JPS6372750A - Impact-resistant styrene polymer composition - Google Patents
Impact-resistant styrene polymer compositionInfo
- Publication number
- JPS6372750A JPS6372750A JP19828687A JP19828687A JPS6372750A JP S6372750 A JPS6372750 A JP S6372750A JP 19828687 A JP19828687 A JP 19828687A JP 19828687 A JP19828687 A JP 19828687A JP S6372750 A JPS6372750 A JP S6372750A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- component
- vinyl
- impact
- substituted aromatic
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title description 34
- 229920001400 block copolymer Polymers 0.000 claims abstract description 34
- 150000001993 dienes Chemical class 0.000 claims abstract description 14
- 229920001519 homopolymer Polymers 0.000 claims abstract description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 16
- 229920001971 elastomer Polymers 0.000 abstract description 10
- 239000000945 filler Substances 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000000806 elastomer Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 3
- 238000000034 method Methods 0.000 description 9
- 239000005060 rubber Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- -1 1.3-dimethylstyrene Chemical compound 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002900 organolithium compounds Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 101100072643 Arabidopsis thaliana IPS2 gene Proteins 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 235000010215 titanium dioxide Nutrition 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、耐衝撃性及び成形品の外観特性に優れたスチ
レン系重合体組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a styrenic polymer composition having excellent impact resistance and appearance characteristics of molded articles.
従来、ポリスチレンの耐衝撃性や耐油性等を改良した耐
衝撃性ゴム変性スチレン系重合体として耐衝撃性ゴム変
性スチレン重合体、アクリロニトリル−ブタジェン−ス
チレン共重合体、アクリル酸エステル−ブタジェン−ス
チレン共重合体、メタクリル酸エステル−ブタジェン−
スチレン共重合体、耐衝撃性ゴム変性スチレン−無水マ
レイン酸共重合体などが市販されている。Conventionally, impact-resistant rubber-modified styrene polymers, acrylonitrile-butadiene-styrene copolymers, and acrylic ester-butadiene-styrene copolymers have been used as impact-resistant rubber-modified styrenic polymers that improve the impact resistance and oil resistance of polystyrene. Polymer, methacrylic acid ester-butadiene-
Styrene copolymers, impact-resistant rubber-modified styrene-maleic anhydride copolymers, and the like are commercially available.
これらのゴム変性スチレン系重合体は剛性、耐衝撃性、
加工性などの特徴をいかし、包装材料、電気部品、自動
車部品、建築の装飾品など種々の製品に使用されている
。These rubber-modified styrenic polymers have rigidity, impact resistance,
Taking advantage of its characteristics such as processability, it is used in a variety of products such as packaging materials, electrical parts, automobile parts, and architectural decorations.
従来、製造業者は価格および物性などを勘案し市場で入
手可能なこれらゴム変性スチレン系重合体を選択し、こ
れを単独又は配合物にして使用し、末端ユーザーの要望
に適合した製品を作っている。Traditionally, manufacturers have selected rubber-modified styrenic polymers available on the market based on price and physical properties, and used them alone or in combination to create products that meet the needs of end users. There is.
しかし市場で入手可能なゴム変性スチレン系重合体では
耐衝撃性が不足で、末端ユーザーの要望する耐衝撃性製
品を製造することが出来ない事態がしばしば生じている
。このため、他の物性を低下させることなく、市場で入
手可能なゴム変性スチレン系重合体の耐衝撃性を向上さ
せる配合技術の開発が切望されている。However, the rubber-modified styrenic polymers available on the market lack impact resistance, and it is often impossible to manufacture impact-resistant products desired by end users. Therefore, there is a strong desire to develop a compounding technique that improves the impact resistance of commercially available rubber-modified styrenic polymers without degrading other physical properties.
ゴム変性スチレン系重合体の耐衝撃性改良方法の一つと
して共役ジオレフィン−ビニル置換芳香族化合物ブロッ
ク共重合体を強靭化剤として使用することが既に知られ
ている。例えば、特公昭５２−２１０１２号公輻及び特
開昭４８−５６２５０号公報には耐衝撃性ゴム変性スチ
レン重合体の強靭化剤として、比較的共役ジオレフィン
含有量の多いブロック共重合体を使用することが記載さ
れている。しかしながら、前者においては耐衝撃性は改
良されるもののゴム変性スチレン系重合体の表面光沢が
悪化するという欠点があり、また後者においては良好な
耐衝撃性及び表面光沢を有するゴム変性ポリスチレン組
成物が得られるものの、その特性はゴム変性ポリスチレ
ンのメチルエチルケトン可溶部の極限粘度とスチレン−
ジエンブロック共重合体の極限粘度との差を０．１ｄｌ
／ｇ以下にしたときにのみ発現されるものであり、組成
物の構成成分として極めて特殊の成分を使用しなければ
上記特性は達成されないという欠点を有している。It is already known that one of the methods for improving the impact resistance of rubber-modified styrenic polymers is to use a conjugated diolefin-vinyl substituted aromatic compound block copolymer as a toughening agent. For example, in Japanese Patent Publication No. 52-21012 and Japanese Patent Application Laid-open No. 48-56250, a block copolymer with a relatively high content of conjugated diolefin is used as a toughening agent for impact-resistant rubber-modified styrene polymer. It is stated that However, in the former, although the impact resistance is improved, the surface gloss of the rubber-modified styrenic polymer is deteriorated, and in the latter, the rubber-modified polystyrene composition has good impact resistance and surface gloss. However, its properties are determined by the intrinsic viscosity of the methyl ethyl ketone soluble portion of rubber-modified polystyrene and the styrene-
The difference from the intrinsic viscosity of the diene block copolymer is 0.1 dl.
