JPH0755995B2 - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH0755995B2 JPH0755995B2 JP61101928A JP10192886A JPH0755995B2 JP H0755995 B2 JPH0755995 B2 JP H0755995B2 JP 61101928 A JP61101928 A JP 61101928A JP 10192886 A JP10192886 A JP 10192886A JP H0755995 B2 JPH0755995 B2 JP H0755995B2
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- thermoplastic resin
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- styrene
- poly
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は熱可塑性樹脂組成物に関し、詳しくは耐熱性の
すぐれた熱可塑性樹脂組成物に関する。The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition having excellent heat resistance.
一般に、熱可塑性樹脂は他の素材に比べて成形性にすぐ
れ、また充分な剛性を有していることから、家庭用品を
はじめ、電気製品,機械器具の部品など様々な製品の成
形材料に用いられている。In general, thermoplastic resins have superior moldability compared to other materials and have sufficient rigidity, so they are used as molding materials for various products such as household products, electrical products, and parts of machinery and equipment. Has been.
しかし、熱可塑性樹脂はこのようなすぐれた性質を有し
ているものの、耐熱性の点で充分であるとは言い難いと
いう欠点がある。熱可塑性樹脂の耐熱性を向上させるた
めには、無機充填材を添加することが有効であるが、成
形性の低下や比重の増大など様々な不都合が生ずる。However, although the thermoplastic resin has such excellent properties, it has a drawback that it is difficult to say that it is sufficient in terms of heat resistance. In order to improve the heat resistance of the thermoplastic resin, it is effective to add an inorganic filler, but various disadvantages such as a decrease in moldability and an increase in specific gravity occur.
そこで、本発明者らはこのような不都合がなく、しかも
耐熱性の向上した熱可塑性樹脂を開発すべく鋭意研究を
重ねた。Therefore, the present inventors have conducted earnest research to develop a thermoplastic resin that does not have such inconvenience and has improved heat resistance.
その結果、シンジオタクチック構造を有するスチレン系
の重合体を一定割合で含有せしめた熱可塑性樹脂組成物
が、目的とする物性を備えたものであることを見出し、
本発明を完成するに至った。As a result, it was found that the thermoplastic resin composition containing a styrene-based polymer having a syndiotactic structure at a constant ratio has the desired physical properties,
The present invention has been completed.
すなわち本発明は、主としてシンジオタクチック構造を
有するスチレン系重合体1〜99重量%と、前記シンジオ
タクチック構造を有するスチレン系重合体以外の熱可塑
性樹脂99〜1重量%とからなる熱可塑性樹脂組成物を提
供するものである。That is, the present invention mainly relates to a thermoplastic resin composed of 1 to 99% by weight of a styrene polymer having a syndiotactic structure and 99 to 1% by weight of a thermoplastic resin other than the styrene polymer having a syndiotactic structure. A composition is provided.
本発明の組成物においては、主としてシンジオタクチッ
ク構造を有するスチレン系重合体を含有せしめることが
必要である。このスチレン系重合体は、主としてシンジ
オタクチック構造、即ち炭素−炭素結合から形成される
主鎖に対して側鎖であるフェニル基あるいは置換フェニ
ル基が交互に反対方向に位置する新規な立体構造を有す
るものであり、そのタクティシティーは核磁気共鳴法
(NMR法)により定量される。In the composition of the present invention, it is necessary to mainly contain a styrene polymer having a syndiotactic structure. This styrene polymer mainly has a syndiotactic structure, that is, a novel three-dimensional structure in which a phenyl group or a substituted phenyl group, which is a side chain, is alternately located in the opposite direction with respect to the main chain formed from carbon-carbon bonds. The tacticity is determined by the nuclear magnetic resonance method (NMR method).
