JPS62179552A - Impact-resistant polystyrene resin composition - Google Patents
Impact-resistant polystyrene resin compositionInfo
- Publication number
- JPS62179552A JPS62179552A JP2038586A JP2038586A JPS62179552A JP S62179552 A JPS62179552 A JP S62179552A JP 2038586 A JP2038586 A JP 2038586A JP 2038586 A JP2038586 A JP 2038586A JP S62179552 A JPS62179552 A JP S62179552A
- Authority
- JP
- Japan
- Prior art keywords
- impact
- resistant polystyrene
- weight
- polystyrene resin
- flame
- 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
- 229920005990 polystyrene resin Polymers 0.000 title claims description 34
- 239000011342 resin composition Substances 0.000 title claims description 18
- 239000003063 flame retardant Substances 0.000 claims abstract description 24
- 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 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001993 dienes Chemical class 0.000 claims abstract description 13
- 230000008961 swelling Effects 0.000 claims abstract description 11
- 239000005063 High cis polybutadiene Substances 0.000 claims abstract description 3
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 14
- 229920001971 elastomer Polymers 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 3
- 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 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 4
- -1 furniture Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-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
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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、耐衝撃性及び難燃性の要求される種々の成形
品、例えば、電気製品、家具、建材の成形材料として利
用される耐衝撃性ポリスチレン系樹脂組成物に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention is applicable to various molded products that require impact resistance and flame retardancy, such as electrical products, furniture, and construction materials used as molding materials. The present invention relates to an impact polystyrene resin composition.
耐衝撃性ポリスチレン系樹脂は、耐ｉｈ＠性の他に、成
形性その他種々の物性に優れているため、耐衝撃性の要
求される成形品の成形材料として汎用されている。Impact-resistant polystyrene resins have excellent moldability and other various physical properties in addition to IH@ resistance, and are therefore widely used as molding materials for molded products that require impact resistance.
また、Ｗｉ衝撃性ポリスチレン系樹脂は、易燃性樹脂で
あるため、その難燃化付与に関する開発も種々行われて
おり、例えば、特公昭５７−２６６９５号公報には、難
燃剤の添加による問題を回避した、難燃性の耐衝撃性ポ
リスチレン系樹脂組成物が開示されている。In addition, since Wi-impact polystyrene resin is a flammable resin, various developments have been made to impart flame retardancy to it. A flame-retardant, impact-resistant polystyrene-based resin composition is disclosed that avoids this.
通常の耐衝撃性ポリスチレン系樹脂は、ポリスチレン系
樹脂をその製造時にポリブタジェンゴムで変性したもの
であるが、特公昭５７−２６６９５号公報にも記載され
ているように、耐衝撃性ポリスチレン系樹脂に難燃性を
付与するために単に難燃剤を添加すると耐衝撃性を著し
く低下させ、また耐衝撃性の低下を防ぐためにポリブタ
ジェンゴムの添加量を多くするとセルフクツピング特性
を低下させる問題がある。Ordinary impact-resistant polystyrene-based resins are made by modifying polystyrene-based resins with polybutadiene rubber during production, but as described in Japanese Patent Publication No. 57-26695, impact-resistant polystyrene Simply adding a flame retardant to impart flame retardancy to the resin will significantly reduce the impact resistance, and adding a large amount of polybutadiene rubber to prevent the drop in impact resistance will reduce the self-cutting properties. There's a problem.
特公昭５７−２６６９５号公報に記載の発明は、難燃剤
の添加による上記の問題を、高シスポリブタジェンを含
むゴム状弾性体とビニル系単量体を主成分として得られ
るゴム変性重合体の膨潤指数を７．０−１４．０とする
ことにより、排除したもので、耐衝撃性及びセルフタッ
ピング特性に優れたＨ燃性熱可塑性樹脂組成物である。The invention described in Japanese Patent Publication No. 57-26695 solves the above problems caused by the addition of flame retardants by using a rubber-modified polymer obtained mainly from a rubber-like elastic body containing high cis polybutadiene and a vinyl monomer. This is a H-flammable thermoplastic resin composition with excellent impact resistance and self-tapping properties.
