーテル、ぼり（
２，６−ジ−ｎプロピル−１゜４−フェニレン）エーテ
ル、ポリ（２−メチル−６−ｎブチル−１，４−）ユニ
レン）エーテル、ポリ（２−エチル−６−イツプロビル
ー１．４−）ユニレン）エーテル、ポリ（２−メチル−
６−クロル−１，４−）ユニレン）エーテル、ｚｖ（２
−メチル−６−ヒドロキシエチル−１，４−フェニレン
）エーテル、ポリ（２−メチル−６−クロロエチル−１
，４−フェニレン）エーテル等のホモポリマーが挙げら
れる。Typical examples of homopolymers of polyphenylene ether resins include poly(2,6-,7methyl-1,4-)unilene) ether, polyJ(2-methyl-6-ethyl-1,
4-phenylene) ether, poly(2,6-dinityl-1,4-)unilene) ether, poly(2-ethyl-6)
-npropyl-1,4-phenylene) ether, stream (
2,6-di-n-propyl-1°4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-)unilene) ether, poly(2-ethyl-6-itsuprobyl-1,4-) ) unilene) ether, poly(2-methyl-
6-chloro-1,4-)unilene) ether, zv(2
-Methyl-6-hydroxyethyl-1,4-phenylene)ether, poly(2-methyl-6-chloroethyl-1)
, 4-phenylene) ether and the like.
ポリフェニレンエーテル共重合体は、一般式（ここにＲ
３＊ Ｒ４ｅ Ｒ５＊ Ｒ＝は前記と同一の意味を有す
る。）で表わされる２、３．６−ドリメチルフエノール
等のアルキル置換フェノールと例えば、０−クレゾール
等とを共重合して得られるポリフェニレンエーテル構造
を主体としてなるポリフェニレンエーテル共重合体を包
含する。The polyphenylene ether copolymer has the general formula (where R
3*R4e R5*R= has the same meaning as above. ) includes a polyphenylene ether copolymer mainly having a polyphenylene ether structure obtained by copolymerizing an alkyl-substituted phenol such as 2,3,6-drimethylphenol with, for example, 0-cresol.
本発明に使用し得るスチレン系樹脂は、具体的には、次
式：
（式中、Ｒは水素、低級アルキルまたは７％ロゲンを示
し、Ｚはビニル、水素、塩素および低級アルキルよシな
る群から選択され、ｐは０〜５の整数である）で表わさ
れる化合物から誘導されるポリマ一単位を少なくとも２
５重量％有するものである。本明細書で使用する用語「
スチレン系樹脂」は、上記の式で定義され、例示すると
、ホモポリマー、例えばポリスチレンおよびポリクロロ
スチレン、変性ポリスチレン、例えばゴム変性ポリスチ
レンならびにスチレン含有コポリマー、例えばスチレン
ーアクリロニトリルコホリマー（ＳＡＮ ）、スチレン
ーブタジエンコテリマー、スチレン−アクリロニトリル
−ブタジェンコポリマー（ＡＢＳ）、ホリα−メチルス
チレン、エチルビニルベンゼンとジビニルベンゼンのコ
ポリマーなどを包含する。Specifically, the styrenic resin that can be used in the present invention has the following formula: and p is an integer of 0 to 5).
5% by weight. As used herein, the term “
"Styrenic resins" are defined in the above formula and include, by way of example, homopolymers such as polystyrene and polychlorostyrene, modified polystyrenes such as rubber-modified polystyrene and styrene-containing copolymers such as styrene-acrylonitrile copolymer (SAN), styrene-acrylonitrile copolymer (SAN), These include butadiene coterimer, styrene-acrylonitrile-butadiene copolymer (ABS), polyα-methylstyrene, copolymer of ethylvinylbenzene and divinylbenzene, and the like.