NMRにより測定されるタクティシティーは、連続する複
数個の構造単位の存在割合、例えば2個の場合はダイア
ッド,3個の場合はトリアッド,5個の場合はペンタッドに
よって示すことができるが、本発明に言う主としてシン
ジオタクチック構造を有するスチレン系重合体とは、総
じてダイアッドで85%以上若しくはペンタッドで35%以
上のシンジオタクチック構造を有するポリスチレン,ポ
リ(アルキルスチレン),ポリ(ハロゲン化スチレ
ン),ポリ(アルコキシスチレン),ポリ(安息香酸エ
ステルスチレン)およびこれらの混合物、あるいはこれ
らを主成分とする共重合体を指称する。なお、ここでポ
リ(アルキルスチレン)としては、ポリ(メチルスチレ
ン),ポリ(エチルスチレン),ポリ(イソプロピルス
チレン),ポリ(ターシャリーブチルスチレン)などが
あり、ポリ(ハロゲン化スチレン)としては、ポリ(ク
ロロスチレン),ポリ(ブロモスチレン)などがあル。
また、ポリ(アルコキシスチレン)としては、ポリ(メ
トキシスチレン),ポリ(エトキシスチレン)などがあ
る。The tacticity measured by NMR can be indicated by the abundance ratio of a plurality of continuous structural units, for example, diad in the case of 2, triad in the case of 3 and pentad in the case of 5 The styrene-based polymer mainly having a syndiotactic structure means polystyrene, poly (alkylstyrene), poly (halogenated styrene), which has a syndiotactic structure of 85% or more in diads or 35% or more in pentads in general. The poly (alkoxystyrene), poly (benzoic acid ester styrene) and mixtures thereof, or copolymers containing these as the main components are referred to. Here, as the poly (alkylstyrene), there are poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiarybutylstyrene), etc., and as the poly (halogenated styrene), Examples include poly (chlorostyrene) and poly (bromostyrene).
Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
本発明の熱可塑性樹脂組成物において、上記のシンジオ
タクチック構造を有するスチレン系重合体は、組成物全
体の1〜99重量%の範囲で配合されていることが必要で
ある。1重量%未満では、熱可塑性樹脂の耐熱性の向上
の効果が充分でなく、99重量%を超えると一般の熱可塑
性樹脂の耐熱性の向上という本発明の目的が失われる。In the thermoplastic resin composition of the present invention, the styrene polymer having a syndiotactic structure needs to be blended in the range of 1 to 99% by weight based on the total weight of the composition. If it is less than 1% by weight, the effect of improving the heat resistance of the thermoplastic resin is not sufficient, and if it exceeds 99% by weight, the object of the present invention of improving the heat resistance of general thermoplastic resins is lost.
本発明の熱可塑性樹脂組成物は、上記のシンジオタクチ
ック構造を有するスチレン系重合体と、このシンジオタ
クチック構造を有するスチレン系重合体以外の熱可塑性
樹脂(以下、一般の熱可塑性樹脂と称することがあ
る。)とからなるものである。このような熱可塑性樹脂
としては、組成物の用途等により様々なものが選定さ
れ、特に制限はない。例えばアタクチック構造のポリス
チレン,アイソタクチック構造のポリスチレン,AS樹脂,
ABS樹脂などのスチレン系重合体をはじめ、ポリエステ
ル,ポリカーボネート,ポリエーテル,ポリアミド,ポ
リオキシメチレンなどの縮合系重合体、ポリアクリル
酸,ポリアクリル酸エステル,ポリメチルメタクリレー
トなどのアクリル系重合体、ポリエチレン,ポリプロピ
レン,ポリブテン,ポリ4−メチルペンテン−1,エチレ
ン−プロピレン共重合体などのポリオレフィン、あるい
はポリ塩化ビニル,ポリ塩化ビニリデン,ポリ弗化ビニ
リデンなどの含ハロゲンビニル化合物重合体などが挙げ
られる。The thermoplastic resin composition of the present invention comprises a styrene polymer having the syndiotactic structure, and a thermoplastic resin other than the styrene polymer having the syndiotactic structure (hereinafter referred to as a general thermoplastic resin. Sometimes it is). As such a thermoplastic resin, various resins are selected depending on the application of the composition and the like, and are not particularly limited. For example, polystyrene with atactic structure, polystyrene with isotactic structure, AS resin,
In addition to styrene polymers such as ABS resin, condensation polymers such as polyester, polycarbonate, polyether, polyamide, polyoxymethylene, acrylic polymers such as polyacrylic acid, polyacrylic acid ester, polymethylmethacrylate, polyethylene, etc. , Polypropylene, polybutene, poly-4-methylpentene-1, ethylene-propylene copolymers and the like, and halogen-containing vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride and polyvinylidene fluoride.
