JPH06271717A - Thermoplastic resin composition - Google Patents

Thermoplastic resin composition

Info

Publication number
JPH06271717A
JPH06271717A JP8673093A JP8673093A JPH06271717A JP H06271717 A JPH06271717 A JP H06271717A JP 8673093 A JP8673093 A JP 8673093A JP 8673093 A JP8673093 A JP 8673093A JP H06271717 A JPH06271717 A JP H06271717A
Authority
JP
Japan
Prior art keywords
weight
polymer
conjugated diene
block
compound
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
Application number
JP8673093A
Other languages
Japanese (ja)
Other versions
JP3367136B2 (en
Inventor
Junji Kamishina
順二 神品
Yoshifumi Kato
嘉文 加藤
Yoshihisa Fujinaga
吉久 藤永
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
Japan Synthetic Rubber Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Synthetic Rubber Co Ltd filed Critical Japan Synthetic Rubber Co Ltd
Priority to JP08673093A priority Critical patent/JP3367136B2/en
Publication of JPH06271717A publication Critical patent/JPH06271717A/en
Application granted granted Critical
Publication of JP3367136B2 publication Critical patent/JP3367136B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

PURPOSE:To obtain the subject composition excellent in impact resistance and molding appearance by using a hydrogenated block copolymer having a specified structure. CONSTITUTION:This resin composition comprises 100 pts.wt. polymer mixture of 2-98 pts.wt. olefin polymer with 98-2 pts.wt. styrenic polymer and 2-50 pts.wt. hydrogenated block copolymer of a weight-average molecular weight of 200000-500000 derived by saturating at least 80% of the double bonds of the conjugated diene part of an (A1)-(B)-(A2) block copolymer comprising a vinylaromatic compound polymer block (A1) of a weight-average molecular weight of 15000 or above, a vinylaromatic compound polymer block (A2) of a weight-average molecular weight of 9000 or below and a vinylaromatic compound/conjugated diene compound random copolymer block (B) and satisfying the requirement: (1) the weight ratio of the total vinyl aromatic compound to the total conjugated diene compound is 15/85 to 60/40, and (2) the vinyl bond content of the conjugated diene compound part of component B is above 60% or above.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、オレフィン系重合体と
スチレン系重合体を主たる成分とし、成形外観の改良さ
れた熱可塑性樹脂組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing an olefin polymer and a styrene polymer as main components and having an improved molding appearance.

【0002】[0002]

【従来の技術】オレフィン系重合体やスチレン系重合体
は安価であり、最も大量に生産されている樹脂である。
しかしながら、オレフィン系重合体では、成形加工時の
収縮が大きく、深絞り成形の不良など、加工時の欠点が
多く指摘されており、改良が望まれている。また、スチ
レン系重合体は、高剛性であるが、脆く、機械的強度が
劣ること、フィルム、シート状成形物の水素透過性や引
裂強度が劣ることなどの問題がある。オレフィン系重合
体とスチレン系重合体を組み合わせることにより、それ
ぞれ単独の重合体の欠点を補った組成物が得られること
が分かり、種々の検討がなされている。しかしながら、
このオレフィン系重合体とスチレン系重合体は、お互い
に非相溶性であるため、単純な混合物は相剥離を起こす
脆いものであり、実用に耐えるものではない。
2. Description of the Related Art Olefin-based polymers and styrene-based polymers are inexpensive and are the most mass-produced resins.
However, the olefin-based polymer has a large shrinkage during molding and many defects such as defective deep drawing have been pointed out during processing, and improvement is desired. Further, styrene-based polymers have high rigidity, but have problems such as brittleness, poor mechanical strength, and poor hydrogen permeability and tear strength of film or sheet-shaped moldings. It has been found that by combining an olefin polymer and a styrene polymer, a composition in which the drawbacks of the individual polymers are compensated can be obtained, and various studies have been made. However,
Since the olefin-based polymer and the styrene-based polymer are incompatible with each other, a simple mixture is fragile and causes phase separation, and is not practical.