然し乍ら、特公昭５７−２６６９５号公報に記載の耐衝
撃性ポリスチレン系樹脂組成物は、合成樹脂成形品の成
形材料として用途によっては特に重要な物性である光沢
を低下させる問題があり、また、難燃剤の添加による耐
衝撃性の低下を必ずしも充分に抑制できない要素がある
。However, the impact-resistant polystyrene resin composition described in Japanese Patent Publication No. 57-26695 has the problem of reducing gloss, which is a particularly important physical property, depending on its use as a molding material for synthetic resin molded products. There are factors in which it is not always possible to sufficiently suppress a decrease in impact resistance due to the addition of a fuel.
従って、本発明の目的は、光沢が良好で且つ難燃剤を添
加した場合の耐衝撃性を充分に改良した、耐衝撃性ポリ
スチレン系樹脂組成物を提供することにある。Therefore, an object of the present invention is to provide an impact-resistant polystyrene resin composition that has good gloss and sufficiently improved impact resistance when a flame retardant is added.
Ｃ問題点を解決するための手段〕
本発明者らは、上記目的を達成すべく種々検討した結果
、ジエン系ゴム状重合体で変性し、膨潤を計数を、従来
耐衝撃性を低下させるとされていた大きな膨潤指数とな
した耐衝撃性ポリスチレン系樹脂が、難燃剤を添加した
場合の光沢及び耐衝撃性を改良できることを知見した。Means for Solving Problem C] As a result of various studies in order to achieve the above object, the present inventors have found that the present inventors have modified the resin with a diene rubber-like polymer to reduce swelling and impact resistance. It has been found that high-impact polystyrene-based resins with high swelling index, which had previously been used, can improve gloss and impact resistance when flame retardants are added.
本発明は、上記知見に基づいてなされたもので、ジエン
系ゴム状重合体で変性して得た、膨潤指数１５〜２５の
耐衝撃性ポリスチレン系樹脂に、ハロゲン系難燃剤及び
難燃補助剤を添加してなる、耐衝撃性ポリスチレン系樹
脂組成物を提供するものである。The present invention was made based on the above findings, and consists of adding a halogen flame retardant and a flame retardant auxiliary agent to an impact-resistant polystyrene resin with a swelling index of 15 to 25 obtained by modifying with a diene rubber polymer. The object of the present invention is to provide an impact-resistant polystyrene resin composition.
以下、本発明の耐衝撃性ポリスチレン系樹脂組成物につ
いて詳述する。Hereinafter, the impact-resistant polystyrene resin composition of the present invention will be explained in detail.
本発明に係る耐衝撃性ポリスチレン系樹脂は、ジエン系
ゴム状重合体とスチレンとから得られるもので、ジエン
系ゴム状重合体としては、ポリブタジェンゴム、スチレ
ン−ブタジェン共重合体、ブタジェン−アクリロニトリ
ル共重合体、ポリクロロプレン、イソブチレン−イソプ
レン共重合体等が挙げられ、ポリブタジェンゴムとして
は、好ましくは、シス−１，４構造含有率が８０％以上
のもの、更に好ましくは、例えば、シス−１，４構造含
有率８０〜９９％、トランス−１，４構造含有率０．５
〜２０％、１．ｚｔｌ造含有率０．５〜２０％のものが
用いられる。このようなポリブタジェンゴムは、有機ア
ルミニウム化合物と、コバルト又はニッケル化合物とを
含む触媒を用いる等の公知の製造法によって製造できる
。The impact-resistant polystyrene resin according to the present invention is obtained from a diene-based rubbery polymer and styrene. Examples of the diene-based rubbery polymer include polybutadiene rubber, styrene-butadiene copolymer, and butadiene-based rubbery polymer. Examples include acrylonitrile copolymer, polychloroprene, isobutylene-isoprene copolymer, etc., and polybutadiene rubber preferably has a cis-1,4 structure content of 80% or more, more preferably, for example, Cis-1,4 structure content 80-99%, trans-1,4 structure content 0.5
~20%, 1. Those having a ZTL content of 0.5 to 20% are used. Such polybutadiene rubber can be produced by a known production method, such as using a catalyst containing an organoaluminum compound and a cobalt or nickel compound.