本発明に好適なスチレン何月１成分は、ゴム変性耐衝撃
性スチレン樹脂、例えば天然または合成ゴムで変性され
たポリスチレンである。尚、ここで言うゴム変性耐衝撃
性スチレン樹脂とは、ゴムにスチレンをグラフト重合し
たもの及び単にゴムと、４リスチレンを機械的に混練し
たものを包括する。A preferred styrene component for the present invention is a rubber-modified impact styrenic resin, such as polystyrene modified with natural or synthetic rubber. Note that the rubber-modified impact-resistant styrene resin referred to herein includes those obtained by graft polymerizing styrene onto rubber and those obtained by simply mechanically kneading rubber and 4-listyrene.
変性用合成ゴムは、例えば？リプタジエン、？リイソゾ
レン、ジエンと他のコモノマー、例えばスチレン、アク
リロニトリル、アクリル酸エステルなどとよシなシ、人
−Ｂ−人および人−ＢＷ（人はビニル芳香族、例えばス
チレン、Ｂはジエン、例えばブタジェン）のブロックコ
Ｉリマーを含むゴム状コポリマーならびにエチレン−プ
ロピレン−ジェンターポリマー（ＥＰＤＭ）ゴムなどで
ある。−リスチレンをブタジェンゴムで変性するのがも
つとも好適である。For example, what is the modified synthetic rubber? Liptadiene? Lysozolene, dienes and other comonomers such as styrene, acrylonitrile, acrylic esters etc., B-BW and BW (where B is a vinyl aromatic, e.g. styrene and B is a diene, e.g. butadiene). Rubbery copolymers, including block copolymers, and ethylene-propylene-genterpolymer (EPDM) rubbers. - It is also preferred to modify listyrene with butadiene rubber.
本発明にいう架橋ポリマーは、特に限定されるものでは
ないが、一般的にはスチレン系化合物、メタクリル酸エ
ステル類、アクリル酸エステル類または不飽和ニトリル
化合物等のラジカル重合可能なモノマーの重合体または
共重合体の架橋体が用いられる。耐衝撃性の低下を最大
限に抑制するためには、スチレン系樹脂の架橋体である
事が量も望ましい。The crosslinked polymer referred to in the present invention is not particularly limited, but is generally a polymer of radically polymerizable monomers such as styrene compounds, methacrylic esters, acrylic esters, or unsaturated nitrile compounds, or A crosslinked copolymer is used. In order to suppress the decrease in impact resistance to the maximum extent possible, it is desirable that the amount be a crosslinked product of styrene resin.
本発明にいう金属酸化物は隠ぺい性のあるものであれば
良い。その具体例としては、酸化チタン、酸化亜鉛、珪
酸、酸化マグネシウム、酸化アルミニウムまたは珪酸カ
ルシウム、珪酸アルミニウム等の珪酸塩類等が挙げられ
る。隠ぺい性の面から特に好ましい金属酸化物は酸化チ
タンである。The metal oxide referred to in the present invention may be any metal oxide as long as it has hiding properties. Specific examples thereof include titanium oxide, zinc oxide, silicic acid, magnesium oxide, aluminum oxide, and silicates such as calcium silicate and aluminum silicate. A particularly preferred metal oxide from the viewpoint of concealment is titanium oxide.
本発明において、架橋ポリマーの架橋度は特に限定され
るものではないが、架橋度が極端に高い場合は耐衝撃性
が低下するため好ましくなく、低過ぎる場合は赤リンあ
るいは金属酸化物と赤リンを保護できず、隠ぺい効果や
耐衝撃性が低下するため好ましくない。全く架橋してい
々いポリマーで被覆した場合は、溶融混練時に被覆、ｌ
リマーが流動し、被覆状態をとらないため、本発明の
効果を全く発揮しない。In the present invention, the degree of cross-linking of the cross-linked polymer is not particularly limited, but if the degree of cross-linking is extremely high, impact resistance will decrease, which is undesirable, and if it is too low, red phosphorus or metal oxides and red phosphorus This is undesirable because it cannot protect the objects and reduces the concealment effect and impact resistance. When completely crosslinked and coated with polymer, the coating and l are removed during melt-kneading.