【0003】そのため、特開昭56−38338号公
報、特開昭56−50943号公報では、オレフィン系
重合体とスチレン系重合体の相溶性改良剤として、スチ
レン−ブタジエンブロック共重合体の水素添加物を添加
する技術が提案されている。しかしながら、この技術で
用いられているスチレン−ブタジエンブロック共重合体
の水素添加物は、スチレン系重合体に対してはポリスチ
レンブロックセグメントを有するため良好な相溶性を示
すが、オレフィン系重合体に対しては相溶性が十分でな
く、このため相溶化剤としての性能が劣るものである。
Therefore, in JP-A-56-38338 and JP-A-56-50943, hydrogenation of a styrene-butadiene block copolymer is used as a compatibility improving agent for an olefin polymer and a styrene polymer. Techniques for adding substances have been proposed. However, the hydrogenated product of the styrene-butadiene block copolymer used in this technology shows good compatibility with the styrene-based polymer because it has a polystyrene block segment, but it has good compatibility with the olefin-based polymer. However, the compatibility is not sufficient and therefore the performance as a compatibilizer is poor.

【0004】[0004]

【発明が解決しようとする課題】本発明は、前記従来技
術の課題を背景になされたもので、オレフィン系重合体
とスチレン系重合体からなる重合体混合物に、相溶化改
良剤として特別に分子設計された水添ブロック共重合体
を添加し、耐衝撃性および成形外観に優れた熱可塑性樹
脂組成物を得ることを目的とする。
SUMMARY OF THE INVENTION The present invention has been made against the background of the above-mentioned problems of the prior art. In a polymer mixture consisting of an olefin polymer and a styrene polymer, a special molecule as a compatibilizer is added. The purpose is to add a designed hydrogenated block copolymer to obtain a thermoplastic resin composition excellent in impact resistance and molding appearance.

【0005】[0005]

【課題を解決するための手段】本発明は、(イ)オレフ
ィン系重合体2〜98重量%、およびスチレン系重合体
98〜2重量%を含む重合体混合物100重量部に対し
て、(ロ)重量平均分子量が1.5万以上のビニル芳香
族化合物重合体ブロック(A1)と、重量平均分子量が
0.9万以下のビニル芳香族化合物重合体ブロック(A
2)、およびビニル芳香族化合物と共役ジエン化合物と
のランダム共重合体ブロック(B)からなり、 全ビニル芳香族化合物/全共役ジエン化合物の重量
比率は15/85〜60/40。 (B)成分中の共役ジエン化合物部分のビニル結合
含量が60%を超える。 の条件を満たす(A1)−(B)−(A2)ブロック共
重合体の共役ジエン部分の二重結合が80%以上飽和さ
れた、重量平均分子量が20万〜50万の水添ブロック
共重合体2〜50重量部、を含有してなる熱可塑性樹脂
組成物を提供するものである。
The present invention relates to (a) 100 parts by weight of a polymer mixture containing 2 to 98% by weight of an olefin polymer and 98 to 2% by weight of a styrene polymer. ) A vinyl aromatic compound polymer block (A1) having a weight average molecular weight of 15,000 or more and a vinyl aromatic compound polymer block (A) having a weight average molecular weight of 90,000 or less
2) and a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene compound, and the weight ratio of all vinyl aromatic compounds / all conjugated diene compounds is 15/85 to 60/40. The vinyl bond content of the conjugated diene compound portion in the component (B) exceeds 60%. Of the (A1)-(B)-(A2) block copolymer satisfying the condition of 80% or more of the double bond of the conjugated diene moiety of the hydrogenated block copolymer having a weight average molecular weight of 200,000 to 500,000. The present invention provides a thermoplastic resin composition containing 2 to 50 parts by weight of the combined product.