また、本発明に係る耐衝撃性ポリスチレン系樹脂を得る
に際しての上記ジエン系ゴム状正合体とスチレンとの好
ましい使用割合は、スチレン７５〜９８重量部に対して
上記ジエン系ゴム状重合体２〜２５重量部であり、ジエ
ン系ゴム状重合体が２未満であると耐衝撃性を改良し難
く、２５を超えると溶液粘度が過大になるため工業的生
産が困難になる。In addition, when obtaining the impact-resistant polystyrene resin according to the present invention, the preferable ratio of the diene-based rubbery polymer and styrene is 2 to 98 parts by weight of the diene-based rubbery polymer to 75 to 98 parts by weight of styrene. If the amount of the diene rubber-like polymer is less than 25 parts by weight, it is difficult to improve impact resistance, and if it exceeds 25 parts by weight, the solution viscosity becomes excessive, making industrial production difficult.
本発明に係る耐衝撃性ポリスチレン系樹脂は、公知の方
法、例えば、塊状重合法、又は塊状−懸濁重合法、具体
的には、例えば特開昭５７−１４３３１３号公報に記載
の方法に準じて製造でき、その際、有機過酸化物の使用
量あるいは温度を変えることにより、膨潤指数１５〜２
５の耐衝撃性ポリスチレン系樹脂を製造することができ
る。The impact-resistant polystyrene resin according to the present invention can be produced by a known method, such as a bulk polymerization method or a bulk-suspension polymerization method, specifically, for example, according to the method described in JP-A-57-143313. At that time, by changing the amount of organic peroxide used or the temperature, the swelling index can be increased from 15 to 2.
No. 5 impact-resistant polystyrene resin can be produced.
また、本発明に係る耐衝撃性ポリスチレン系樹脂の製造
に際し、必要に応じ、上記ジエン系ゴム状重合体に他の
化合物、例えば、スチレン−ブタジェン共重合体、エチ
レン−プロピレン共重合体、エチレン−酢酸ビニル共重
合体等を上記ジエン系ゴム状重合体に対し５０重量％以
内において併用することができ、また上記スチレンに該
スチレンと共ｍ合可能なビニル系モノマーを該スチレン
に対し５０ｆｆｌｆｆ１％以内において併用できる。In addition, when producing the impact-resistant polystyrene resin according to the present invention, other compounds may be added to the diene rubber-like polymer, such as styrene-butadiene copolymer, ethylene-propylene copolymer, ethylene- A vinyl acetate copolymer or the like may be used together in an amount of up to 50% by weight based on the diene rubber-like polymer, and a vinyl monomer capable of co-merging with the styrene may be used in an amount of up to 50fflff1% based on the styrene. Can be used together.
上述の如くして得られる本発明に係る耐衝撃性ポリスチ
レン系樹脂の膨潤指数が１５未満の場合には良好な光沢
を有する成形品を得難く且つ難燃剤を添加した場合の耐
１１撃性の改良が不充分であり、また、膨潤指数が２５
を超えると、成形品の表面の平滑さが損なわれ、光沢も
劣るため、本発明の目的は達成されない。If the swelling index of the impact-resistant polystyrene resin according to the present invention obtained as described above is less than 15, it will be difficult to obtain a molded product with good gloss, and the 11 impact resistance will be lower when a flame retardant is added. The improvement was insufficient and the swelling index was 25.