本発明では、上述の一般の熱可塑性樹脂に、新規な立体
構造を有するシンジオタクチック構造のスチレン系重合
体を配合するわけであるが、さらに必要に応じて成形
性,安定性,機械的強度の向上のために、従来から用い
られている滑剤,酸化安定剤,無機充填材などを配合す
ることもできる。In the present invention, the above-mentioned general thermoplastic resin is blended with a styrene-based polymer having a syndiotactic structure having a novel three-dimensional structure. Further, moldability, stability, and mechanical strength are further added as required. In order to improve the above, a lubricant, an oxidation stabilizer, an inorganic filler and the like which have been conventionally used can be added.
本発明において、主としてシンジオタクチック構造を有
するスチレン系重合体と一般の熱可塑性樹脂、また所望
により加える他成分を混練するにあたっては、状況に応
じて適宜条件を選定すればよいが、一般にはバンバリー
ミキサー,ヘンシェルミキサーや混練ロール、単軸押出
機,二軸押出機等による通常の溶融混練によればよい。In the present invention, when kneading mainly a styrene polymer having a syndiotactic structure and a general thermoplastic resin, and optionally other components to be kneaded, appropriate conditions may be selected depending on the situation, but generally Banbury. Usual melt-kneading with a mixer, a Henschel mixer, a kneading roll, a single-screw extruder, a twin-screw extruder or the like may be used.
このようにして得られる本発明の熱可塑性樹脂組成物
は、従来の一般の熱可塑性樹脂に比べて耐熱性の著しく
向上したものである。The thermoplastic resin composition of the present invention thus obtained has significantly improved heat resistance as compared with conventional general thermoplastic resins.
そのため、本発明の熱可塑性樹脂組成物は、耐熱性の要
求される各種産業用資材,機械部品素材等に幅広く、か
つ有効に利用される。Therefore, the thermoplastic resin composition of the present invention can be widely and effectively used for various industrial materials, machine parts materials and the like that require heat resistance.
次に本発明を実施例によりさらに詳しく説明する。 Next, the present invention will be described in more detail with reference to Examples.
参考例1 反応容器の溶媒としてトルエン2と、触媒成分である
シクロペンタジエニルチタニウムトリクロライド20ミリ
モル、およびメチルアミノキサンをアルミニウム原子と
して0.8モル加え、20℃においてスチレン3.6を加えて
1時間重合反応を行なった。反応終了後、生成物を塩酸
−メタノール混合液で洗浄し、触媒成分を分解除去し
た。ついで乾燥して重合体330gを得た。つぎに、この重
合体をメチルエチルケトンを溶媒としてソックスレー抽
出し、抽出残分95重量%を得た。この重合体は重量平均
分子量が280000,数平均分子量57000であり、融点は270
℃であった。また、この重合体は同位体炭素の核磁気共
鳴(13C−NMR)による分析からシンジオタクチック構造
に基因する145.35ppmに吸収が認められ、そのピーク面
積から算出したペンタッドでのシンジオタクティシティ
ーは96%のものであった。Reference Example 1 Toluene 2 as a solvent in a reaction vessel, 20 mmol of cyclopentadienyl titanium trichloride as a catalyst component, and 0.8 mol of methylaminoxane as an aluminum atom were added, and styrene 3.6 was added at 20 ° C. for 1 hour for polymerization reaction Was done. After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixed solution to decompose and remove the catalyst component. Then, it was dried to obtain 330 g of a polymer. Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. This polymer has a weight average molecular weight of 280000, a number average molecular weight of 57,000 and a melting point of 270.
It was ℃. This polymer was also found to have an absorption at 145.35 ppm due to the syndiotactic structure from the analysis of isotopic carbon nuclear magnetic resonance ( 13 C-NMR), and the syndiotacticity in the pentad calculated from the peak area. Was 96%.
