JPH07247403A - Shock-resistant styrenic resin composition - Google Patents
Shock-resistant styrenic resin compositionInfo
- Publication number
- JPH07247403A JPH07247403A JP4154894A JP4154894A JPH07247403A JP H07247403 A JPH07247403 A JP H07247403A JP 4154894 A JP4154894 A JP 4154894A JP 4154894 A JP4154894 A JP 4154894A JP H07247403 A JPH07247403 A JP H07247403A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin composition
- average molecular
- pts
- 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
- 229920001890 Novodur Polymers 0.000 title claims description 4
- 239000011342 resin composition Substances 0.000 title abstract description 9
- 230000035939 shock Effects 0.000 title abstract 2
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 10
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 8
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 239000004711 α-olefin Substances 0.000 claims abstract description 5
- 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 class 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 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 26
- 229920005989 resin Polymers 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- 230000000703 anti-shock Effects 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 229920005638 polyethylene monopolymer Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- MPJLLBLFMGXUNW-UHFFFAOYSA-N 1,3,5-tribromocyclohexa-2,4-dien-1-ol Chemical compound OC1(Br)CC(Br)=CC(Br)=C1 MPJLLBLFMGXUNW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 101100042631 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SIN3 gene Proteins 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、流動性に優れ、かつ難
燃性が良好であり、家電製品、ＯＡ機器、自動車部品な
どの分野に好適な耐衝撃性スチレン系樹脂組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact-resistant styrene-based resin composition which has excellent fluidity and flame retardancy and is suitable for the fields of home appliances, office automation equipment, automobile parts and the like.
【０００２】[0002]
【従来の技術】従来、ＨＩポリスチレン、ＡＢＳ樹脂な
どの耐衝撃性スチレン系樹脂は、家電、ＯＡ機器部分野
のハウジング材料として広く利用されている。近年、こ
れらのハウジング材に難燃化の要求とともに、大画面テ
レビに代表される製品の大型化の要求が高まってきてい
る。難燃化に関する技術としては、例えば難燃剤と塩素
化ポリエチレンを併用する方法（例えば、特開昭49-591
53号公報）が提案されている。また、大型化に関して
は、樹脂の流動性を改善する目的でミネラルオイルなど
の可塑剤を添加する方法が用いられている。2. Description of the Related Art Conventionally, high-impact styrene resins such as HI polystyrene and ABS resin have been widely used as housing materials in the fields of home appliances and OA equipment. In recent years, along with the demand for flame-retardant properties of these housing materials, there is an increasing demand for larger products such as large-screen televisions. As a technique for flame retardation, for example, a method in which a flame retardant and chlorinated polyethylene are used in combination (for example, JP-A-49-591).
No. 53) is proposed. In addition, in order to increase the size, a method of adding a plasticizer such as mineral oil is used for the purpose of improving the fluidity of the resin.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、難燃剤
と塩素化ポリエチレンの併用では、添加される塩素化ポ
リエチレンによって流動性が低下するという問題があ
る。また、可塑剤を添加する方法は、ドリッピングなど
の難燃性が低下するという問題がある。このように、高
流動性と難燃性を両立させた樹脂組成物は、いまだ得ら
れていないのが現状である。本発明は、かかる状況に鑑