If it exceeds this, the object of the present invention will not be achieved because the surface smoothness of the molded product will be impaired and the gloss will be poor.
また、本発明において、ジエン系ゴム状重合体としてポ
リブタジェンゴムを用いる場合には、シス−１，４構造
含有率が８０％以上のものを用いるのが好ましく、８０
％未満のものを用いた場合には、難燃剤添加後の耐衝撃
性が不充分になる惧れがある。In addition, in the present invention, when polybutadiene rubber is used as the diene-based rubbery polymer, it is preferable to use one with a cis-1,4 structure content of 80% or more, and 80% or more.
If less than % is used, there is a risk that the impact resistance after addition of the flame retardant will be insufficient.
尚、上記の膨潤指数は、上記耐衝撃性ポリスチレン系樹
脂１ｇをベンゼン５０ｎｉ１に溶解した後、これを遠心
分離（１０，ＯＯＯｒ、ｐ、ｍ、Ｘ ６０ｍｌｎ。The above swelling index was determined by dissolving 1 g of the above impact-resistant polystyrene resin in 50 ni1 of benzene and then centrifuging it (10, OOOr, p, m, x 60 mln.
）し、その上澄液を除去後、再度不溶分にベンゼン５０
ｍｌを加えて遠心分離した後のベンゼン不溶分の重量を
Ａとし、該Ａの乾燥重量をＢとした場合のＡ／Ｂの値で
ある。), and after removing the supernatant, add 50% benzene to the insoluble matter again.
ml is added and centrifuged, the weight of the benzene-insoluble matter is A, and the dry weight of A is B. This is the value of A/B.
また、本発明の耐衝撃性ポリスチレン系樹脂組成物にお
いて、前記耐衝撃性ポリスチレン系樹脂に添加されるハ
ロゲン系難燃剤としては、通常のもの、例えば、デカブ
ロムジフェニルエーテル、ヘキサブロムベンゼン、テト
ラプロブビスフェノールＡ１テトラブロムビスフエノー
ルＡのオリゴマー、トリブロムフェニル−２，３−ジブ
ロムプロピルエーテル、ヘキサブロムシクロドデカン、
テトラブロムエタン、トリス（２，３−ジブロムプロピ
ル）フォスフェート等が挙げられ、難燃補助剤としては
、二酸化アンチモン、硼砂、メタホウ酸バリウム、酸化
ジルコニウム等が挙げられ、特に二酸化アンチモンが好
ましい。In addition, in the impact-resistant polystyrene resin composition of the present invention, the halogen flame retardant added to the impact-resistant polystyrene resin is a usual one, such as decabrom diphenyl ether, hexabromobenzene, tetraprobu bisphenol. A1 oligomer of tetrabromobisphenol A, tribromphenyl-2,3-dibromopropyl ether, hexabromocyclododecane,
Examples include tetrabromoethane, tris(2,3-dibromopropyl) phosphate, etc., and flame retardant aids include antimony dioxide, borax, barium metaborate, zirconium oxide, etc., with antimony dioxide being particularly preferred.
また、上記ハロゲン系難燃剤及び難燃補助剤の添加量は
、耐ｉＦ１撃性ポリスチレン系樹脂１００重量部に対し
、それぞれ２〜３０重量部及び２〜２０重量部とするの
が好ましい。The amounts of the halogen flame retardant and flame retardant auxiliary agent added are preferably 2 to 30 parts by weight and 2 to 20 parts by weight, respectively, per 100 parts by weight of the iF1 impact-resistant polystyrene resin.
更に、本発明の耐衝撃性ポリスチレン系樹脂組成物には
、通常の合成樹脂組成物と同様に、必要に応じ、種々の
添加剤、例えば、安定剤、着色剤、可塑剤、紫外線吸収
剤を適宜添加できる。Furthermore, the impact-resistant polystyrene resin composition of the present invention may contain various additives, such as stabilizers, colorants, plasticizers, and ultraviolet absorbers, as necessary, as in ordinary synthetic resin compositions. It can be added as appropriate.