実施例1 熱可塑性樹脂としてポリカーボネート(商品名:出光ポ
リカーボネートA2500,出光石油化学(株)製)80重量部
に対して、上記参考例1において得られたシンジオタク
チック構造のポリスチレン20重量部を配合し、ミニマッ
ト成形機により混練して試験片を作成し、このものの機
械的強度を測定した。また熱的性質についてはビカット
軟化点を測定した。これら結果を第1表に示す。Example 1 As a thermoplastic resin, 20 parts by weight of polystyrene having a syndiotactic structure obtained in Reference Example 1 was mixed with 80 parts by weight of a polycarbonate (trade name: Idemitsu Polycarbonate A2500, manufactured by Idemitsu Petrochemical Co., Ltd.). Then, it was kneaded with a mini mat molding machine to prepare a test piece, and the mechanical strength of this was measured. For the thermal properties, the Vicat softening point was measured. The results are shown in Table 1.
実施例2 ポリカーボネートの配合割合を50重量部,参考例1にお
いて得られたポリスチレンの配合割合を50重量部とした
ほかは、実施例1と同様の操作を行なった。結果を第1
表に示す。Example 2 The same operation as in Example 1 was carried out except that the mixing ratio of the polycarbonate was 50 parts by weight and the mixing ratio of the polystyrene obtained in Reference Example 1 was 50 parts by weight. First result
Shown in the table.
実施例3 熱可塑性樹脂としてポリエチレンテレフタレート(商品
名:パイロペットRY533,東洋紡績(株)製)80重量部を
用いたほかは、実施例1と同様の操作を行なった。結果
を第1表に示す。Example 3 The same operation as in Example 1 was carried out except that 80 parts by weight of polyethylene terephthalate (trade name: Pyropet RY533, manufactured by Toyobo Co., Ltd.) was used as the thermoplastic resin. The results are shown in Table 1.
実施例4 ポリエチレンテレフタレート(実施例3と同じもの)の
配合割合を50重量部,参考例1において得られたポリス
チレンの配合割合を50重量部としたほかは、実施例1と
同様の操作を行なった。結果を第1表に示す。Example 4 The same operation as in Example 1 was carried out except that the mixing ratio of polyethylene terephthalate (the same as that of Example 3) was 50 parts by weight and the mixing ratio of the polystyrene obtained in Reference Example 1 was 50 parts by weight. It was The results are shown in Table 1.
実施例5 熱可塑性樹脂としてABS樹脂(商品名:JSRABS15,日本合
成ゴム(株)製)80重量部を用いたほかは、実施例1と
同様の操作を行なった。結果を第1表に示す。Example 5 The same operation as in Example 1 was performed except that 80 parts by weight of an ABS resin (trade name: JSRABS15, manufactured by Japan Synthetic Rubber Co., Ltd.) was used as the thermoplastic resin. The results are shown in Table 1.
実施例6 ABS樹脂(実施例5と同じもの)の配合割合を50重量
部,参考例1において得られたポリスチレンの配合割合
を50重量部としたほかは、実施例1と同様の操作を行な
った。結果を第1表に示す。Example 6 The same operation as in Example 1 was carried out except that the mixing ratio of the ABS resin (the same as that of Example 5) was 50 parts by weight and the mixing ratio of the polystyrene obtained in Reference Example 1 was 50 parts by weight. It was The results are shown in Table 1.
実施例7 熱可塑性樹脂としてポリスルホン(商品名:ユーデルポ
リサルホンP−1700,ユニオン・カーバイト社製)80重
量部を用いたほかは、実施例1と同様の操作を行なっ
た。結果を第1表に示す。Example 7 The same operation as in Example 1 was performed except that 80 parts by weight of polysulfone (trade name: Udel Polysulfone P-1700, manufactured by Union Carbide) was used as the thermoplastic resin. The results are shown in Table 1.
実施例8 ポリスルホン(実施例7と同じもの)の配合割合を50重
量部,参考例1において得られたポリスチレンの配合割
合を50重量部としたほかは、実施例1と同様の操作を行
なった。結果を第1表に示す。Example 8 The same operation as in Example 1 was carried out except that the blending ratio of polysulfone (the same as that of Example 7) was 50 parts by weight and the blending ratio of the polystyrene obtained in Reference Example 1 was 50 parts by weight. . The results are shown in Table 1.
