JPS6231017B2 - - Google Patents
Info
- Publication number
- JPS6231017B2 JPS6231017B2 JP54145435A JP14543579A JPS6231017B2 JP S6231017 B2 JPS6231017 B2 JP S6231017B2 JP 54145435 A JP54145435 A JP 54145435A JP 14543579 A JP14543579 A JP 14543579A JP S6231017 B2 JPS6231017 B2 JP S6231017B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- component
- composition
- styrene
- 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.)
- Expired
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004793 Polystyrene Substances 0.000 claims description 22
- 229920002223 polystyrene Polymers 0.000 claims description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 9
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- 229920001400 block copolymer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 27
- 238000002156 mixing Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Description
本発明は耐衝撃性および耐亀裂性にすぐれた押
出し成形用ポリスチレン樹脂組成物に関し、詳し
くは汎用ポリスチレンをベースとしてこれに２種
類の特定のスチレン―ブタジエンブロツク共重合
体を一定割合で加え、さらに耐衝撃性ポリスチレ
ンを添加することによつて得られる押出し成形に
適したポリスチレン樹脂組成物に関する。
一般に汎用ポリスチレンは成形しやすく、また
透明性が良好であるため広範囲にわたつて用いら
れているが、耐衝撃性に劣るという欠点がある。
そのため従来から、この汎用ポリスチレンにス
チレン―ブタジエンブロツク共重合体を添加する
ことが広く行われているが、得られる組成物は耐
衝撃性の向上と引換えに透明性が著しく低下し、
これを原料とする成形品の商品価値が低減すると
いう欠点があつた。
そこで本発明者らは上記従来技術の欠点を克服
し、透明性を可能な限り維持しつつ耐衝撃性を改
善したポリスチレン樹脂組成物を開発すべく鋭意
研究を重ねた。その研究過程においてポリスチレ
ンに一定範囲でスチレン成分を含有する２種類の
線状スチレン―ブタジエンブロツク共重合体を一
定量添加することにより、すぐれた物性の組成物
が得られることを見出した。しかしながら、この
組成物は通常の用途には有効に利用できるもの
の、押出し成形のようなダイリツプの剪断力に著
しく影響される成形法を用いる場合には、得られ
る成形物中のスチレン―ブタジエンブロツク共重
合体が機械方向に配向し、横方向の亀裂が生じや
すいため、不測の外力が働くおそれのある器物の
素材としては、あまり好適でないことが予想され
ている。
そのため本発明者らは上記不都合を解消すべく
さらに研究を続け、その結果、汎用ポリスチレン
に２種類の線状スチレン―ブタジエンブロツク共
重合体のほかに耐衝撃性ポリスチレンを所定量添
加混合することによつて、その成形物が商品価値
を失わない程度に透明性を維持しつつ耐衝撃性を
有する、特に押出し成形品として横方向の亀裂の
生じ難い組成物を形成しうることを見出した。
すなわち本発明は、(A)汎用ポリスチレン88〜50
重量部、(B)スチレン成分を60重量％以上含有する
線状スチレン―ブタジエンブロツク共重合体５〜
20重量部、(C)スチレン成分を60重量％以下含有す
る線状スチレン―ブタジエン共重合体５〜20重量
部および(D)耐衝撃性ポリスチレン２〜10重量部よ
りなる耐衝撃性および耐亀裂性に優れた押出し成
形用ポリスチレン樹脂組成物を提供するものであ
る。
本発明の組成物においてベースとして用いられ
る成分は(A)成分である汎用ポリスチレンである。
この汎用ポリスチレンは通常、重量平均分子量
200000〜400000であり、メルトインデツクスは
0.1〜40g／10分（200℃）、好ましくは１〜10g／
10分（200℃）のものである。耐衝撃性は不充分
であるが透明性にすぐれたものである。本発明で
は(B)，(C)および(D)成分を加えることによつて上記
汎用ポリスチレンの本来有する優れた透明性を可
能な限り維持しつつ耐衝撃性を高め、同時に押出
し成形の際に成形物の横方向の亀裂を防止するも
のである。従つて本発明の組成物のベースである
(A)成分として汎用ポリスチレンに代えて透明性の
小さい耐衝撃性ポリスチレン等を用いた場合、得
られる組成物は耐衝撃性は大きなものとなるが、
透明性が不充分であるため、本発明の目的を達成
することができない。
また本発明の(A)成分である汎用ポリスチレンの
配合量は、目的とする組成物全体100重量部あた
り88〜50重量部、好ましくは81〜62重量部とすべ
きである。
次に本発明の(B)成分としては、スチレン成分を
60重量％以上含有する線状スチレン―ブタジエン
ブロツク共重合体が用いられる。この(B)成分の配
合量は目的とする組成物全体100重量部あたり５
〜20重量部、好ましくは８〜15重量部の範囲とす
べきである。５重量部以下では得られる組成物の
透明性が著しく不良となり、また20重量部以上に
すると組成物の剛性が低下する。
さらに本発明の(C)成分としては、スチレン成分
を60重量％以下含有する線状スチレン―ブタジエ
ンブロツク共重合体が用いられる。この(C)成分の
配合量は目的とする組成物全体100重量部あたり
５〜20重量部、好ましくは８〜15重量部とすべき
である。５重量部以下では得られる組成物の衝撃
強度が不充分なものとなり、また20重量部以上に
すると、組成物の透明性が低下する。
上記の(B)，(C)成分である線状スチレン―ブタジ
エンブロツク共重合体の分子構造は、スチレン重
合ブロツクをＳ、ブタジエン重合ブロツクをＢで
表わすと（Ｓ―Ｂ―）oＳ、（Ｓ―Ｂ）o，Ｂ―（Ｓ―
Ｂ）oの如く示されるものの１種または２種以上の
組合わせであり、各共重合体全体として(B)成分は