/g or less, and has the disadvantage that the above characteristics cannot be achieved unless very specific components are used as constituents of the composition.
一方、特開昭５０−１２１３５１号公報や特開昭５１−
１２８３４７号公報には耐衝撃性ゴム変性スチレン重合
体の強靭化剤として、比較的ビニル置換芳香族含有量の
多いブロック共重合体を使用することが記載されており
、かかる方法によって得られた組成物は良好な表面光沢
を有する。しかしながら、これらの組成物は耐衝撃性が
低下するという欠点を有し、必ずしも満足できる方法で
はなかった。On the other hand, JP-A-50-121351 and JP-A-51-
Publication No. 128347 describes the use of a block copolymer with a relatively high vinyl-substituted aromatic content as a toughening agent for impact-resistant rubber-modified styrene polymers, and the composition obtained by this method The object has good surface gloss. However, these compositions have the drawback of reduced impact resistance, and the method has not always been satisfactory.
〔問題点を解決するための手段及びその作用〕本発明者
らはかかる現状に鑑み、耐衝撃性ゴム変性スチレン系重
合体を含有する組成物において耐衝撃性と表面光沢に優
れた組成物を得るべく鋭意検討した結果、比較的共役ジ
オレフィン含有量の多いブロック共重合体と比較的ビニ
ル置換芳香族化合物含有量の多いブロック共重合体とを
、耐衝撃性ゴム変性スチレン系重合体と組合せることに
よりその目的が達成されることを見出し、本発明をなす
に至った。[Means for solving the problems and their effects] In view of the current situation, the present inventors have developed a composition containing an impact-resistant rubber-modified styrenic polymer that has excellent impact resistance and surface gloss. As a result of intensive studies, we found that a block copolymer with a relatively high content of conjugated diolefins and a block copolymer with a relatively high content of vinyl-substituted aromatic compounds were combined with an impact-resistant rubber-modified styrenic polymer. The inventors have discovered that the object can be achieved by doing so, and have come up with the present invention.
即ち、本発明のスチレン系重合体組成物は、（ｉ）ビニ
ル置換芳香族化合物の含有量が１０重量％以上５５重量
％未満である、共役ジオレフィンとビニル置換芳香族化
合物とからなるブロック共重合体３〜３５重量％、
（ｉｉ ）ビニル置換芳香族化合物の含有量が６５重量
％以上９５重１１％以下である、共役ジオレフィンとビ
ニル置換芳香族化合物とからなるブロック共重合体であ
り、しかも
であるブロック共重合体５〜９２重量％、並びに（ｉｉ
ｉ ）耐衝撃性ゴム変性スチレン系重合体５〜９２重量
％からなる耐衝撃性と外観特性に優れた組成物に関する
。That is, the styrenic polymer composition of the present invention comprises (i) a block polymer comprising a conjugated diolefin and a vinyl-substituted aromatic compound, in which the content of the vinyl-substituted aromatic compound is 10% by weight or more and less than 55% by weight; A block copolymer consisting of a conjugated diolefin and a vinyl-substituted aromatic compound, in which the polymer is 3 to 35% by weight, and (ii) the content of the vinyl-substituted aromatic compound is 65% by weight or more and 95% by weight or less and 11% or less. , and 5 to 92% by weight of the block copolymer, and (ii
i) A composition comprising 5 to 92% by weight of an impact-resistant rubber-modified styrenic polymer and having excellent impact resistance and appearance characteristics.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
まず、成分（ｉ）のブロック共重合体は、ビニル置換芳
香族化合物の含有量が１０重量％以上５５重量％未満、
好ましくは２０〜５３重量％、更に好ましくは２５〜５
０重量％のものである。又成分（ｉｉ ）のブロック共
重合体はビニル置換芳香族化合物の含有量が６５重量％
以上９５重量％以下、好ましくは６７〜９０重量％のも
のである０本発明においては、ビニル置換芳香族化合物
の含有量が上記範囲内にある二種類のブロック共重合体
を使用することにより耐衝撃性と表面光沢に優れた組成
物が得られる。First, the block copolymer of component (i) has a vinyl-substituted aromatic compound content of 10% by weight or more and less than 55% by weight,
Preferably 20 to 53% by weight, more preferably 25 to 5% by weight
0% by weight. In addition, the block copolymer of component (ii) has a vinyl-substituted aromatic compound content of 65% by weight.