比較例1〜4 実施例1〜8で用いたポリカーボネート,ポリエチレン
テレフタレート,ABS樹脂,ポリスルホンの各樹脂単独の
性質を実施例1と同様に測定した。結果を第1表に示
す。Comparative Examples 1 to 4 The properties of each of the polycarbonate, polyethylene terephthalate, ABS resin and polysulfone used in Examples 1 to 8 were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例9 ポリカーボネートの配合割合を95重量部,参考例1にお
いて得られたポリスチレンの配合割合を5重量部とした
ほかは、実施例1と同様の操作を行なった。結果を第2
表に示す。 Example 9 The same operation as in Example 1 was carried out except that the blending ratio of the polycarbonate was 95 parts by weight and the blending ratio of the polystyrene obtained in Reference Example 1 was 5 parts by weight. Second result
Shown in the table.
実施例10 ポリカーボネートの配合割合を5重量部,参考例1にお
いて得られたポリスチレンの配合割合を95重量部とした
ほかは、実施例1と同様の操作を行なった。結果を第2
表に示す。Example 10 The same operation as in Example 1 was carried out except that the compounding ratio of the polycarbonate was 5 parts by weight and the compounding ratio of the polystyrene obtained in Reference Example 1 was 95 parts by weight. Second result
Shown in the table.
実施例11 実施例3において、ポリエチレンテレフタレートの配合
割合を20重量部とし、かつ参考例1において得られたポ
リスチレンの配合割合を80重量部としたほかは、実施例
3と同様の操作を行なった。結果を第2表に示す。Example 11 The same operation as in Example 3 was carried out except that in Example 3, the mixing ratio of polyethylene terephthalate was 20 parts by weight, and the mixing ratio of the polystyrene obtained in Reference Example 1 was 80 parts by weight. . The results are shown in Table 2.
Claims (2)
スチレン系重合体1〜99重量%と、前記シンジオタクチ
ック構造を有するスチレン系重合体以外の熱可塑性樹脂
99〜1重量%とからなる熱可塑性樹脂組成物。1. A thermoplastic resin other than the styrene-based polymer having a syndiotactic structure and 1 to 99% by weight, and the styrene-based polymer having a syndiotactic structure.
A thermoplastic resin composition comprising 99 to 1% by weight.
レン系重合体以外の熱可塑性樹脂が、ポリカーボネー
ト,ポリエチレンテレフタレート,ABS樹脂,ポリスルホ
ン,アタクチック構造のポリスチレン,アイソタクチッ
ク構造のポリスチレン,ポリブチレンテレフタレート,
ポリエーテル,ポリアミド,ポリエチレンおよびポリプ
ロピレンから選ばれた少なくとも1種の樹脂である特許
請求の範囲第1項記載の組成物。2. The thermoplastic resin other than the styrene polymer having a syndiotactic structure is polycarbonate, polyethylene terephthalate, ABS resin, polysulfone, polystyrene having an atactic structure, polystyrene having an isotactic structure, polybutylene terephthalate,
The composition according to claim 1, which is at least one resin selected from polyether, polyamide, polyethylene and polypropylene.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61101928A JPH0755995B2 (en) | 1986-05-06 | 1986-05-06 | Thermoplastic resin composition |
US09/075,867 US5990217A (en) | 1986-05-06 | 1998-05-12 | Styrene based resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61101928A JPH0755995B2 (en) | 1986-05-06 | 1986-05-06 | Thermoplastic resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62257950A JPS62257950A (en) | 1987-11-10 |
JPH0755995B2 true JPH0755995B2 (en) | 1995-06-14 |
Family
ID=14313572
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61101928A Expired - Lifetime JPH0755995B2 (en) | 1986-05-06 | 1986-05-06 | Thermoplastic resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0755995B2 (en) |
Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5891951A (en) * | 1987-09-14 | 1999-04-06 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
US5166238A (en) * | 1986-09-22 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