Since the remer flows and does not maintain a coating state, the effects of the present invention are not exhibited at all.
本発明において、赤リンを被覆する金属酸化物の量は、
赤リンの色を隠ぺいできる量であれば良い。隠ぺいする
に必要な量は金属酸化物の持つ、隠ぺい性によって異な
るが一般的には、赤リン１００重量部に対し、５０〜３
００重量部の範囲よシ選ばれる。５０重量部以下であれ
ば、隠ぺい効果が十分に発揮されず好ましくなく、３０
０重量部以上になると耐衝撃性を低下させるため好まし
くない。In the present invention, the amount of metal oxide coating red phosphorus is
It is sufficient as long as the amount can hide the color of red phosphorus. The amount required for hiding varies depending on the hiding power of the metal oxide, but in general, it is 50 to 3 parts by weight per 100 parts by weight of red phosphorus.
00 parts by weight. If it is less than 50 parts by weight, the concealing effect will not be sufficiently exhibited, which is undesirable;
If it exceeds 0 parts by weight, it is not preferable because it lowers impact resistance.
赤リンまたは赤リンおよび金属酸化物を被覆する架橋−
リマーの量は特に限定されないが、一般的には、赤リン
１００重量部に対し、３０〜３００重量部の範囲よシ選
ばれる。３０重量部以下で多れば、赤リンおよび／また
は金属酸化物の保護が不完全になシ、耐衝撃性の低下や
、隠ぺい効果の低下が生ずるため好ましくなく、３００
１ｉ量部以上になると、難燃性あるいは耐熱性等を損う
ため好ましくない。Crosslinking covering red phosphorus or red phosphorus and metal oxides -
The amount of remer is not particularly limited, but is generally selected from a range of 30 to 300 parts by weight per 100 parts by weight of red phosphorus. If the amount is less than 30 parts by weight, the protection of the red phosphorus and/or metal oxide will be incomplete, resulting in a decrease in impact resistance and a decrease in the hiding effect, which is undesirable.
If it exceeds 1 part by weight, flame retardancy, heat resistance, etc. will be impaired, which is not preferable.
本発明において、架橋ポリマーあるいは金属酸化物およ
び架橋ホリマーで被覆された赤リンの配合量は、ポリフ
ェニレンエーテル系樹脂とスチレン系樹脂とよりなる樹
脂組成物１００重量部に対して１〜２０重量部であるこ
とが必要である。１重量部以下であれば、難燃効果が十
分に発揮されなく２０重量部以上になると、樹脂が暗赤
色化し、樹脂組成物の持つ本来の特性を失うため好まし
くない。In the present invention, the amount of red phosphorus coated with a crosslinked polymer or metal oxide and crosslinked polymer is 1 to 20 parts by weight based on 100 parts by weight of the resin composition consisting of a polyphenylene ether resin and a styrene resin. It is necessary that there be. If it is less than 1 part by weight, the flame retardant effect will not be sufficiently exhibited, and if it is more than 20 parts by weight, the resin will turn dark red and lose the original properties of the resin composition, which is not preferable.
本発明において架橋−リマーあるいは金属酸化物および
架橋ポリマーで被覆された赤リンの製造方法は特に限定
されるものではないが、例えば、水中において、赤リン
ｉ＆は赤リン粒子表面上に金属酸化物を電気的に凝集沈
着させた凝集沈着物の存在下に、モノマーおよび架橋剤
を重合するなどの方法が用いられる。In the present invention, the method for producing red phosphorus coated with cross-linked remer or metal oxide and cross-linked polymer is not particularly limited. For example, in water, red phosphorus i & A method is used in which a monomer and a crosslinking agent are polymerized in the presence of a coagulated deposit obtained by electrically coagulating and depositing.