In the present invention, the content of the vinyl-substituted aromatic compound is 95% by weight or less, preferably 67 to 90% by weight. A composition with excellent impact resistance and surface gloss can be obtained.
本発明で使用される成分（ｉ）のブロック共重合体の製
造方法としては、特公昭３６−１９２８６号公報、特公
昭４３−１４９７９号公報、特公昭４９−３６９５７号
公報などに記載されている通りであり、又成分（ｉｉ
）のブロック共重合体の製造方法としては前記三者の公
報のほか、更に特公昭４Ｂ −２４２３号公報、特公昭
４８−４１０６号公報などに記載されている通りである
。The method for producing the block copolymer of component (i) used in the present invention is described in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-14979, Japanese Patent Publication No. 49-36957, etc. This is true, and the component (ii
) The method for producing the block copolymer is as described in Japanese Patent Publication No. 4B-2423, Japanese Patent Publication No. 48-4106, etc. in addition to the above-mentioned three publications.
これらはすべて、炭化水素？′ｊＩｉ中で有機リチウム
化合物等のアニオン重合開始剤を用い、共役ジオレフィ
ンとビニル置換芳香族化合物をブロック共重合する方法
であり、−Ｃ式、
（Ａ−Ｂ）、、Ａ−（−Ｂ−Ａ）、、Ｂ−（−Ａ−Ｂ）
、（上式において、Ａはビニル置換芳香族化合物を主と
する重合体ブロックであり、Ｂは共役ジオレフィンを主
とする重合体ブロックである。ＡブロックとＢブロック
との境界は必ずしも明瞭に区別される必要はない。又、
ｎは１以上の整数である。）
で表わされる線状ブロック共重合体、あるいは一般式
％式％
（上式において、Ａ、Ｂは前記と同じであり、Ｘは例え
ば四塩化ケイ素、四塩化スズなどのカップリング剤の残
基又は多官能有機リチウム化合物の残基を示す０ｍおよ
びｎは１以上の整数である。）で表わされるラジアルブ
ロック共重合体として得られる。尚、上記ブロック共重
合体の構造には、完全型のブロック共重合体も、又テー
パー型のブロック共重合体も含みうる。Are all these hydrocarbons? 'jIi is a method of block copolymerizing a conjugated diolefin and a vinyl-substituted aromatic compound using an anionic polymerization initiator such as an organolithium compound. -A),,B-(-A-B)
, (In the above formula, A is a polymer block mainly composed of a vinyl-substituted aromatic compound, and B is a polymer block mainly composed of a conjugated diolefin. The boundary between the A block and the B block is not necessarily clear. There is no need to differentiate.Also,
n is an integer of 1 or more. ), or a linear block copolymer represented by the general formula % (In the above formula, A and B are the same as above, and X is a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride. or 0m and n, which represent residues of a polyfunctional organolithium compound, are integers of 1 or more. The structure of the above block copolymer may include a complete block copolymer and a tapered block copolymer.
本発明において、成分（ｉ）及び成分（ｉｉ）のブロッ
ク共重合体の製造に用いられるビニル置換芳香族炭化水
素としては、スチレン、Ｏ−メチルスチレン、ｐ−メチ
ルスチレン、ｐ−ｔｅｒｔブチルスチレン、１．３−ジ
メチルスチレン、α−メチルスチレン、ビニルナフタレ
ン、ビニルアントラセン等で、特に一般的なものとして
はスチレンがあげられる。これらは１種のみならず２種
以上の混合物として用いても良い、また、共役ジエンと
しては、炭素数が４ないし８０１対の共役二重結合を有
するジオレフィンであり、例えば、１．３−ブタジェン
、２−メチル−１，３−ブタジェン（イソプレン）、２
．３−ジメチル−１，３−ブタジェン、１．３−ペンタ
ジェン、１．３−へキサジエン等があげられるが、特に
一般的なものとしては、１．３−ブタジェン、イソプレ
ンがあげられる。これらは１種のみならず２種以上の混
合物として用いても良い。In the present invention, the vinyl-substituted aromatic hydrocarbons used in the production of the block copolymers of component (i) and component (ii) include styrene, O-methylstyrene, p-methylstyrene, p-tertbutylstyrene, 1.3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, etc., and styrene is particularly common. These may be used not only as a single type but also as a mixture of two or more types. Also, examples of conjugated dienes include diolefins having 4 to 801 carbon atoms and conjugated double bonds, such as 1.3- Butadiene, 2-methyl-1,3-butadiene (isoprene), 2
．． Examples include 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and particularly common ones include 1,3-butadiene and isoprene. These may be used not only as a single type but also as a mixture of two or more types.