みてなされたものであり、流動性に優れ、かつ難燃性も
良好な耐衝撃性スチレン系樹脂組成物を提供することを
目的とする。However, when the flame retardant is used in combination with chlorinated polyethylene, there is a problem in that the fluidity is lowered due to the added chlorinated polyethylene. Further, the method of adding a plasticizer has a problem that flame retardancy such as dripping is lowered. As described above, at present, a resin composition having both high fluidity and flame retardancy has not been obtained yet. The present invention has been made in view of such circumstances, and an object of the present invention is to provide an impact-resistant styrene-based resin composition having excellent fluidity and good flame retardancy.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、鋭意研究
を重ねた結果、特定のスチレン系樹脂と塩素化ポリエチ
レンとを組み合わせることにより上記目的を達成しうる
ことを見出し、この知見に基づいて本発明を完成するに
至った。すなわち、本発明は（Ａ）メルトフローレート
が１０ｇ／１０分以上である耐衝撃性スチレン系樹脂
１００重量部、（Ｂ）チタニウム含有コゲル触媒の存在
下、エチレン単独またはエチレンと炭素数３〜１２のα
−オレフィンを共重合して得られる下記(i) および(ii)
の性状を有するポリエチレンを塩素化して得られる塩素
含有量が１５〜５０重量％である塩素化ポリエチレン
１〜３０重量部、 (i) 重量平均分子量 １０万〜１８万 (ii)重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）と
の比（Ｍｗ／Ｍｎ）７〜１４ （Ｃ）臭素系難燃剤 ５〜３０重量部 および（Ｄ）酸
化アンチモン １〜２０重量部からなる耐衝撃性スチレ
ン系樹脂組成物を提供するものである。以下、本発明を
具体的に説明する。As a result of intensive studies, the present inventors have found that the above object can be achieved by combining a specific styrene resin and chlorinated polyethylene, and based on this finding As a result, the present invention has been completed. That is, the present invention provides (A) an impact-resistant styrene-based resin having a melt flow rate of 10 g / 10 minutes or more.
In the presence of 100 parts by weight of (B) titanium-containing cogel catalyst, ethylene alone or ethylene and α having 3 to 12 carbon atoms
-The following (i) and (ii) obtained by copolymerizing olefins
Chlorinated polyethylene having a chlorine content of 15 to 50% by weight obtained by chlorinating polyethylene having the property of
1 to 30 parts by weight, (i) weight average molecular weight 100,000 to 180,000 (ii) ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) 7 to 14 (C) brominated system difficult An impact-resistant styrenic resin composition comprising 5 to 30 parts by weight of a flame retardant and 1 to 20 parts by weight of (D) antimony oxide. Hereinafter, the present invention will be specifically described.
【０００５】本発明における（Ａ）耐衝撃性スチレン系
樹脂は、ポリブタジエンなどのゴム分にスチレン、アク
リロニトリルなどの単量体のうちの少なくとも１種をグ
ラフトさせて得られる樹脂である。これらの具体的例と
しては、ＨＩポリスチレン、ＡＢＳ樹脂、ＭＢＳ樹脂、
ＡＣＳ樹脂、ＡＡＳ樹脂およびＡＥＳ樹脂などが挙げら
れる。これらの樹脂のメルトフローレート（温度２００
℃、荷重５ｋｇにおいて測定）（以下「ＭＦＲ」とい
う）は１０ｇ／１０分以上であることが必要である。Ｍ
ＦＲが１０ｇ／１０分未満では流動性が低下するので好
ましくない。The (A) impact-resistant styrenic resin in the present invention is a resin obtained by grafting a rubber component such as polybutadiene with at least one monomer selected from styrene and acrylonitrile. Specific examples of these include HI polystyrene, ABS resin, MBS resin,
Examples include ACS resin, AAS resin and AES resin. Melt flow rate of these resins (temperature 200
(Measured at a temperature of 5 ° C. and a load of 5 kg) (hereinafter referred to as “MFR”) needs to be 10 g / 10 minutes or more. M
When the FR is less than 10 g / 10 minutes, the fluidity is lowered, which is not preferable.