【0006】以下、本発明について詳細に説明する。本
発明において、(イ)成分を構成するオレフィン系共重
合体としては、炭素数2〜8のα−モノオレフィンを主
たる単量体成分とする重合体である。このオレフィン系
重合体の具体例としては、低密度ポリエチレン、高密度
ポリエチレン、線状低密度ポリエチレン、ポリプロピレ
ン、エチレン−プロピレンランダム共重合体、エチレン
−プロピレンブロック共重合体、ポリメチルペンテン、
ポリブテン−1、オレフィンとエチレン、プロピレン以
外の他の単量体との共重合体などが挙げられ、これらは
1単独で、あるいは2種以上混合して使用される。特に
好ましいオレフィン系重合体は、エチレンあるいはプロ
ピレンを主たる単量体成分とする重合体であり、具体的
には、各種ポリエチレン、ポリプロピレン、エチレン−
酢酸ビニルランダム共重合体、エチレン−(メタ)アク
リル酸ランダム共重合体、エチレン−グリシジルメタク
リレートランダム共重合体などのエチレン系ランダム共
重合体、プロピレン系ブロック共重合体、さらにはこれ
らの混合物である。
The present invention will be described in detail below. In the present invention, the olefin-based copolymer constituting the component (a) is a polymer containing a C 2-8 α-monoolefin as a main monomer component. Specific examples of the olefin polymer include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, polymethylpentene,
Examples thereof include polybutene-1, copolymers of olefins with monomers other than ethylene and propylene, and these may be used alone or in admixture of two or more. A particularly preferred olefin polymer is a polymer containing ethylene or propylene as a main monomer component, and specifically, various polyethylene, polypropylene, ethylene-
A vinyl acetate random copolymer, an ethylene- (meth) acrylic acid random copolymer, an ethylene-based random copolymer such as an ethylene-glycidyl methacrylate random copolymer, a propylene block copolymer, and a mixture thereof. .

【0007】また、(イ)成分を構成するスチレン系重
合体は、スチレン、p−メチルスチレン、α−メチルス
チレンなどを主たる単量体成分とする(共)重合体であ
る。このスチレン系重合体の具体例としては、ポリスチ
レン、スチレン−アクリロニトリル共重合体、スチレン
−メチルメタクリレート共重合体、スチレン−無水マレ
イン酸共重合体、ゴム変性ポリスチレン、スチレン−ブ
タジエン共重合体、アクリロニトリル−(ポリブタジエ
ン)−スチレン共重合体(ABS樹脂)、アクリロニト
リル−(エチレン−プロピレンゴム)−スチレン共重合
体(AES樹脂)、スチレン−α−メチルスチレン共重
合体、スチレン−p−メチルスチレン共重合体などの、
一般にスチレン系重合体と称される重合体からなる群か
ら選ばれる少なくとも1種の(共)重合体である。スレ
チン系重合体としては、これらのほか、例えば該重合体
と相溶する他の樹脂が適当量混合したもの、例えばポリ
スチレンにポリフェニレンエーテルを適当量配合したも
のであってもよい。好ましいスチレン系重合体は、少な
くとも50重量%のスチレン含量を持つものであり、ポ
リスチレン、ゴム変性ポリスチレンなどが好ましい。
The styrene polymer constituting the component (a) is a (co) polymer having styrene, p-methylstyrene, α-methylstyrene and the like as main monomer components. Specific examples of the styrene-based polymer include polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, rubber-modified polystyrene, styrene-butadiene copolymer, acrylonitrile- (Polybutadiene) -styrene copolymer (ABS resin), acrylonitrile- (ethylene-propylene rubber) -styrene copolymer (AES resin), styrene-α-methylstyrene copolymer, styrene-p-methylstyrene copolymer Such as
It is at least one (co) polymer selected from the group consisting of polymers generally called styrene-based polymers. In addition to these, the threthin-based polymer may be, for example, a mixture of an appropriate amount of another resin compatible with the polymer, for example, a mixture of polystyrene and an appropriate amount of polyphenylene ether. A preferred styrene polymer has a styrene content of at least 50% by weight, and polystyrene, rubber-modified polystyrene and the like are preferable.