本発明で使用する成分（ｉ）及び成分（ｉｉ ）のブロ
ック共重合体の分子量は、１０．０００〜ｉ、ｏｏｏ、
ｏｏｏ、好ましくは３０．０００〜８００，０００であ
る。The molecular weight of the block copolymer of component (i) and component (ii) used in the present invention is 10.000 to i, ooo,
ooo, preferably 30,000 to 800,000.
本発明において、成分（ｉｉ ）のブロック共重合体と
して、一般式Ａ−Ｂ （Ａ及びＢの意味は前記と同じ）
で表わされる構造を有するブロック共重合体を使用する
場合には、特に光沢に優れた組成物が得られる。In the present invention, as the block copolymer of component (ii), the general formula AB (the meanings of A and B are the same as above) is used.
When using a block copolymer having the structure represented by the following, a composition particularly excellent in gloss can be obtained.
又、成分（ｉｉ）のブロック共重合体は、共重合体中に
ブロック状ホモ重合体セグメントとして存在しているビ
ニル置換芳香族化合物の割合が７５重量％を超えるもの
でなければならない。ブロック状ホモ重合体セグメント
として存在しているビニル置換芳香族化合物の割合が少
なくなると剛性や耐熱性が低下する傾向がみられるため
好ましくない、ビニル置換芳香族化合物のブロック状ホ
モ重合体セグメントに組込まれていないビニル置換芳香
族化合物、換言すれば、共役ジエンと共重合しているビ
ニル置換芳香族化合物はビニル置換芳香族化合物のブロ
ック状ホモ重合体セグメント以外の重合体鎖中の全体又
は特定領域に均一に分布していても、又テーパー状に分
布していてもよい。In addition, the block copolymer of component (ii) must have a proportion of the vinyl-substituted aromatic compound present as a block homopolymer segment in the copolymer in excess of 75% by weight. Incorporating vinyl-substituted aromatic compounds into block-like homopolymer segments is undesirable because a decrease in the proportion of vinyl-substituted aromatic compounds present as block-like homopolymer segments tends to reduce rigidity and heat resistance. In other words, the vinyl-substituted aromatic compound copolymerized with a conjugated diene is a vinyl-substituted aromatic compound that is not copolymerized with a conjugated diene. It may be distributed uniformly or may be distributed in a tapered manner.
共重合体中のビニル置換芳香族化合物のブロック状ホモ
重合体セグメントは、四酸化オスミウムを触媒としてジ
−ターシャリ−ブチルハイドロパーオキサイドにより共
重合体を酸化分解する方法（例えば、Ｌ、Ｍ、Ｋｏｌｔ
ｈｏｆｆｒｄａｌ、 Ｊ、Ｐｏｌｙｍｅｒ Ｓｃｉ、。The block homopolymer segment of the vinyl-substituted aromatic compound in the copolymer can be obtained by oxidative decomposition of the copolymer with di-tert-butyl hydroperoxide using osmium tetroxide as a catalyst (for example, L, M, Kolt
hoffrdal, J., Polymer Sci.
１．４２９（１９４６）記載の方法）などにより定量す
ることができる。従って、ブロック共重合体中にブロッ
ク状ホモ重合体セグメントとして存在しているビニル置
換芳香族化合物の割合は、かかる方法などで定量された
ブロック状ホモ重合体セグメントの量をブロック共重合
体中に含有されている全ビニル置換芳香族化合物の量で
除して把握することができる。1.429 (1946)). Therefore, the proportion of vinyl-substituted aromatic compounds present as block-like homopolymer segments in a block copolymer can be determined by calculating the amount of block-like homopolymer segments in the block copolymer determined by such a method. It can be determined by dividing by the amount of all vinyl-substituted aromatic compounds contained.
次に、本発明において使用する耐衝撃性ゴム変性スチレ
ン系重合体は、ビニル置換芳香族化合物もしくはこれと
共重合可能なモノマーとエラストマーとの混合物を重合
することにより得られ、重合方法としては懸濁重合、乳
化重合、塊状重合、塊状−懸ｓｍ合などが一般に行なわ
れている。ビニル置換芳香族化合物と共重合可能なモノ
マーとしては、α−メチルスチレン、アクリロニトリル
、アクリル酸エステル、メタクリル酸エステル、無水マ
レイン酸などがあげられる。又、エラストマーとしては
、天然ゴム、合成イソプレンゴム、ブタジェンゴム、ス
チレン−ブタジェンゴム、ハイスチレンゴム、ポリブタ
ジェンゴム、クロロプレンゴム、ポリブテンゴム、ゴム
状エチレン−プロピレン共重合体、ゴム状ブタジェン−
アクリロニトリル共重合体、ブチルゴム、各種ニトリル
系ゴム、ゴム状エチレン−酢酸ビニル共重合体、ゴム状
エチレン−アクリル酸エステル共重合体、ゴム状アタク
チックポリプロピレン樹脂、ゴム状エチレン−アクリル
酸アイオノマー等が使用される。Next, the impact-resistant rubber-modified styrenic polymer used in the present invention is obtained by polymerizing a mixture of a vinyl-substituted aromatic compound or a monomer copolymerizable therewith with an elastomer. Turbid polymerization, emulsion polymerization, bulk polymerization, bulk-suspension SM polymerization, etc. are generally carried out. Examples of monomers copolymerizable with the vinyl-substituted aromatic compound include α-methylstyrene, acrylonitrile, acrylic esters, methacrylic esters, and maleic anhydride. Examples of elastomers include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, high styrene rubber, polybutadiene rubber, chloroprene rubber, polybutene rubber, rubbery ethylene-propylene copolymer, and rubbery butadiene rubber.