本発明の耐衝撃性ポリスチレン系樹脂組成物は、通常、
各成分を混合し常法によりベレット化されて用いられる
。The impact-resistant polystyrene resin composition of the present invention usually has
The components are mixed and made into pellets using a conventional method.
以下に本発明の耐衝撃性ポリスチレン系樹脂組成物に用
いられる、ポリブタジェン及び耐衝撃性ポリスチレン系
樹脂の製造例及び本発明の実施例を挙げる。Examples of manufacturing polybutadiene and impact resistant polystyrene resin used in the impact resistant polystyrene resin composition of the invention and examples of the invention are listed below.
製造例１ （ポリブタジェンの製造例）ベンゼン１５０
０ｍｌに、１．３−ブタジェン３８０ｇを加え、次いで
水１．８ ＋ｕ＋ｏｌｓジエチルアルミニウムモノクロ
ライド３．１１１１１０１％シクロオクタジエン１２ｍ
ｍｏｌ及びオクテン酸コバルト０．０１＋ａｍｏｌを加
えた後、６０℃下に３０分間攪拌して１゜３−ブタジェ
ンの重合反応を行わせた０重合反応終了後、重合溶液に
少量の２．６−ジ第三ブチルパラクレゾールを含むメタ
ノール５ｍｌを注入して重合を停止させて、ついで重合
溶液を水洗し、簡易型コアギユレータ−装置にてゴムを
クラムとして回収し、６０ ’Ｃで乾燥してポリブタジ
ェンゴム１３０ｇを得た。このポリブタジェンゴムは、
１゜２構造含有率が４．１％、シス−１，４構造含有率
９３．３％、トランス−１，４構造含有率２．６％であ
り、固有粘度〔η）−１，８であった。Production example 1 (Production example of polybutadiene) Benzene 150
Add 380 g of 1.3-butadiene to 0 ml, then add 1.8 m of water + u + ols diethylaluminum monochloride 3.1111101% cyclooctadiene 12 m
After adding 0.01+amol of cobalt octenoate, the polymerization reaction of 1°3-butadiene was carried out by stirring at 60°C for 30 minutes. After the polymerization reaction was completed, a small amount of 2,6-di Polymerization was stopped by injecting 5 ml of methanol containing tert-butyl para-cresol, and the polymerization solution was then washed with water. The rubber was collected as crumbs using a simple coagulator device, and dried at 60'C to form polybutadiene. 130 g of rubber was obtained. This polybutadiene rubber is
The 1°2 structure content is 4.1%, the cis-1,4 structure content is 93.3%, the trans-1,4 structure content is 2.6%, and the intrinsic viscosity is [η)-1,8. there were.
製造例２〜５
（耐衝撃性ポリスチレン系樹脂の製造例）１ａセパラブ
ルフラスコを窒素ガスで置換し、スチレン５５８ｇと上
記製造例１で得られたポリブタジェンゴム４２ｇ（ゴム
？ｆｆ１１％）とを加えて溶解し、ついでｎ−ドデシル
メルカプタン０．２４ｇを加えて、１２０℃でスチレン
重合率が３０％になるまで攪拌下に重合した。ついで重
合溶液を、０．５ｆｌｉ１％のポリビニルアルコール０
０ｍｌを加えた１．５７！のオートクレーブに注入し、
ベンゾイルパーオキサイド０．９３ｇおよびジクミルパ
ーオキサイドをそれぞれ下記表−１に示す如く変化させ
て加えて、１００℃で２時間、ついで１２５℃で３時間
、ついで１４０℃で２時間攪拌下に重合した．重合反応
混合物からビーズ状のボリマーをＩ簗し、水洗し、乾燥
し、押出機でペレット化して、それぞれ耐衝撃性ポリス
チレン樹脂５００ｇを得た。得られた耐衝撃性ポリスチ
レン樹脂をそれぞれ射出成形して、物性測定用の試験片
を作成し、それぞれ下記表−１に示す物性を測定した。Production Examples 2 to 5 (Production Examples of Impact-Resistant Polystyrene Resin) A separable flask 1a was replaced with nitrogen gas, and 558 g of styrene and 42 g of polybutadiene rubber (rubber?ff 11%) obtained in Production Example 1 were added. was added and dissolved, and then 0.24 g of n-dodecyl mercaptan was added and polymerized with stirring at 120° C. until the styrene polymerization rate reached 30%. The polymerization solution was then mixed with 0.5fli1% polyvinyl alcohol.