【0008】(イ)成分を構成するオレフィン系重合体
とスチレン系重合体の混合比率は、オレフィン系重合体
2〜98重量%、好ましくは10〜90重量%、さらに
好ましくは15〜85重量%、スチレン系重合体98〜
2重量%、好ましくは90〜10重量%、さらに好まし
くは85〜15重量%である。オレフィン系重合体ある
いはスチレン系重合体が2重量%未満の場合には、異な
る重合体を混合することによって期待される性能の発現
が認められない。
The mixing ratio of the olefin polymer and the styrene polymer constituting the component (a) is 2 to 98% by weight, preferably 10 to 90% by weight, more preferably 15 to 85% by weight. , Styrene polymer 98-
It is 2% by weight, preferably 90 to 10% by weight, more preferably 85 to 15% by weight. When the amount of the olefin-based polymer or the styrene-based polymer is less than 2% by weight, the expected performance cannot be obtained by mixing different polymers.

【0009】次に、(ロ)成分である(A1)−(B)
−(A2)ブロック共重合体を説明する。(A1)また
は(A2)のビニル芳香族化合物重合体ブロックセグメ
ントに用いられるビニル芳香族化合物は、スチレン、α
−メチルスチレン、p−メチルスチレンなどが挙げら
れ、これらは単独で、あるいは混合して使用される。ブ
ロック(A1)の重量平均分子量は1.5万以上であ
り、1.5万未満では組成物の耐衝撃性が劣り好ましく
ない。上限は好ましくは15万以下である。また、ブロ
ック(A2)の重量平均分子量は0.9万以下、好まし
くは0.7万以下、さらに好ましくは0.6万以下であ
り、その下限は好ましくは0.01万以上であり、0.
9万を超えると成形外観が劣るため好ましくない。ブロ
ック(B)は、ビニル芳香族化合物と共役ジエン化合物
とのランダム共重合体ブロックであり、ビニル芳香族化
合物としては、スチレンやα−メチルスチレン、p−メ
チルスチレンなどが挙げられ、スチレンが特に好まし
く、共役ジエン化合物としては、ブタジエンやイソプレ
ンが挙げられ、ブタジエンが特に好ましい。
Next, the (B) component (A1)-(B)
The (A2) block copolymer will be described. The vinyl aromatic compound used in the vinyl aromatic compound polymer block segment of (A1) or (A2) is styrene, α
-Methyl styrene, p-methyl styrene, etc. are mentioned, and these are used individually or in mixture. The weight average molecular weight of the block (A1) is 15,000 or more, and if it is less than 15,000, the composition is inferior in impact resistance, which is not preferable. The upper limit is preferably 150,000 or less. The weight average molecular weight of the block (A2) is 90,000 or less, preferably 70,000 or less, more preferably 60,000 or less, and the lower limit thereof is preferably 10,000,000 or more. .
If it exceeds 90,000, the molding appearance is inferior, which is not preferable. The block (B) is a random copolymer block of a vinyl aromatic compound and a conjugated diene compound, and examples of the vinyl aromatic compound include styrene, α-methylstyrene and p-methylstyrene, and styrene is particularly preferable. Preferred examples of the conjugated diene compound include butadiene and isoprene, with butadiene being particularly preferred.

【0010】ブロック(B)中のビニル結合含量は、高
含率にすることが特に好ましい。すなわち、ブロック
(B)中のジエン部分のビニル結合含量は60%以上、
好ましくは65〜95%、特に好ましくは70〜90%
の範囲内である。60%未満では、組成物の耐衝撃性が
劣り好ましくない。
The vinyl bond content in block (B) is particularly preferably high. That is, the vinyl bond content of the diene portion in the block (B) is 60% or more,
Preferably 65-95%, particularly preferably 70-90%
Within the range of. If it is less than 60%, the composition is inferior in impact resistance, which is not preferable.