本発明の難燃化された樹脂組成物の製造方法は、通常樹
脂を溶融、可塑化し、造粒、加工するいかなる方法を用
いても良い。例えば、ポリフェニレンエーテル系樹脂、
スチレン系樹脂および被覆赤リンを、押出機、加熱ロー
ル、ニーグー、・々ン、６リーミキサー等を用いて、溶
融混合する方法などが用いられる。また、樹脂を安定化
するなめに通常用いらレー′ル酸化防止剤、紫外線吸収
剤やその他の安定剤を配合したシ、リン系難燃剤等の他
の難燃剤を併用したシ、樹脂を強化するためにガラス繊
維やその他の無機フィラーを配合したシすることは本発
明を妨げるものではない。The method for producing the flame-retardant resin composition of the present invention may be any method in which a resin is normally melted, plasticized, granulated, and processed. For example, polyphenylene ether resin,
A method is used in which the styrene resin and the coated red phosphorus are melt-mixed using an extruder, a heated roll, a Nigu, a 6-Lee mixer, or the like. In addition, we can also strengthen the resin by adding other flame retardants, such as phosphorus-based flame retardants, to stabilize the resin. It does not impede the present invention to blend glass fiber or other inorganic fillers to achieve this.
以下、実施例および比較例により、本発明を更に具体的
に説明するが、本発明はこれらに゛よって限定されるも
のではない。実施例における部あるいは％は、それぞれ
、重量部あるいは重量％を示す。実施例および比較例に
示す各物性値は、組成物をベレット化し、射出成形し念
試験片につき、以下の方法により測定したものである。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Parts and % in the examples indicate parts by weight and % by weight, respectively. The physical property values shown in Examples and Comparative Examples were measured by the following method using a test piece made by pelletizing the composition and injection molding.
熱変形温度： ＡＳＴＭ Ｄ ６４８
成形品寸法・・・１２７ Ｘ １２．７ Ｘ ６．４間
荷重・・・・・・・・・・・・１８．６１４／σ２アイ
ゾツトｉｓ強さ： Ａ８ＴＭ Ｄ ２５６成形品形状・
・・厚さ６．４ｍ１ノツチ付き難燃性：ＵＬ規格９４
成形品寸法・・・１２７ Ｘ １２．７ Ｘ １．６フ
色調二目視
実施例１
攪拌機、温度計、窒素導入管および環流用冷却管を備え
た３００ｔｌ！のガラス製反応容器に１５０ ｙｔｌの
水を入れ、次いで窒素を吹込みながら２０１の未処理の
赤リンを仕込み、攪拌し分散させつ＼内温をｓｏ’ｃｉ
で昇温した。これに２０ｔのスチレン、０．２ｆのジビ
ニルベンゼンおよびｏ、ｏｓ ｔのα、α′−アゾビス
イソブチルニトリル（λよりＮ）を加え、攪拌しながら
４時間反応させた。反応終了後、冷却しこの懸濁液を濾
別、水洗し、減圧乾燥し、被覆赤リンを得た。該赤リン
２．３部、ポリ（２，６−ジメチル−１．４−）ユニレ
ン）エーテルｓｏｉお！び１０％のプリブタジェン成分
を含むスチレン−ブタジェングラフトコポリマー５０部
とを押出機を用い、２８０℃にて混線し組成物を得た。Heat distortion temperature: ASTM D 648 Molded product dimensions: 127 x 12.7 x 6.4 Load: 18.614/σ2 Izot is strength: A8TM D 256 molding Product shape/
・・Thickness 6.4 m 1 notch Flame retardant: UL standard 94 Molded product dimensions ・・127 300tl with tube! Pour 150 ytl of water into a glass reaction vessel, then charge 201 untreated red phosphorus while blowing nitrogen, stir and disperse, and bring the internal temperature to so'ci.
The temperature was raised. To this were added 20 t of styrene, 0.2 f of divinylbenzene, and o, ost of α, α'-azobisisobutylnitrile (N from λ), and the mixture was reacted for 4 hours with stirring. After the reaction was completed, the suspension was cooled, separated by filtration, washed with water, and dried under reduced pressure to obtain coated red phosphorus. 2.3 parts of the red phosphorus, poly(2,6-dimethyl-1,4-)unilene) ether soi! and 50 parts of a styrene-butadiene graft copolymer containing 10% of a prbutadiene component were mixed at 280° C. using an extruder to obtain a composition.