1.57 with 0ml added! inject into the autoclave of
0.93 g of benzoyl peroxide and dicumyl peroxide were added in different amounts as shown in Table 1 below, and the mixture was polymerized with stirring at 100°C for 2 hours, then at 125°C for 3 hours, and then at 140°C for 2 hours. ．． Bead-like polymers were collected from the polymerization reaction mixture, washed with water, dried, and pelletized using an extruder to obtain 500 g of impact-resistant polystyrene resin. The obtained impact-resistant polystyrene resins were each injection molded to prepare test pieces for measuring physical properties, and the physical properties shown in Table 1 below were measured.
それらの測定結果を下記表−１に示す。The measurement results are shown in Table 1 below.
製造例６〜９
上記！Ｉｉ！！造例２〜５におけるポリブタジェンゴム
の代わりにジエン３５ＡＳ（旭化成ｉ１瀞製、ポリブタ
ジェンゴム）（製造例６．７）及びタフデン２０００
（旭化成■製、スチレン−ブタジェンゴム）（製造例
８．９）を用い、ジクミルパーオキサイドをそれぞれ下
記表−１に示す如く変化させて加えた以外は、製造例２
〜５と同様にして耐衝撃性ポリスチレン系樹脂を得た。Production Examples 6 to 9 Above! Ii! ! Diene 35AS (manufactured by Asahi Kasei I1 Co., Ltd., polybutadiene rubber) (Production Example 6.7) and Tuffden 2000 were used instead of polybutadiene rubber in Preparation Examples 2 to 5.
(manufactured by Asahi Kasei ■, styrene-butadiene rubber) (Production Example 8.9) was used, except that dicumyl peroxide was added with changes as shown in Table 1 below.
An impact-resistant polystyrene resin was obtained in the same manner as in 5.
得られた耐衝撃性ポリスチレン樹脂をそれぞれ射出成形
して、物性測定用の試験片を作成し、それぞれ下記表−
１に示す物性を測定した。それらの測定結果を下記表−
１に示す。The resulting impact-resistant polystyrene resins were each injection molded to create test pieces for measuring physical properties, each of which was shown in the table below.
The physical properties shown in 1 were measured. The measurement results are shown in the table below.
Shown in 1.
表−１ 各物性の測定は、次の基準によった。Table-1 Measurement of each physical property was based on the following criteria.
ＤＣＰニジクミルパーオキサイドの使用量Ｓｌ（膨潤指
数） ：前記の通り。Amount Sl (swelling index) of DCP rainbow cumyl peroxide used: As described above.