Acrylonitrile copolymer, butyl rubber, various nitrile rubbers, rubbery ethylene-vinyl acetate copolymer, rubbery ethylene-acrylic acid ester copolymer, rubbery atactic polypropylene resin, rubbery ethylene-acrylic acid ionomer, etc. are used. be done.
特に好ましい耐衝撃性ゴム変性スチレン系重合体として
は、耐衝撃性ゴム変性スチレン重合体、アクリロニトリ
ル−ブタジェン−スチレン共重合体、アクリル酸エステ
ル−ブタジェン−スチレン共重合体、メタクリル酸エス
テル−ブタジェン−スチレン共重合体、耐衝撃性ゴム変
性スヂレンー無水マレイン酸共重合体などがあげられ、
これらは単独もしくは二種以上の混合物として使用する
こともできる。Particularly preferred impact-resistant rubber-modified styrenic polymers include impact-resistant rubber-modified styrene polymers, acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and methacrylic ester-butadiene-styrene copolymers. copolymers, impact-resistant rubber-modified styrene-maleic anhydride copolymers, etc.
These can be used alone or as a mixture of two or more.
本発明においては、成分（ｉ）、（ｉｉ）及び（ｉｉｉ
）に加えて更に非ゴム変性スチレン系重合体を含有さ
せて組成物の剛性等を改良することができる。In the present invention, components (i), (ii) and (iii)
), a non-rubber modified styrenic polymer can be further added to improve the rigidity of the composition.
非ゴム変性スチレン系重合体は、ビニル置換芳香族化合
物もしくはこれと共重合可能なモノマーを重合すること
により得られるものである。ビニル置換芳香族化合物と
共重合可能な七ツマ−としてはα−メチルスチレン、ア
クリロニトリル、アクリル酸エステル、メタクリル酸エ
ステル、無水マレイン酸などがあげられる。The non-rubber modified styrenic polymer is obtained by polymerizing a vinyl-substituted aromatic compound or a monomer copolymerizable therewith. Examples of heptamers copolymerizable with vinyl-substituted aromatic compounds include α-methylstyrene, acrylonitrile, acrylic esters, methacrylic esters, and maleic anhydride.
特に好ましい非ゴム変性スチレン系重合体としては、ポ
リスチレン、スチレン−α−メルスチレン共重合体、ア
クリロニトリル−スチレン共重合体、スチレン−メタク
リル酸エステル共重合体、スチレン−無水マレイン酸共
重合体などがあげられ、これらは単独もしくは二種以上
の混合物として使用することができる。Particularly preferred non-rubber modified styrenic polymers include polystyrene, styrene-α-merstyrene copolymer, acrylonitrile-styrene copolymer, styrene-methacrylic acid ester copolymer, and styrene-maleic anhydride copolymer. These can be used alone or as a mixture of two or more.
本発明において各成分の好ましい配合重量比は、成分（
ｉ）が３〜３５重量％、好ましくは５〜２５重量％であ
り、成分（ｉｉ）が５〜９２重量％であり、そして成分
（ｉｉ ）が５〜９２重量％である。かかる成分（ｉ）
、（ｉｉ）及び（ｉｉｉ ）の配合比範囲は、耐衝撃性
と表面光沢に優れた組成物を得る上で推奨される使用範
囲である。かかる組成物において成分（ｉｉ ）と成分
（ｉｉｉ ）の組成比が１／１以上の場合は比較的透明
性の良好な組成物が得られる。In the present invention, the preferred blending weight ratio of each component is as follows:
i) is 3 to 35% by weight, preferably 5 to 25% by weight, component (ii) is 5 to 92% by weight and component (ii) is 5 to 92% by weight. Such ingredient (i)
, (ii) and (iii) are recommended ranges for use in obtaining a composition with excellent impact resistance and surface gloss. In such a composition, when the composition ratio of component (ii) to component (iii) is 1/1 or more, a composition with relatively good transparency can be obtained.
本発明のスチレン系重合体組成物は、必要に応じて、任
意の充填剤を含むことができる０本発明において充填剤
を配合する場合の配合量は、本発明のスチレン系重合体
組成物１００重量部に対して、好ましくは５０重量部以
下である。充填剤の配合量が５０重量部を超えると、組
成物の耐衝撃性が低下する傾向がみられる。The styrenic polymer composition of the present invention may contain any filler if necessary. In the case of blending the filler in the present invention, the blending amount is 100% of the styrenic polymer composition of the present invention. It is preferably 50 parts by weight or less. If the amount of filler added exceeds 50 parts by weight, the impact resistance of the composition tends to decrease.