該組成物の物性試験結果を表に示す。The physical property test results of the composition are shown in the table.
比較例１
被覆赤リン２．３部を未処理の赤リン１．５部に代えた
以外は実施例１を繰返して混線を行い組成物を得た。該
組成物の物性試験結果を表に示す。Comparative Example 1 A composition was obtained by repeating Example 1, except that 2.3 parts of coated red phosphorus was replaced with 1.5 parts of untreated red phosphorus, and crosstalk was performed. The physical property test results of the composition are shown in the table.
実施例２
実施例１と同様な装置および操作で１５０ ＦＪの水に
２ｏｆの赤リンを分散させた。ついで攪拌しつつルチル
型酸化チタン（５原産業（株）社製、商品名；タイベー
クＲ−６３０）２０Ｆを添加して赤リンに凝集沈着させ
た。内温を８０′Ｃまで昇温し念後、２０？のスチレン
、０．２ｆのジビニルベンゼンおよび０．０５ ＰのＡ
Ｉ ＢＮを加え４時間反応させた後、実施例１と同様の
操作で被覆赤リンを得た。該被覆赤リン４．５部、ポリ
（２，６−ジメチル−１．４−）ユニレン）エーテル５
０部および１０％のブタジェン成分を含むスチレン−ブ
タジェングラフトコポリマー５０部とを押出機を用い、
２８０℃にて混練し組成物を得た。該組成物の物性試験
結果を表に示す。Example 2 Using the same equipment and operation as in Example 1, 2 of red phosphorus was dispersed in 150 FJ of water. Then, while stirring, rutile-type titanium oxide (manufactured by Gohara Sangyo Co., Ltd., trade name: Tybake R-630) 20F was added to coagulate and deposit on the red phosphorus. Raise the internal temperature to 80'C and then raise it to 20? of styrene, 0.2f of divinylbenzene and 0.05P of A
After adding IBN and reacting for 4 hours, the same procedure as in Example 1 was performed to obtain coated red phosphorus. 4.5 parts of the coated red phosphorus, 5 parts of poly(2,6-dimethyl-1,4-)unilene)ether
Using an extruder, 50 parts of a styrene-butadiene graft copolymer containing 0 parts and 10% of butadiene components,
A composition was obtained by kneading at 280°C. The physical property test results of the composition are shown in the table.
比較例２
被覆赤リン４．５部の代シに、赤リン１．５部およびル
チル型酸化チタン１．５部を使用した以外は実施例２を
繰返して混線を行い組成物を得た。該組成物の物性試験
結果を表に示す。Comparative Example 2 Example 2 was repeated except that 1.5 parts of red phosphorus and 1.5 parts of rutile titanium oxide were used in place of 4.5 parts of coated red phosphorus to obtain a composition. The physical property test results of the composition are shown in the table.
比較例３
トリフェニルホスフェート８部、ルチル型酸化チタン１
．５部、ポリ（２，６−ジメチル−１．４−）ユニレン
）エーテル５０部および１０％のブタジェン成分を含む
スチレン−ブタジェングラフトコポリマー５０部とを押
出機を用い、２８０℃にて混練し組成物を得た。該組成
物の物性試験結果を表に示す。Comparative Example 3 8 parts of triphenyl phosphate, 1 part of rutile titanium oxide
．． 5 parts of poly(2,6-dimethyl-1.4-)unilene) ether and 50 parts of a styrene-butadiene graft copolymer containing 10% butadiene component were kneaded at 280°C using an extruder. A composition was obtained. The physical property test results of the composition are shown in the table.