JPH07103284B2 (en) * | 1987-12-04 | 1995-11-08 | 出光興産株式会社 | Impact-resistant polystyrene resin composition |
JP2683035B2 (en) * | 1988-05-20 | 1997-11-26 | 出光興産株式会社 | Styrene resin composition |
US5395890A (en) * | 1987-09-14 | 1995-03-07 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
JP2681642B2 (en) * | 1988-01-14 | 1997-11-26 | 出光興産株式会社 | Styrene polymer resin composition |
JP2681643B2 (en) * | 1988-01-14 | 1997-11-26 | 出光興産株式会社 | Polystyrene resin composition |
JP2828982B2 (en) * | 1988-01-14 | 1998-11-25 | 出光興産株式会社 | Film, sheet or tape, and method for producing the same |
US6013726A (en) * | 1987-04-12 | 2000-01-11 | Idemitsu Kosan Co., Ltd. | Composition of styrene resin, thermoplastic resin and rubber |
CA1326095C (en) * | 1987-05-18 | 1994-01-11 | Toshikazu Ijitsu | Styrene-based resin composition and moldings produced from said composition |
US6093768A (en) * | 1987-09-14 | 2000-07-25 | Idemitsu Kosan Co., Ltd. | Syndiotactic styrene resin, thermoplastic resin and rubber |
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JPH083008B2 (en) * | 1987-11-17 | 1996-01-17 | 三井東圧化学株式会社 | Polypropylene resin composition |
JP2768483B2 (en) * | 1988-01-13 | 1998-06-25 | 出光興産株式会社 | Thermoplastic resin composition |
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JP2837162B2 (en) * | 1988-01-14 | 1998-12-14 | 出光興産株式会社 | Flame retardant resin composition |
JPH01197546A (en) * | 1988-02-01 | 1989-08-09 | Asahi Chem Ind Co Ltd | Heat-resistant resin composition |
JP2931597B2 (en) * | 1988-02-11 | 1999-08-09 | ザ・ダウ・ケミカル・カンパニー | Electrical connection device, base material thereof, wiring board and wiring connector made of the base material |
JP2759658B2 (en) * | 1988-09-07 | 1998-05-28 | 出光興産株式会社 | Polyarylene sulfide resin composition |
IT1227058B (en) * | 1988-09-09 | 1991-03-14 | Montedipe Spa | QUICK CRYSTALLIZATION POLYESTER COMPOSITIONS. |
US5089353A (en) * | 1988-10-14 | 1992-02-18 | Kuraray Co., Ltd. | Multi-layer material having gas barrier properties |
US5270353A (en) * | 1989-02-10 | 1993-12-14 | Idemitsu Kosan Co., Ltd. | Resin composition |
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JP2945404B2 (en) * | 1989-02-10 | 1999-09-06 | 出光興産株式会社 | Resin composition |
JP2885432B2 (en) * | 1989-08-31 | 1999-04-26 | 出光興産株式会社 | Polyester resin composition |
JP3166788B2 (en) * | 1992-03-04 | 2001-05-14 | 出光興産株式会社 | Styrene resin composition |
US5391603A (en) * | 1992-03-09 | 1995-02-21 | The Dow Chemical Company | Impact modified syndiotactic vinyl aromatic polymers |
JP3121113B2 (en) * | 1992-04-17 | 2000-12-25 | 出光興産株式会社 | Method for producing styrenic resin composition |
JP3292320B2 (en) * | 1993-03-03 | 2002-06-17 | 出光興産株式会社 | Impact resistant polystyrene resin composition |
KR100366424B1 (en) | 2000-08-14 | 2003-01-09 | 삼성종합화학주식회사 | Reactor Alloy of Syndiotactic Polystyrene Having High Impact Strength |
CN108948638A (en) * | 2018-06-07 | 2018-12-07 | 安庆市洁达塑业有限公司 | A kind of potent Wear-resistant plastic flitch and preparation method thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61101929A (en) * | 1984-10-24 | 1986-05-20 | 株式会社日立製作所 | Buffer type gas breaker |
-
1986
- 1986-05-06 JP JP61101928A patent/JPH0755995B2/en not_active Expired - Lifetime
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