充填剤の種類はプラスチックの配合に一般に用いられる
ものであれば特に制限はないが、例えば、ガラス繊維、
ガラスピーズ、シリカ、炭カル、タルクなどの無機補強
剤、有機繊維、クマロンインデン樹脂などの有機補強剤
、有機パーオキサイド、無機パーオキサイドなどの架橋
剤、チタン白、カーボンブラック、酸化鉄などの顔料、
染料、難燃剤、酸化防止剤、紫外線吸収剤、帯電防止剤
、滑剤、可塑剤、その他の増量剤或いはこれらの混合物
などが挙げられる。The type of filler is not particularly limited as long as it is commonly used in plastic formulations, but examples include glass fiber,
Inorganic reinforcing agents such as glass peas, silica, charcoal, talc, organic fibers, organic reinforcing agents such as coumaron indene resin, crosslinking agents such as organic peroxide and inorganic peroxide, titanium white, carbon black, iron oxide, etc. pigment,
Examples include dyes, flame retardants, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, other fillers, and mixtures thereof.
本発明において各成分からなるスチレン系重合体組成物
は、従来公知のあらゆる配合方法によって製造すること
ができる。In the present invention, the styrenic polymer composition consisting of each component can be produced by any conventionally known compounding method.
例えば、オープンロール、インテンシブミキサー、イン
ターナルミキサー、コニーダー、二軸ローター付の連続
混練機、押出機等の一般的な混和機を用いた溶融混練方
法、各成分を溶剤に溶解又は分散混合後湾剤を加熱除去
する方法が用いられる。For example, melt-kneading methods using general kneading machines such as open rolls, intensive mixers, internal mixers, co-kneaders, continuous kneaders with twin-screw rotors, extruders, etc. After dissolving or dispersing each component in a solvent and mixing, A method of removing the agent by heating is used.
この様にして得た本発明のスチレン系重合体組成物は、
従来公知の任意の成形加工法、例えば、押出成形、射出
成形、中空成形などによってシート、発泡体、フィルム
１．各種形状の射出成形品、中空成形品、圧空成形品、
真空成形品２軸延伸成形品等極めて多種多様にわたる実
用上有用な製品に容易に成形加工出来る。The styrenic polymer composition of the present invention thus obtained is
Sheets, foams, films 1. are formed by any conventionally known forming process such as extrusion molding, injection molding, blow molding, etc. Injection molded products of various shapes, hollow molded products, pressure molded products,
It can be easily molded into a wide variety of practically useful products such as vacuum formed products and biaxially stretched products.
本発明を更に詳細に説明するために以下に本発明の実施
例を示すが、本発明の内容をこれらの実施例に限定する
ものでないことは云うまでもない。Examples of the present invention will be shown below to explain the present invention in more detail, but it goes without saying that the content of the present invention is not limited to these Examples.
尚、実施例で使用した溶媒、単量体及びランダマイグー
等の添加剤は、予め精製、乾燥したものを使用した。Note that the solvents, monomers, and additives such as Randomy Goo used in the Examples were purified and dried in advance.
１〜４び １，２
Ｂ−Ａ−Ｂ−Ａ （Ｂはブタジェンを主体とする重合体
ブロックを、Ａはスチレンを主体とする重合体ブロック
を示す）の構造を有するスチレン含有量４０重量％、分
子量約８０，０００のテーパー型ブロツク共重合体（サ
ンプル１とする）と、同様の構造を有するスチレン含有
量８０重量％、全スチレンに対するブロックスチレンの
割合が８３重量％、分子量約１４０．０００．１．２−
ビニル結合金有量１１％のテーパー型ブロツク共重合体
くサンプル２とする）及びゴム含有量８重量％でメルト
フロー（条件Ｇ）２の耐衝撃性ゴム変性ポリスチレン（
旧ＰＳ１とする）を第１表に示した配合割合に従ってヘ
ンシェルミキサーで充分混合した後、押出機によりペレ
ット化した。得られたベレットを射出成形して物性測定
試験片を作成し、それらの物性を測定した。1 to 4 and 1,2 B-A-B-A (B indicates a polymer block mainly composed of butadiene, A indicates a polymer block mainly composed of styrene) with a styrene content of 40% by weight , a tapered block copolymer (referred to as sample 1) with a molecular weight of approximately 80,000, a styrene content of 80% by weight having a similar structure, a ratio of block styrene to the total styrene of 83% by weight, and a molecular weight of approximately 140.000. .1.2-
A tapered block copolymer with a vinyl bond content of 11% (referred to as sample 2) and an impact-resistant rubber-modified polystyrene (referred to as sample 2) with a rubber content of 8% by weight and a melt flow (condition G) of 2.