スチレン成分を60重量％以上含有。したものであ
り、(C)成分はスチレン成分を60重量％以下の範囲
で含有したものである。
次いで本発明の(D)成分としては、耐衝撃性ポリ
スチレンが用いられる。この耐衝撃性ポリスチレ
ンは通常メルトインデツクス１〜10g／10分、重
量平均分子量100000〜300000であり、またゴム成
分含有量５〜７％程度のものであり、得られる組
成物の透明性を可能な限り維持しつつ耐衝撃性を
向上せしめる作用、特に押出し成形の際に横方向
の亀裂を防止する作用を示す。この(D)成分である
耐衝撃性ポリスチレンの配合量は目的とする組成
物全体100重量部あたり２〜10重量部、好ましく
は３〜８重量部となるようにすべきである。２重
量部以下では得られる組成物の耐衝撃性の向上が
充分でなく、また10重量部以上では透明性が低下
する。
本発明においては上述の(A)成分である汎用ポリ
スチレンに、(B)，(C)および(D)成分のすべてを添加
することが必要である。いずれか一成分でも添加
しないと所望する物性を付与することができな
い。
本発明の組成物は、上述の(A)，(B)，(C)および(D)
成分を所定範囲内の割合にて混合することによつ
て製造する。上記各成分の混練にあたつては、乾
燥混合と溶融混合の併用法、一段溶融混合法、多
段溶融混合法等各種の方法を用いることができ
る。混合および混練の順序は特に制限はなく、た
とえば４成分を同時に混合、混練してもよく、ま
た(A)成分である汎用ポリスチレンに、(B)，(C)およ
び(D)成分のいずれか一成分を加えて混合、混練
し、得られた中間混合物に残りの成分を順次加え
て混合、混練し、目的とする組成物を製造しても
よい。
なお、この際に用いる混練機はバンバリーミキ
サー、コニーダー、押出機等各種のものをあげる
ことができる。
かくして得られた本発明のポリスチレン樹脂組
成物は、全光線透過率、かすみ度等で表示される
透明性を、これを素材とする成形品の商品価値を
失なわない程度に維持するものであるとともに、
フイルムインパクト強さ、引張衝撃強さ等で示さ
れる耐衝撃性の大きなものである。従つて、押出
し成形に際して横方向に亀裂を生ずることなく、
シート状成形物をはじめとして様々な押出し成形
物を得ることができる。そのため本発明の組成物
は、各種成形材料、特に不測な衝撃、例えば引張
衝撃などを受けやすい薄物成形容器の成形材料と
して有効に利用することができる。
次に本発明の実施例を示す。
実施例および比較例
所定量の(A)汎用ポリスチレン（メルトインデツ
クス4.1g／10分、重量平均分子量286000）、(B)線
状スチレン―ブタジエンブロツク共重合体（スチ
レン成分含量62重量％）、(C)線状スチレン―ブタ
ジエンブロツク共重合体（スチレン成分含量39重
量％）および(D)耐衝撃性ポリスチレン（メルトイ
ンデツクス1.9g／10分、重量平均分子量208000）
の各ペレツトをＶ型ブレンダーにて乾燥混合し
た。次いで得られた混合物をシリンダー直径50mm
のシート製造装置を用い、200℃にて均一に混練
しつつ厚さ0.35mmの目的組成物のシートを成形し
た。混合比を段階的に変化させつつ上述の方法で
得られる各組成物のシートについて各種物性を23
℃で測定した。結果を第１表に示す。
The present invention relates to a polystyrene resin composition for extrusion molding that has excellent impact resistance and crack resistance, and more specifically, it is made of general-purpose polystyrene as a base, to which two specific styrene-butadiene block copolymers are added at a certain ratio, and The present invention relates to a polystyrene resin composition suitable for extrusion molding obtained by adding high-impact polystyrene. In general, general-purpose polystyrene is widely used because it is easy to mold and has good transparency, but it has the drawback of poor impact resistance. For this reason, it has been widely practiced to add a styrene-butadiene block copolymer to general-purpose polystyrene, but the resulting composition has significantly reduced transparency in exchange for improved impact resistance.
The drawback was that the commercial value of molded products made from this material was reduced. Therefore, the present inventors have conducted extensive research in order to overcome the drawbacks of the above-mentioned conventional techniques and to develop a polystyrene resin composition that has improved impact resistance while maintaining transparency as much as possible. In the course of this research, it was discovered that a composition with excellent physical properties could be obtained by adding certain amounts of two types of linear styrene-butadiene block copolymers containing styrene components within a certain range to polystyrene. However, although