【０００６】また、本発明における（Ｂ）塩素化ポリエ
チレンは、粉末状ポリエチレンを水性懸濁液中で、もし
くは有機溶媒に溶解させたのち、塩素化して得られるも
のである。なかでも、本発明には前者の方法で得られた
塩素化ポリエチレンが望ましい。該塩素化ポリエチレン
の塩素含有量は１５〜５０重量％であり、好ましくは２
０〜４５重量％、さらに好適には２５〜４０重量％であ
る。塩素含有量が１５重量％未満では難燃性が低下す
る。一方、５０重量％を超えると耐衝撃性が低下するの
で好ましくない。The chlorinated polyethylene (B) in the present invention is obtained by chlorinating powdery polyethylene in an aqueous suspension or in an organic solvent and then chlorinating. Among them, the chlorinated polyethylene obtained by the former method is preferable for the present invention. The chlorine content of the chlorinated polyethylene is 15 to 50% by weight, preferably 2
It is 0 to 45% by weight, and more preferably 25 to 40% by weight. If the chlorine content is less than 15% by weight, the flame retardancy will decrease. On the other hand, if it exceeds 50% by weight, impact resistance is deteriorated, which is not preferable.
【０００７】前記ポリエチレンは、エチレン単独または
エチレンとα−オレフィンを後記の触媒を用いて共重合
して得られるものである。α−オレフィンとしては、通
常炭素数３〜１２、好ましくは３〜８のものが用いられ
る。具体例としては、プロピレン、ブテン−１、ヘキセ
ン−１、４−メチルペンテン−１およびオクテン−１が
挙げられる。該α−オレフィンの共重合割合は、通常４
０重量％以下であり、２０重量％以下が好ましい。The polyethylene is obtained by copolymerizing ethylene alone or ethylene and α-olefin using a catalyst described below. As the α-olefin, one having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms is usually used. Specific examples include propylene, butene-1, hexene-1, 4-methylpentene-1 and octene-1. The copolymerization ratio of the α-olefin is usually 4
It is 0% by weight or less, preferably 20% by weight or less.
【０００８】本発明におけるチタニウム含有コゲル触媒
は、シリカアルミナと酸化クロムおよびチタニウム化合
物とのコゲルからなる触媒である。かかるコゲル触媒
は、例えば、ケイ酸ナトリウムを硫酸などの酸性物質と
接触させてヒドロゲルを形成し、このヒドロゲルにチタ
ニウム化合物を加えて共沈殿させ、かくして形成された
ヒドロゲルを噴霧乾燥させてキセロゲルを形成し、次い
で焼成して触媒を形成し、該触媒に対し三酸化クロム換
算で０．１〜２０重量％のクロムを上記工程中または焼
成後の触媒に混合する方法により製造される。前記チタ
ニウム化合物としては、四塩化チタニウム、硫酸チタニ
ウムなどが使用される。これらの製造方法については、
例えば、特開昭５２−２７０８３号公報に詳しく記載さ
れている。The titanium-containing cogel catalyst according to the present invention is a catalyst composed of a cogel of silica-alumina, chromium oxide and a titanium compound. Such a cogel catalyst is obtained by, for example, contacting sodium silicate with an acidic substance such as sulfuric acid to form a hydrogel, adding a titanium compound to the hydrogel to coprecipitate, and spray-drying the hydrogel thus formed to form a xerogel. And then calcined to form a catalyst, and 0.1 to 20% by weight of chromium of the catalyst, calculated as chromium trioxide, is mixed with the catalyst during or after the above steps. As the titanium compound, titanium tetrachloride, titanium sulfate or the like is used. For these manufacturing methods,
For example, it is described in detail in JP-A-52-27083.
【０００９】また、本発明に用いるポリエチレンは、重
量平均分子量が１０万〜１８万であり、好適には１２万
〜１７万である。重量平均分子量が１０万未満では耐衝
撃性に劣る。一方、１８万を超えると流動性が不十分と
なる。さらに、重量平均分子量（Ｍｗ）と数平均分子量
（Ｍｎ）との比（Ｍｗ／Ｍｎ）が７〜１４、であり、好
適には８〜１２である。Ｍｗ／Ｍｎが７未満では流動性
が不十分である。一方、１４を超えると耐衝撃性が低下
するので好ましくない。The polyethylene used in the present invention has a weight average molecular weight of 100,000 to 180,000, preferably 120,000 to 170,000. If the weight average molecular weight is less than 100,000, the impact resistance is poor. On the other hand, if it exceeds 180,000, the fluidity becomes insufficient. Furthermore, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 7 to 14, and preferably 8 to 12. When Mw / Mn is less than 7, the fluidity is insufficient. On the other hand, if it exceeds 14, the impact resistance decreases, which is not preferable.