PS1) were sufficiently mixed in a Henschel mixer according to the blending ratio shown in Table 1, and then pelletized using an extruder. The obtained pellets were injection molded to prepare specimens for measuring physical properties, and their physical properties were measured.
結果を第１表に示したが、この結果から本発明の組成物
は耐衝撃性及び表面光沢の点でバランスのとれた組成物
であることが明らかである。The results are shown in Table 1, and it is clear from the results that the composition of the present invention is well-balanced in terms of impact resistance and surface gloss.
尚、実施例１の組成物の曲げ弾性率は１４５００ｋｇ／
−であったが、実施例１のサンプル２の代わりにスチレ
ン含有量８０重量％、全スチレンに対するブロックスチ
レンの割合が５６重量％であるブロック共重合体を用い
た組成物の曲げ弾性率は１３０００ ｋｇ／ｃｆｆｌで
あった。The flexural modulus of the composition of Example 1 was 14,500 kg/
- However, the flexural modulus of the composition using a block copolymer with a styrene content of 80% by weight and a block styrene ratio of 56% by weight to the total styrene in place of Sample 2 of Example 1 was 13,000. kg/cffl.
以下余白 気」−表 Ｑ主１） ＪＩＳ−に田ｎに準拠。Margin below "Ki" - table Q Main 1) Compliant with JIS-Niden.
牲２） ＪＩＳ−Ｚ ８７４１ニａ
−・ ５び ３
サンプル１の代わりにＡ−Ｂ−Ａの構造を有するスチレ
ン含有量３０重量％、分子量約１２０，０００の完全型
ブロツク共重合体（サンプル３とする）を用い、サンプ
ル２の代わりにＢ−Ａの構造を有するスチレン含有ｆｆ
１８０重量％、全スチレンに対するブロックスチレンの
割合が８３重量％、分子量約１４０．０００．１．２−
ビニル結合含有ｆｆ１１１％のテーパー型ブロツク共重
合体（サンプル４とする）又はＡ−Ｂ−Ａの構造を有す
るスチレン含有１１６０重量％、分子量約１４０．００
０．１．２−ビニル結合含有Ｍｉｌ１％の完全型ブロツ
ク共重合体（サンプル５とする）を用いた他は実施例１
と同様にして物性測定試験片を作成し、物性を測定した
。2) JIS-Z 8741 Nia - 5 and 3 Instead of Sample 1, a complete block copolymer with 30% styrene content and a molecular weight of about 120,000 having the structure ABA (Sample 3 ), and instead of sample 2, a styrene-containing ff having the structure B-A was used.
180% by weight, proportion of block styrene to total styrene is 83% by weight, molecular weight approximately 140.000.1.2-
A tapered block copolymer with a vinyl bond content of 111% ff (referred to as sample 4) or a styrene content of 1160% by weight with an A-B-A structure, a molecular weight of approximately 140.00.
Example 1 except that a 1% Mil complete block copolymer containing 0.1.2-vinyl bonds (referred to as sample 5) was used.
A physical property measurement test piece was prepared in the same manner as above, and the physical properties were measured.
結果を第２表に示したが、この結果からサンプル４を用
いたものはより表面光沢に優れるが、サンプル５を用い
たものは表面光沢に劣ることが分かる。The results are shown in Table 2, and it can be seen from the results that the sample using sample 4 has better surface gloss, but the sample using sample 5 has poorer surface gloss.
６ び ″ ４，５
第３表に示した配合割合に従って、サンプル１、サンプ
ル２及びゴム含有量６型景％でメルトフロー２の耐衝撃
性ゴム変性ポリスチレン（ＨＩＰＳ ２とする）からな
る組成物のベレットを作成し、次いでシート押出機を用
いて厚さＱ、３ ｘｍのシートを成形した。又、比較例
としてサンプル１もしくは）！ＩＰＳ２を含有しない組
成物を作成し、同様にシート成形した。6 and '' 4,5 Compositions consisting of sample 1, sample 2 and impact-resistant rubber-modified polystyrene (referred to as HIPS 2) with a rubber content of 6% and a melt flow of 2 according to the compounding ratios shown in Table 3. A pellet was prepared, and then a sheet with a thickness Q of 3 x m was formed using a sheet extruder.Also, as a comparative example, a composition not containing sample 1 or )!IPS2 was prepared, and a sheet was formed in the same manner. .
得られたシートの特性を第３表に示したが、この結果か
ら本発明の組成物は比較例に比べて透明性、耐衝撃性の
点でバランスのとれた組成物であることが明らかである
。The properties of the obtained sheet are shown in Table 3, and it is clear from the results that the composition of the present invention is a composition with better balance in terms of transparency and impact resistance than the comparative example. be.