this composition can be effectively used for ordinary purposes, when using a molding method such as extrusion that is significantly affected by the shear force of the die lip, the styrene-butadiene block in the resulting molded product may be Because the polymer is oriented in the machine direction and is prone to cracking in the lateral direction, it is predicted that it is not very suitable as a material for vessels that are likely to be subjected to unexpected external forces. Therefore, the present inventors continued their research to solve the above-mentioned disadvantages, and as a result, they decided to add and mix a predetermined amount of impact-resistant polystyrene in addition to two types of linear styrene-butadiene block copolymers to general-purpose polystyrene. Therefore, it has been found that it is possible to form a composition that has impact resistance while maintaining transparency to the extent that the molded product does not lose its commercial value, and in particular, is difficult to cause lateral cracks as an extrusion molded product. That is, the present invention provides (A) general-purpose polystyrene 88-50
Parts by weight, (B) Linear styrene-butadiene block copolymer containing 60% by weight or more of styrene component 5~
20 parts by weight, (C) 5 to 20 parts by weight of a linear styrene-butadiene copolymer containing 60% by weight or less of a styrene component, and (D) 2 to 10 parts by weight of impact-resistant polystyrene. The present invention provides a polystyrene resin composition for extrusion molding with excellent properties. The component used as a base in the composition of the present invention is component (A), a general-purpose polystyrene.
This general purpose polystyrene typically has a weight average molecular weight of
200000 to 400000, and the melt index is
0.1-40g/10 minutes (200℃), preferably 1-10g/
10 minutes (200℃). Although impact resistance is insufficient, transparency is excellent. In the present invention, by adding components (B), (C), and (D), the excellent transparency originally inherent in the above-mentioned general-purpose polystyrene is maintained as much as possible while increasing the impact resistance, and at the same time, during extrusion molding. This prevents horizontal cracks in the molded product. Therefore, it is the basis of the composition of the invention.
If a low-transparency impact-resistant polystyrene or the like is used as component (A) instead of general-purpose polystyrene, the resulting composition will have high impact resistance, but
Due to insufficient transparency, the object of the present invention cannot be achieved. The amount of general-purpose polystyrene, which is component (A) of the present invention, should be 88 to 50 parts by weight, preferably 81 to 62 parts by weight, per 100 parts by weight of the entire target composition. Next, as the component (B) of the present invention, a styrene component is used.