【００１０】本発明におけるスチレン系樹脂１００重量
部に対する塩素化ポリエチレンの配合量は１〜３０重量
部であり、好ましくは３〜２５重量部、さらに好ましく
は５〜２０重量部である。塩素化ポリエチレンの配合量
が１重量部未満では耐衝撃性が不十分となる。一方、３
０重量部を超えると曲げ弾性率が低下し実用上問題とな
る。The blending amount of chlorinated polyethylene with respect to 100 parts by weight of the styrene resin in the present invention is 1 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight. If the blending amount of chlorinated polyethylene is less than 1 part by weight, the impact resistance becomes insufficient. On the other hand, 3
If it exceeds 0 parts by weight, the flexural modulus decreases, which is a practical problem.
【００１１】また、本発明における（Ｃ）臭素系難燃剤
は、一般に樹脂の難燃剤として広く用いられている添加
剤である。該難燃剤の代表例としては、デカブロムジフ
ェニルエーテル、テトラブロムビスフェノールＡ、臭素
含有エポキシ化合物と１，３，５−トリブロムフェノー
ルとの臭素含有反応生成物などが挙げられ、これらの難
燃剤は２種以上を混合して使用してもよい。The brominated flame retardant (C) in the present invention is an additive which is generally widely used as a flame retardant for resins. Representative examples of the flame retardant include decabromodiphenyl ether, tetrabromobisphenol A, a bromine-containing reaction product of a bromine-containing epoxy compound and 1,3,5-tribromophenol, and the like. You may use it in mixture of 2 or more types.
【００１２】本発明におけるスチレン系樹脂１００重量
部に対する臭素系難燃剤の配合割合は５〜３０重量部で
あり、好ましくは８〜２５重量部、さらに好ましくは１
０〜２５重量部である。臭素系難燃剤の配合量が５重量
部未満では難燃性が不十分となる。一方、３０重量部を
超えると機械的強度が低下するので好ましくない。The blending ratio of the brominated flame retardant to 100 parts by weight of the styrene resin in the present invention is 5 to 30 parts by weight, preferably 8 to 25 parts by weight, and more preferably 1 part.
It is 0 to 25 parts by weight. If the blending amount of the brominated flame retardant is less than 5 parts by weight, the flame retardancy becomes insufficient. On the other hand, if it exceeds 30 parts by weight, the mechanical strength is lowered, which is not preferable.
【００１３】さらに、本発明における（Ｄ）酸化アンチ
モンは、樹脂業界において前記難燃剤の難燃助剤として
広く用いられているものである。その代表例としては、
三酸化アンチモン、五酸化アンチモンなどが挙げられ
る。本発明におけるスチレン系樹脂１００重量部に対す
る酸化アンチモンの配合割合は１〜２０重量部であり、
好ましくは２〜１８重量部、さらに好ましくは２〜１５
重量部である。酸化アンチモンの配合割合が１重量部未
満では臭素系難燃剤との相乗効果が期待できない。一
方、２０重量部を超えると機械的強度が低下するので好
ましくない。Further, the antimony oxide (D) in the present invention is widely used as a flame retardant aid for the above flame retardant in the resin industry. As a typical example,
Examples thereof include antimony trioxide and antimony pentoxide. The compounding ratio of antimony oxide to 100 parts by weight of the styrene resin in the present invention is 1 to 20 parts by weight,
Preferably 2-18 parts by weight, more preferably 2-15
Parts by weight. If the compounding ratio of antimony oxide is less than 1 part by weight, a synergistic effect with the brominated flame retardant cannot be expected. On the other hand, if it exceeds 20 parts by weight, the mechanical strength is lowered, which is not preferable.