実施例３
実施例３
実施例２と同様な装置および操作で、赤リン２０ｔにル
チル型酸化チタン３０ｆを凝集沈着させた４１ｋ、４
ｆのアクリロニトリル、１６ｆのスチレン、０゜２ｔの
ジビニルベンゼンおよびｏ、ｏｓ ｔのＡＩ ＢＮを加
え、反応させて被覆赤リンを得た。該被覆赤リンフ部、
Ｉす（２，６−ジメテルー１．４−７二二レン）エーテ
ル６０部と、１５％のアクリロニトリル、３０％のブタ
ジェンおよび５５％のスチレンとよシなるＡＢ！３４０
部とを押出機を用い、２９０℃にて混疎し組成物を得た
。該組成物の物性試験結果を表に示す。Example 3 Example 3 Using the same apparatus and operation as in Example 2, 41k, 4 was prepared by coagulating and depositing 30f of rutile titanium oxide on 20t of red phosphorus.
f acrylonitrile, 16f styrene, 0°2t divinylbenzene and o, ost AI BN were added and reacted to obtain coated red phosphorus. The covered red rim part,
60 parts of Isu(2,6-dimeteru-1.4-7-dinilene) ether with 15% acrylonitrile, 30% butadiene and 55% styrene AB! 340
Using an extruder, the components were mixed at 290° C. to obtain a composition. The physical property test results of the composition are shown in the table.
比較例４
被覆赤リンを製造するに際し、ジビニルベンゼンを全く
使用しなかった以外は、実施例２を繰返し組成物を得九
。該組成物の物性試験結果を表に示す。Comparative Example 4 Example 2 was repeated to obtain a composition, except that no divinylbenzene was used in producing the coated red phosphorus. The physical property test results of the composition are shown in the table.
実施例４
実施例２と同様な装置および操作で、赤リン２０ｔにル
チル型酸化チタン１２ｆを凝集沈着させた後、ａｔのス
チレン、０．３ｆのジビニルペンぜンおよび０．０３
ｆの人ＩＢＮを加え、反応させて被覆赤リンを得た。該
被覆赤リン１．７部ポリ（２，６−ジメチル−１．４−
フェニレン）エーテ／Ｌ／７０部、４０％のブタジェン
成分を含む、スチレン■−ブタジェン（Ｂ）のＡ−Ｂ−
大型ブロックコーリマー４部、１０χのブタジェン成分
を含むスチレン−ブタジェングラフトコポリマー２６部
と２．６−シーｔｃｒｔ−ブチル−４−メチルフェノー
ル１部とを押出機を用い、窒素雰囲気下にて３００℃で
混練し組成物を得た。該組成物の物性試験結果を表に示
す。Example 4 Using the same equipment and operation as in Example 2, 12f of rutile titanium oxide was coagulated and deposited on 20t of red phosphorus, and then styrene of at, divinylpenzene of 0.3f and divinylpenzene of 0.03
Human IBN of f was added and reacted to obtain coated red phosphorus. The coated red phosphorus 1.7 parts poly(2,6-dimethyl-1.4-
phenylene)ether/L/70 parts, containing 40% butadiene component, A-B- of styrene ■-butadiene (B)
Using an extruder, 4 parts of large block colimer, 26 parts of a styrene-butadiene graft copolymer containing a 10x butadiene component, and 1 part of 2.6-sheet tcrt-butyl-4-methylphenol were mixed in an extruder under a nitrogen atmosphere for 300 g. A composition was obtained by kneading at ℃. The physical property test results of the composition are shown in the table.
比較例５
被覆赤リンの量を１．５部から０．８部に減じた以外は
実施例４を繰返して組成物を得た。該組成物の物性試験
結果を表に示す。Comparative Example 5 A composition was obtained by repeating Example 4 except that the amount of coated red phosphorus was reduced from 1.5 parts to 0.8 parts. The physical property test results of the composition are shown in the table.