ＭＩ：ＡＳＴＭ Ｄ １２３８ Ｇ法（２００℃
−５Ｋｇ＞実施例１〜４及び比較例１〜４
上記製造例２〜９でそれぞれ得た耐衝撃性ポリスチレン
系樹脂ｌｏｏ重量部に、それぞれ、デカブロムジフェニ
ルエーテル１５重量部及び二酸化アンチモン５ｉ（１）
１部を添加しそれらを混合した後、それぞれの混合物を
押出し機で押出し温度２１０℃でペレット化し、それぞ
れ難燃性樹脂組成物を得、これらの組成物を成形温度２
３０℃で射出成形し試験片を作成した。MI: ASTM D 1238 G method (200℃
-5Kg>Examples 1 to 4 and Comparative Examples 1 to 4 15 parts by weight of decabromidiphenyl ether and 5i(1) antimony dioxide were added to 1 part by weight of the impact-resistant polystyrene resin loo obtained in Production Examples 2 to 9, respectively.
After adding 1 part and mixing them, each mixture was pelletized with an extruder at an extrusion temperature of 210°C to obtain a flame retardant resin composition, and these compositions were pelletized at a molding temperature of 210°C.
Test pieces were prepared by injection molding at 30°C.
上記の各試験片についての物性の測定結果を下記表−２
に示す。The measurement results of the physical properties of each of the above test pieces are shown in Table 2 below.
Shown below.
尚、上記の二酸化アンチモンとしては、ＰＡＴＯＸ−Ｌ
（日本精鉱社製、粒ｐｉ６〜７μ）を用いた。In addition, as the above antimony dioxide, PATOX-L
(manufactured by Nippon Seiko Co., Ltd., grain size pi 6-7μ) was used.
表−２
上記表−２に示す結果から、本発明品（実施例１〜４）
は、比較品（比較例１〜４）に比して、難燃剤添加によ
る耐衝撃性の低下が小さく、耐衝撃性に優れ且つ光沢が
良好であり、更に硬度の低下は極めて小さい（実用上支
障のない程度）ことが判る。Table 2 From the results shown in Table 2 above, the products of the present invention (Examples 1 to 4)
Compared to the comparative products (Comparative Examples 1 to 4), the drop in impact resistance due to the addition of flame retardant is small, the impact resistance is excellent, the gloss is good, and the drop in hardness is extremely small (in practical use) (to the extent that there is no problem).
実施例５及び比較例５．６
三酸化アンチモンとして、ＡＴＯＸ−３（日本精鉱社製
、粒径０．５μ）を用いた以外は、それぞれ上記実施例
１及び比較例１．２と同様にして難燃性樹脂組成物を得
、実施例１と同様にそれらの各試験片について行った物
性の測定結果を下記表−３に示す。Example 5 and Comparative Example 5.6 The same procedures as in Example 1 and Comparative Example 1.2 were carried out, respectively, except that ATOX-3 (manufactured by Nippon Seiko Co., Ltd., particle size 0.5μ) was used as antimony trioxide. A flame-retardant resin composition was obtained, and the physical properties of each test piece were measured in the same manner as in Example 1, and the results are shown in Table 3 below.
表−３
上記表−３に示す結果から、本発明品（実施例５）は、
比較品（比較例５．６）に比して、難燃剤添加による耐
ｉｈ撃性の低下が小さく、■（衝撃性に優れ且つ光沢が
良好であり、更に硬度の低下は掘めて小さい（実用上支
障のない程度）ことが判る。Table 3 From the results shown in Table 3 above, the product of the present invention (Example 5)
Compared to the comparative products (Comparative Example 5.6), the reduction in induction shock resistance due to the addition of flame retardants is small (■) (excellent impact resistance and good gloss), and the decrease in hardness is significantly small ( (to the extent that there is no practical problem).
本発明の耐衝撃性ポリスチレン系樹脂組成物は、難燃剤
の添加された従来の耐衝撃性ポリスチレン系樹脂に比し
て、耐衝撃性が改良され且つ良好な光沢を呈するもので
ある。The impact-resistant polystyrene resin composition of the present invention has improved impact resistance and exhibits good gloss compared to conventional impact-resistant polystyrene resins to which a flame retardant is added.