A linear styrene-butadiene block copolymer containing 60% by weight or more is used. The blending amount of this component (B) is 5 parts per 100 parts by weight of the entire target composition.
It should range from ~20 parts by weight, preferably from 8 to 15 parts by weight. If it is less than 5 parts by weight, the transparency of the resulting composition will be extremely poor, and if it is more than 20 parts by weight, the rigidity of the composition will be reduced. Further, as component (C) of the present invention, a linear styrene-butadiene block copolymer containing 60% by weight or less of a styrene component is used. The amount of component (C) to be blended should be 5 to 20 parts by weight, preferably 8 to 15 parts by weight, per 100 parts by weight of the entire intended composition. If the amount is less than 5 parts by weight, the resulting composition will have insufficient impact strength, and if it is more than 20 parts by weight, the transparency of the composition will decrease. The molecular structure of the linear styrene-butadiene block copolymer, which is the component (B) and (C) above, is as follows: (S-B-) o S, ( S-B) o ,B-(S-
B) It is one type or a combination of two or more of the following as shown in o , and each copolymer as a whole contains 60% by weight or more of a styrene component. Component (C) contains a styrene component in a range of 60% by weight or less. Next, as the component (D) of the present invention, impact-resistant polystyrene is used. This impact-resistant polystyrene usually has a melt index of 1 to 10 g/10 minutes, a weight average molecular weight of 100,000 to 300,000, and a rubber component content of about 5 to 7%, which allows the resulting composition to be transparent. It shows the effect of improving impact resistance while maintaining the same properties as possible, especially the effect of preventing lateral cracks during extrusion molding. The amount of high-impact polystyrene, component (D), should be 2 to 10 parts by weight, preferably 3 to 8 parts by weight, per 100 parts by weight of the entire intended composition. If the amount is less than 2 parts by weight, the impact resistance of the resulting composition will not be sufficiently improved, and if it is more than 10 parts by weight, the transparency will decrease. In the present invention, it is necessary to add all of the components (B), (C), and (D) to the general-purpose polystyrene that is the above-mentioned component (A). Unless even one component is added, desired physical properties cannot be imparted. The composition of the present invention comprises the above-mentioned (A), (B), (C) and (D).
It is manufactured by mixing the components in proportions within a predetermined range. In kneading the above-mentioned components, various methods can be used, such as a combination of dry mixing and melt mixing, a single-stage melt-mixing method, and a multi-stage melt-mixing method. The order of mixing and kneading is not particularly limited; for example, the four components may be mixed and kneaded at the same time, and any of the components (B), (C), and (D) may be added to the general-purpose polystyrene that is the (A) component. One component may be added and mixed and kneaded, and the remaining components may be sequentially added to the obtained intermediate mixture and mixed and kneaded to produce the desired composition. The kneading machines used in this case include various types such as a Banbury mixer, a co-kneader, and an extruder. The thus obtained polystyrene resin composition of the present invention maintains transparency as indicated by total light transmittance, degree of haze, etc. to an extent that does not impair the commercial value of molded products made from it. With,
It has high impact resistance as shown by film impact strength, tensile impact strength, etc. Therefore, without causing cracks in the lateral direction during extrusion molding,
Various extruded products including sheet-like products can be obtained. Therefore, the composition of the present invention can be effectively used as a molding material for various types of molding materials, particularly for thin molded containers that are susceptible to unexpected impacts such as tensile impacts. Next, examples of the present invention will be shown. Examples and Comparative Examples Predetermined amounts of (A) general-purpose polystyrene (melt index 4.1 g/10 minutes, weight average molecular weight 286000), (B) linear styrene-butadiene block copolymer (styrene component content 62% by weight), (C) Linear styrene-butadiene block copolymer (styrene content 39% by weight) and (D) impact-resistant polystyrene (melt index 1.9 g/10 min, weight average molecular weight 208000)
The pellets were dry mixed in a V-type blender. The resulting mixture was then poured into a cylinder with a diameter of 50 mm.