比較例６
２０１の赤リンに８ｆのルチル凰酸化チタンを凝集沈着
させた後、４？のスチレンと０．１５ ｆのジビニルペ
ンを重合して得た被覆赤リンでろシ、かつ、該被覆赤リ
ンの量が１．３部部である以外は、実施例４を繰返して
組成物を得た。該組成物の物性試験結果を表に示す。Comparative Example 6 After coagulating and depositing 8f rutile titanium oxide on 201 red phosphorus, 4? A composition was obtained by repeating Example 4, except that the coated red phosphorus obtained by polymerizing styrene and 0.15 f divinyl pen was filtered, and the amount of the coated red phosphorus was 1.3 parts. Ta. The physical property test results of the composition are shown in the table.
実施例５
実施例２と同様な装置および操作で、赤リン、１０２に
ルチル型酸化チタン２７．５ｆを凝集沈着させた後、２
７．５ｔのスチレン、０．２ｆのジビニルベンゼンおよ
び０．０６９のＡＩＢＮを加え、反応させて被覆赤リン
を得た。該被覆赤リン１６部、ポリ（２，６−、）メチ
ル−１，４−フェニレン）エーテル３５部、ポリスチレ
ン２０部と１０％のブタジェン成分を含むスチレン−ブ
タジェングラフトコノリマー４５部とを押出機を用い、
２５０℃にて混練し組成物を得た。該組成物の物性試験
結果を表に示す。Example 5 Rutile titanium oxide 27.5f was coagulated and deposited on red phosphorus, 102 using the same equipment and operation as in Example 2, and then
7.5t styrene, 0.2f divinylbenzene and 0.069 AIBN were added and reacted to obtain coated red phosphorus. Extrude 16 parts of the coated red phosphorus, 35 parts of poly(2,6-,)methyl-1,4-phenylene)ether, 20 parts of polystyrene, and 45 parts of a styrene-butadiene graft copolymer containing 10% butadiene component. using a machine,
A composition was obtained by kneading at 250°C. The physical property test results of the composition are shown in the table.
比較例７
被覆赤リンの量を１６部から２５部に増して、実施例５
を繰返して組成物を得た。該組成物の物性試験結果を表
に示す。Comparative Example 7 Example 5 by increasing the amount of coated red phosphorus from 16 parts to 25 parts
A composition was obtained by repeating the steps. The physical property test results of the composition are shown in the table.
Claims (6)
とよりなる樹脂組成物１００重量部と、架橋ポリマーで
被覆された赤リンあるいは金属酸化物および架橋ポリマ
ーで被覆された赤リン１〜２０重量部とよりなることを
特徴とする難燃化された樹脂組成物(1) 100 parts by weight of a resin composition consisting of a polyphenylene ether resin and a styrene resin and 1 to 20 parts by weight of red phosphorus coated with a crosslinked polymer or red phosphorus coated with a metal oxide and a crosslinked polymer A flame-retardant resin composition characterized by
−ジメチル−１，４−フエニレン）エーテルである特許
請求の範囲第１項記載の組成物(2) Polyphenylene ether resin is poly(2,6
-dimethyl-1,4-phenylene) ether according to claim 1.
ポリスチレンである特許請求の範囲第１項記載の組成物(3) The composition according to claim 1, wherein the styrenic resin is polybutadiene-modified high-impact polystyrene.
ン−スチレンの三元共重合体である特許請求の範囲第１
項記載の組成物(4) Claim 1, wherein the styrenic resin is a terpolymer of acrylonitrile-butadiene-styrene.
Compositions described in section
特許請求の範囲第１項記載の組成物(5) The composition according to claim 1, wherein the crosslinked polymer is a crosslinked styrene resin.