Claims (3)
１５〜２５の耐衝撃性ポリスチレン系樹脂〔但し、膨潤
指数は、耐衝撃性ポリスチレン系樹脂１ｇをベンゼン５
０ｍｌに溶解した後、これを遠心分離（１０，０００ｒ
．ｐ．ｍ．×６０ｍｉｎ、）し、その上澄液を除去後、
再度不溶分にベンゼン５０ｍｌを加えて遠心分離した後
のベンゼン不溶分の重量をＡとし、該Ａの乾燥重量をＢ
とした場合のＡ／Ｂの値〕に、ハロゲン系難燃剤及び難
燃補助剤を添加してなる、耐衝撃性ポリスチレン系樹脂
組成物。(1) Impact-resistant polystyrene resin with a swelling index of 15 to 25 obtained by modifying with a diene-based rubbery polymer [However, the swelling index is as follows:
After dissolving in 0 ml, this was centrifuged (10,000 r
．． p. m. x 60 min), and after removing the supernatant,
After adding 50 ml of benzene to the insoluble matter again and centrifuging it, the weight of the benzene insoluble matter is A, and the dry weight of A is B.
An impact-resistant polystyrene-based resin composition obtained by adding a halogen-based flame retardant and a flame-retardant auxiliary agent to the value of A/B when
率８０％以上のハイシスポリブタジエンゴムである、特
許請求の範囲第（１）項記載の耐衝撃性ポリスチレン系
樹脂組成物。(2) The impact-resistant polystyrene-based resin composition according to claim (1), wherein the diene-based rubbery polymer is a high-cis polybutadiene rubber having a cis-1,4 structure content of 80% or more.
衝撃性ポリスチレン系樹脂１００重量部に対し、それぞ
れ２〜３０重量部及び２〜２０重量部である、特許請求
の範囲第（１）項記載の耐衝撃性ポリスチレン系樹脂組
成物。(3) The amount of the halogen flame retardant and flame retardant auxiliary agent added is 2 to 30 parts by weight and 2 to 20 parts by weight, respectively, based on 100 parts by weight of the impact-resistant polystyrene resin. The impact-resistant polystyrene resin composition described in item 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020385A JPH0674361B2 (en) | 1986-01-31 | 1986-01-31 | Impact-resistant polystyrene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020385A JPH0674361B2 (en) | 1986-01-31 | 1986-01-31 | Impact-resistant polystyrene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62179552A true JPS62179552A (en) | 1987-08-06 |
| JPH0674361B2 JPH0674361B2 (en) | 1994-09-21 |
Family
ID=12025563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61020385A Expired - Fee Related JPH0674361B2 (en) | 1986-01-31 | 1986-01-31 | Impact-resistant polystyrene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674361B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039626A (en) * | 2005-06-28 | 2007-02-15 | Toyo Styrene Co Ltd | Flame-retardant styrenic thermoplastic resin composition |
| JP2015187226A (en) * | 2014-03-27 | 2015-10-29 | 東洋スチレン株式会社 | Styrenic flame-retardant resin composition and molded article made using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5726695A (en) * | 1980-06-05 | 1982-02-12 | Ciba Geigy Ag | Organophosphate, manufacture and noxious organism repellant containing same |
-
1986
- 1986-01-31 JP JP61020385A patent/JPH0674361B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5726695A (en) * | 1980-06-05 | 1982-02-12 | Ciba Geigy Ag | Organophosphate, manufacture and noxious organism repellant containing same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039626A (en) * | 2005-06-28 | 2007-02-15 | Toyo Styrene Co Ltd | Flame-retardant styrenic thermoplastic resin composition |
| JP4616147B2 (en) * | 2005-06-28 | 2011-01-19 | 東洋スチレン株式会社 | Styrenic flame retardant thermoplastic resin composition |
| JP2015187226A (en) * | 2014-03-27 | 2015-10-29 | 東洋スチレン株式会社 | Styrenic flame-retardant resin composition and molded article made using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0674361B2 (en) | 1994-09-21 |
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