A sheet of the target composition with a thickness of 0.35 mm was formed while uniformly kneading the composition at 200°C using a sheet manufacturing apparatus. Various physical properties were determined for sheets of each composition obtained by the above method while changing the mixing ratio stepwise.
Measured at °C. The results are shown in Table 1.
【表】【table】
第１図は成形品座屈強度を測定するために組成
物シートから成形した逆角錐台のトレー（蓋な
し）の斜視図である。
FIG. 1 is a perspective view of an inverted pyramidal tray (without lid) formed from a composition sheet for measuring the buckling strength of a molded article.
Claims (1)
ン成分を60重量％以上含有する線状スチレン―ブ
タジエンブロツク共重合体５〜20重量部、(C)スチ
レン成分を60重量％以下含有する線状スチレン―
ブタジエンブロツク共重合体５〜20重量部および
(D)耐衝撃性ポリスチレン２〜10重量部よりなる耐
衝撃性および耐亀裂性に優れた押出し成形用ポリ
スチレン樹脂組成物。1 (A) 88 to 50 parts by weight of general-purpose polystyrene, (B) 5 to 20 parts by weight of linear styrene-butadiene block copolymer containing 60% by weight or more of styrene component, (C) Containing 60% by weight or less of styrene component Linear styrene
5 to 20 parts by weight of butadiene block copolymer and
(D) A polystyrene resin composition for extrusion molding with excellent impact resistance and crack resistance, comprising 2 to 10 parts by weight of impact-resistant polystyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14543579A JPS5670044A (en) | 1979-11-12 | 1979-11-12 | Polystyrene resin composition for extrusion molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14543579A JPS5670044A (en) | 1979-11-12 | 1979-11-12 | Polystyrene resin composition for extrusion molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5670044A JPS5670044A (en) | 1981-06-11 |
| JPS6231017B2 true JPS6231017B2 (en) | 1987-07-06 |
Family
ID=15385170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14543579A Granted JPS5670044A (en) | 1979-11-12 | 1979-11-12 | Polystyrene resin composition for extrusion molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5670044A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0571123U (en) * | 1992-03-02 | 1993-09-24 | 花王株式会社 | Folding container |
| JPH0676027U (en) * | 1991-07-12 | 1994-10-25 | 凸版印刷株式会社 | Liquid paper container |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58129038A (en) * | 1982-01-27 | 1983-08-01 | Denki Kagaku Kogyo Kk | Transparent impact-resistant polystyrene film |
| JPS638450A (en) * | 1986-06-27 | 1988-01-14 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition |
| JPS6372747A (en) * | 1987-08-26 | 1988-04-02 | Asahi Chem Ind Co Ltd | Styrene polymer composition |
| WO2006068064A1 (en) * | 2004-12-20 | 2006-06-29 | Kraton Jsr Elastomers K.K. | Thermoplastic resin composition |
| WO2008023400A1 (en) * | 2006-08-21 | 2008-02-28 | Shin-Etsu Polymer Co., Ltd. | Styrenic resin sheet and embossed carrier tape |
| CN103998514B (en) * | 2011-12-20 | 2017-04-26 | 东洋苯乙烯股份有限公司 | Styrene-based optical resin composition |
| JP6310219B2 (en) * | 2013-09-27 | 2018-04-11 | 東洋スチレン株式会社 | Styrenic resin composition for optics |
| TWI638847B (en) | 2015-02-09 | 2018-10-21 | 旭化成股份有限公司 | Block copolymer composition, molding material, resin composition, and molded body |
| JP7019298B2 (en) * | 2017-02-13 | 2022-02-15 | 東京インキ株式会社 | Sheets or pellets for plastic scintillators |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53250A (en) * | 1976-06-23 | 1978-01-05 | Denki Kagaku Kogyo Kk | High empact polymer composition |
-
1979
- 1979-11-12 JP JP14543579A patent/JPS5670044A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53250A (en) * | 1976-06-23 | 1978-01-05 | Denki Kagaku Kogyo Kk | High empact polymer composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0676027U (en) * | 1991-07-12 | 1994-10-25 | 凸版印刷株式会社 | Liquid paper container |
| JPH0571123U (en) * | 1992-03-02 | 1993-09-24 | 花王株式会社 | Folding container |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5670044A (en) | 1981-06-11 |
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