第１項記載の組成物(6) The composition according to claim 1, wherein the metal oxide is titanium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10666286A JPS62263247A (en) | 1986-05-12 | 1986-05-12 | Flame-retarded resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10666286A JPS62263247A (en) | 1986-05-12 | 1986-05-12 | Flame-retarded resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62263247A true JPS62263247A (en) | 1987-11-16 |
Family
ID=14439297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10666286A Pending JPS62263247A (en) | 1986-05-12 | 1986-05-12 | Flame-retarded resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62263247A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01297455A (en) * | 1988-05-25 | 1989-11-30 | Mitsubishi Gas Chem Co Inc | Flame-retardant polyphenylene ether resin composition |
| JPH03259956A (en) * | 1990-03-08 | 1991-11-20 | Rin Kagaku Kogyo Kk | Flame-retardant resin composition |
| US7122251B2 (en) | 2001-05-31 | 2006-10-17 | Mitsubishi Rayon Co., Ltd. | Resin composition for plating substrate and resin molding using the same, and metal plated parts |
| CN1322068C (en) * | 2002-07-18 | 2007-06-20 | 日本化学工业株式会社 | Modified red phosphorus, its mfg. process discoloured red phosphorus compsns and fire-retardant polymeric compsn. |
| US7585443B2 (en) | 2004-05-20 | 2009-09-08 | Albemarle Corporation | Pelletized brominated anionic styrenic polymers and their preparation and use |
| CN111349271A (en) * | 2018-12-24 | 2020-06-30 | 中蓝晨光化工研究设计院有限公司 | Method for preparing coated microcapsule red phosphorus and application |
-
1986
- 1986-05-12 JP JP10666286A patent/JPS62263247A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01297455A (en) * | 1988-05-25 | 1989-11-30 | Mitsubishi Gas Chem Co Inc | Flame-retardant polyphenylene ether resin composition |
| JPH03259956A (en) * | 1990-03-08 | 1991-11-20 | Rin Kagaku Kogyo Kk | Flame-retardant resin composition |
| US7122251B2 (en) | 2001-05-31 | 2006-10-17 | Mitsubishi Rayon Co., Ltd. | Resin composition for plating substrate and resin molding using the same, and metal plated parts |
| CN1322068C (en) * | 2002-07-18 | 2007-06-20 | 日本化学工业株式会社 | Modified red phosphorus, its mfg. process discoloured red phosphorus compsns and fire-retardant polymeric compsn. |
| US7585443B2 (en) | 2004-05-20 | 2009-09-08 | Albemarle Corporation | Pelletized brominated anionic styrenic polymers and their preparation and use |
| CN111349271A (en) * | 2018-12-24 | 2020-06-30 | 中蓝晨光化工研究设计院有限公司 | Method for preparing coated microcapsule red phosphorus and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1144680A (en) | Thermoplastic polymer compositions | |
| JPH07268042A (en) | Graft copolymer useful as flameproofing additive | |
| JPH0762175A (en) | Thermoplastic resin composition | |
| JPS62263247A (en) | Flame-retarded resin composition | |
| JPS61162541A (en) | Flame-retardant resin composition | |
| JPH0133485B2 (en) | ||
| JPH04175370A (en) | Resin composition | |
| JP3204412B2 (en) | Flame retardant thermoplastic resin composition | |
| KR100657734B1 (en) | Flame Retardant Rubber-Modified Styrene Resin Composition | |
| JPH0629353B2 (en) | Impact resistant polyphenylene ether resin composition | |
| EP0520096B1 (en) | Flame retardant resin composition | |
| JP2954639B2 (en) | Wire coating material | |
| JP3455715B2 (en) | Thermoplastic flame-retardant resin composition | |
| JPH04370134A (en) | Halogen-free flame-retarding resin composition | |
| JPS61291644A (en) | Flame-retardant abs resin composition | |
| JPS58141239A (en) | Polyphenylene ether resin composition having improved impact resistance | |
| KR102066800B1 (en) | Thermoplastic resin composition and article produced therefrom | |
| EP0578873B1 (en) | Flame-retardant resin composition | |
| JP3524992B2 (en) | Flame retardant resin composition with excellent light resistance | |
| JP3251389B2 (en) | Polyphenylene ether resin composition | |
| JPS5842648A (en) | Heat-resistant resin composition having good flow characteristics | |
| JP3519117B2 (en) | Polyphenylene oxide resin composition | |
| JPS6036179B2 (en) | resin composition | |
| JPS6239650A (en) | Flame-retardant resin composition | |
| JPS6036555A (en) | Polyphenylene ether resin composition |