【００１４】また、本発明の樹脂組成物には、所望によ
り慣用の各種添加剤、例えば安定剤、可塑剤、顔料、充
填剤などを添加することができる。If desired, various conventional additives such as stabilizers, plasticizers, pigments and fillers may be added to the resin composition of the present invention.
【００１５】[0015]
【実施例】以下、本発明を実施例によりさらに詳しく説
明する。なお、メルトフトーレート（以下「ＭＦＲ」と
いう）はＪＩＳ Ｋ７２１０に準拠し、温度２００℃、
荷重５ｋｇの条件で測定した。アイゾット衝撃強度はＡ
ＳＴＭ Ｄ２５６に準拠し、温度２３℃、ノッチ付きで
測定した。難燃性は米国ＵＬ９４法に準拠し、厚さ３ｍ
ｍの試験片を用いた。EXAMPLES The present invention will now be described in more detail with reference to examples. The melt rate (hereinafter referred to as “MFR”) is in accordance with JIS K7210, and the temperature is 200 ° C.
It was measured under the condition of a load of 5 kg. Izod impact strength is A
According to STM D256, it was measured at a temperature of 23 ° C. and with a notch. Flame retardance complies with UL94 law, thickness 3m
m test pieces were used.
【００１６】また、耐衝撃性スチレン系樹脂として、Ｍ
ＦＲが１３ｇ／１０分であるＨＩポリスチレンを用い
た。塩素化ポリエチレンとして、チタニウム含有コゲル
触媒の存在下にエチレンを重合して得られたＭｗが１４
万であり、かつＭｗ／Ｍｎ比が９であるポリエチレンを
塩素含有量３０．５重量％まで塩素化して得られるもの
（以下「ＣＰＥ１」という）、同様にしてＭｗが１７万
であり、かつＭｗ／Ｍｎ比が９であるポリエチレンを塩
素含有量３０．５重量％まで塩素化して得られるもの
（以下「ＣＰＥ２」という）を用いた。As the impact-resistant styrene resin, M
HI polystyrene with an FR of 13 g / 10 min was used. As the chlorinated polyethylene, the Mw obtained by polymerizing ethylene in the presence of a titanium-containing cogel catalyst was 14
Obtained by chlorinating polyethylene having a Mw / Mn ratio of 9 and having a chlorine content of 30.5% by weight (hereinafter referred to as "CPE1"), similarly having Mw of 170,000 and Mw What was obtained by chlorinating polyethylene having a / Mn ratio of 9 to a chlorine content of 30.5 wt% (hereinafter referred to as "CPE2") was used.
【００１７】比較用として、フィリップス触媒を用いて
エチレンを重合して得られるＭｗが１４万であり、かつ
Ｍｗ／Ｍｎ比が７であるポリエチレンを塩素含有量３
０．５重量％まで塩素化して得られるもの（以下「ＣＰ
Ｅ３」という）およびチーグラー触媒を用いてエチレン
を重合して得られるＭｗが１４万であり、かつＭｗ／Ｍ
ｎ比が５であるポリエチレンを塩素含有量３０．５重量
％まで塩素化して得られるもの（以下「ＣＰＥ４」とい
う）を用いた。また、臭素系難燃剤として臭素含有エポ
キシ化合物と１，３，５−トリブロムフェノールとの臭
素含有反応生成物（大日本インキ社製、プラサームＥＣ
−１４）、および酸化アンチモンとして三酸化アンチモ
ンを用いた。For comparison, polyethylene having a Mw of 140,000 and an Mw / Mn ratio of 7 obtained by polymerizing ethylene using a Phillips catalyst has a chlorine content of 3
Those obtained by chlorination up to 0.5% by weight (hereinafter "CP
E3 ”) and Mw obtained by polymerizing ethylene using a Ziegler catalyst, and Mw / M
What was obtained by chlorinating polyethylene having an n ratio of 5 to a chlorine content of 30.5 wt% (hereinafter referred to as "CPE4") was used. Further, a bromine-containing reaction product of a bromine-containing epoxy compound and 1,3,5-tribromophenol as a bromine-based flame retardant (manufactured by Dainippon Ink and Chemicals, Platherm EC
-14), and antimony trioxide was used as the antimony oxide.