ｔＬ表tL table
Claims (1)
％以上５５重量％未満である、共役ジオレフィンとビニ
ル置換芳香族化合物とからなるブロック共重合体３〜３
５重量％、 （ｉｉ）ビニル置換芳香族化合物の含有量が６５重量％
以上９５重量％以下である、共役ジオレフィンとビニル
置換芳香族化合物とからなるブロック共重合体であり、
しかも （共重合体中にブロック状ホモ重合 体セグメントとして存在している ビニル置換芳香族化合物の量） ／ （共重合体中に含有されている全ビ ニル置換芳香族化合物の量） ×１００＞７５ であるブロック共重合体５〜９２重量％並びに（ｉｉｉ
）耐衝撃性ゴム変性スチレン系重合体５〜９２重量％か
らなるスチレン系重合体組成物。[Scope of Claims] 1. (i) Block copolymers 3 to 3 consisting of a conjugated diolefin and a vinyl-substituted aromatic compound, in which the content of the vinyl-substituted aromatic compound is 10% by weight or more and less than 55% by weight.
5% by weight, (ii) the content of vinyl-substituted aromatic compounds is 65% by weight
A block copolymer consisting of a conjugated diolefin and a vinyl-substituted aromatic compound, the amount of which is 95% by weight or less,
Moreover, (amount of vinyl-substituted aromatic compounds present as block homopolymer segments in the copolymer) / (amount of all vinyl-substituted aromatic compounds contained in the copolymer) × 100>75 and (iii
) A styrenic polymer composition comprising 5 to 92% by weight of an impact-resistant rubber-modified styrenic polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19828687A JPS6372750A (en) | 1987-08-10 | 1987-08-10 | Impact-resistant styrene polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19828687A JPS6372750A (en) | 1987-08-10 | 1987-08-10 | Impact-resistant styrene polymer composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9380080A Division JPS5721449A (en) | 1980-07-11 | 1980-07-11 | Impact-resistant styrene polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6372750A true JPS6372750A (en) | 1988-04-02 |
| JPH0312099B2 JPH0312099B2 (en) | 1991-02-19 |
Family
ID=16388595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19828687A Granted JPS6372750A (en) | 1987-08-10 | 1987-08-10 | Impact-resistant styrene polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6372750A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088293A (en) * | 2006-10-02 | 2008-04-17 | Mitsubishi Plastics Ind Ltd | Elastic film and method for producing the elastic film |
| WO2016129532A1 (en) * | 2015-02-09 | 2016-08-18 | 旭化成株式会社 | Block copolymer composition, molding material, resin composition, and molded article |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5189550A (en) * | 1975-02-04 | 1976-08-05 | JUGOTAISOSE IBUTSU | |
| JPS5227447A (en) * | 1975-08-26 | 1977-03-01 | Abbott Lab | Thermoplastic polymer mextures containing medical sealing and resealing material radial block polymers |
| JPS52115855A (en) * | 1976-03-24 | 1977-09-28 | Gunze Kk | Biaxially oriented heat shrinkable polystylene film havig lowwtemperature shrinking property and colddresistance |
| JPS52117947A (en) * | 1976-03-31 | 1977-10-03 | Asahi Chem Ind Co Ltd | High-impact styrene resin compositions |
| JPS52124046A (en) * | 1976-04-12 | 1977-10-18 | Asahi Chem Ind Co Ltd | Styrene resin compositions having excellent melt-flow characteristics |
| JPS53250A (en) * | 1976-06-23 | 1978-01-05 | Denki Kagaku Kogyo Kk | High empact polymer composition |
-
1987
- 1987-08-10 JP JP19828687A patent/JPS6372750A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5189550A (en) * | 1975-02-04 | 1976-08-05 | JUGOTAISOSE IBUTSU | |
| JPS5227447A (en) * | 1975-08-26 | 1977-03-01 | Abbott Lab | Thermoplastic polymer mextures containing medical sealing and resealing material radial block polymers |
| JPS52115855A (en) * | 1976-03-24 | 1977-09-28 | Gunze Kk | Biaxially oriented heat shrinkable polystylene film havig lowwtemperature shrinking property and colddresistance |
| JPS52117947A (en) * | 1976-03-31 | 1977-10-03 | Asahi Chem Ind Co Ltd | High-impact styrene resin compositions |
| JPS52124046A (en) * | 1976-04-12 | 1977-10-18 | Asahi Chem Ind Co Ltd | Styrene resin compositions having excellent melt-flow characteristics |
| JPS53250A (en) * | 1976-06-23 | 1978-01-05 | Denki Kagaku Kogyo Kk | High empact polymer composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088293A (en) * | 2006-10-02 | 2008-04-17 | Mitsubishi Plastics Ind Ltd | Elastic film and method for producing the elastic film |
| WO2016129532A1 (en) * | 2015-02-09 | 2016-08-18 | 旭化成株式会社 | Block copolymer composition, molding material, resin composition, and molded article |
| US10501617B2 (en) | 2015-02-09 | 2019-12-10 | Asahi Kasei Kabushiki Kaisha | Block copolymer composition, molded material, resin composition, and molded product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0312099B2 (en) | 1991-02-19 |
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