【００１８】実施例１〜２、比較例１〜３ 表１に種類および配合量が示されている耐衝撃性ポリス
チレン、塩素化ポリエチレン、臭素系難燃剤および酸化
アンチモンをヘンシェルミキサーにて混合し、３０ｍｍ
径の二軸押出機を用いて２００℃で混練しペレットにし
た。得られた各ペレットを８オンス射出成形機を用いて
試験片を作成した。各試験片についてＭＦＲ、アイゾッ
ト衝撃強度および難燃性を測定した。得られた結果を表
１に示す。Examples 1 to 2 and Comparative Examples 1 to 3 Impact-resistant polystyrene, chlorinated polyethylene, brominated flame retardant and antimony oxide whose types and amounts are shown in Table 1 are mixed in a Henschel mixer, 30 mm
Kneaded into pellets at 200 ° C. using a twin-screw extruder having a diameter. A test piece was prepared from each of the obtained pellets using an 8 ounce injection molding machine. The MFR, Izod impact strength and flame retardancy of each test piece were measured. The results obtained are shown in Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】本発明の耐衝撃性スチレン系樹脂組成物
は、流動性に優れ、かつ難燃性が良好であるので、家電
製品、ＯＡ機器、自動車部品などの分野に有用であり、
特に大型成形品に好適に用いられる。EFFECT OF THE INVENTION Since the impact resistant styrene resin composition of the present invention has excellent fluidity and good flame retardancy, it is useful in the fields of home appliances, office automation equipment, automobile parts, etc.
Especially, it is preferably used for large-sized molded products.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 //(Ｃ０８Ｌ 51/04 23:28） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display part // (C08L 51/04 23:28)
Claims (1)
０分以上である耐衝撃性スチレン系樹脂 １００重量
部、 （Ｂ）チタニウム含有コゲル触媒の存在下、エチレン単
独またはエチレンと炭素数３〜１２のα−オレフィンを
共重合して得られる下記(i) および(ii)の性状を有する
ポリエチレンを塩素化して得られる塩素含有量が１５〜
５０重量％である塩素化ポリエチレン １〜３０重量
部、 (i) 重量平均分子量 １０万〜１８万 (ii)重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）と
の比（Ｍｗ／Ｍｎ）７〜１４ （Ｃ）臭素系難燃剤 ５〜３０重量部 および （Ｄ）酸化アンチモン １〜２０重量部 からなる耐衝撃性スチレン系樹脂組成物。1. A melt flow rate of (A) is 10 g / 1.
100 parts by weight of impact-resistant styrenic resin for 0 minutes or more, (B) in the presence of a titanium-containing cogel catalyst, ethylene alone or obtained by copolymerizing ethylene and an α-olefin having 3 to 12 carbon atoms (i) ) And (ii) have a chlorine content of 15 to 15 obtained by chlorinating polyethylene having the properties
1 to 30 parts by weight of chlorinated polyethylene of 50% by weight, (i) weight average molecular weight of 100,000 to 180,000 (ii) ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) 7 -14 (C) Brominated flame retardant 5 to 30 parts by weight and (D) antimony oxide 1 to 20 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4154894A JPH07247403A (en) | 1994-03-11 | 1994-03-11 | Shock-resistant styrenic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4154894A JPH07247403A (en) | 1994-03-11 | 1994-03-11 | Shock-resistant styrenic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07247403A true JPH07247403A (en) | 1995-09-26 |
Family
ID=12611486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4154894A Pending JPH07247403A (en) | 1994-03-11 | 1994-03-11 | Shock-resistant styrenic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07247403A (en) |
-
1994
- 1994-03-11 JP JP4154894A patent/JPH07247403A/en active Pending
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