【0011】該ブロック共重合体を構成する全ビニル芳
香族化合物/全共役ジエン化合物の重量比率は、15/
85〜60/40、好ましくは40/60〜60/40
の範囲である。全ビニル芳香族化合物が15重量%未満
では、耐衝撃性が劣り好ましくなく、60重量%を超え
ると成形外観が劣り好ましくない。ブロック共重合体の
重量平均分子量は20万以上50万以下であるが、20
万未満では耐衝撃性が劣り好ましくなく、50万を超え
ると成形外観が劣り好ましくない。また、ブロック共重
合体の共役ジエン部分の水添率は80%以上、好ましく
は90%以上、さらに好ましくは95%以上である。水
添率が80%未満では耐衝撃性が低下し好ましくない。
The weight ratio of all vinyl aromatic compounds / all conjugated diene compounds constituting the block copolymer is 15 /
85-60 / 40, preferably 40 / 60-60 / 40
Is the range. If the total vinyl aromatic compound content is less than 15% by weight, the impact resistance is inferior, which is not preferable, and if it exceeds 60% by weight, the molding appearance is inferior and this is not preferable. The weight average molecular weight of the block copolymer is 200,000 or more and 500,000 or less.
If it is less than 10,000, the impact resistance is inferior, and if it exceeds 500,000, the molding appearance is inferior, which is not preferable. The hydrogenation rate of the conjugated diene portion of the block copolymer is 80% or more, preferably 90% or more, more preferably 95% or more. If the hydrogenation rate is less than 80%, the impact resistance is lowered, which is not preferable.

【0012】本発明における組成物中の(ロ)の配合量
は、(イ)100重量部に対して2〜/50重量部、好
ましくは5〜30重量部、さらに好ましくは5〜20重
量部である。2重量部未満では改良の効果は無く、50
重量部を超えると成形外観が劣り好ましくない。本発明
に使用される(ロ)水添ブロック共重合体は、例えば特
開平3−72512号公報に開示されている方法によっ
て得ることができる。
The blending amount of (b) in the composition of the present invention is 2 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight, relative to 100 parts by weight of (a). Is. If the amount is less than 2 parts by weight, there is no improvement effect and 50
If the amount is more than parts by weight, the appearance of molding is poor and it is not preferable. The (b) hydrogenated block copolymer used in the present invention can be obtained, for example, by the method disclosed in JP-A-3-72512.

【0013】本発明の熱可塑性樹脂組成物は、以上の
(イ)成分と(ロ)成分を主成分とするが、酸化防止
剤、帯電防止剤、耐候剤、紫外線吸収剤、滑剤、酸化チ
タン、カーボンブラックなどの着色剤、ガラス繊維、炭
素繊維、金属繊維、アラミド繊維、ガラスビーズ、アス
ベスト、マイカ、炭酸カルシウム、チタン酸カリウムウ
ィスカー、タルク、硫酸バリウム、ガラスフレーク、フ
ッ素樹脂などの充填剤、あるいは他のゴム質重合体、熱
可塑性樹脂などを適宜配合することができる。
The thermoplastic resin composition of the present invention contains the above-mentioned components (a) and (b) as the main components, but includes an antioxidant, an antistatic agent, a weathering agent, an ultraviolet absorber, a lubricant, and titanium oxide. , Coloring agents such as carbon black, glass fibers, carbon fibers, metal fibers, aramid fibers, glass beads, asbestos, mica, calcium carbonate, potassium titanate whiskers, talc, barium sulfate, glass flakes, fillers such as fluororesins, Alternatively, other rubbery polymer, thermoplastic resin or the like can be appropriately blended.

【0014】本発明の組成物は、押出機、ニーダー、バ
ンバリーミキサーなどにより溶融混練りすることによっ
て得ることができる。本発明の組成物を製造するには、
各成分を一括で混合してもよく、任意の成分をあらかじ
め予備混合した後、残りの成分を添加して混合してもよ
い。最も好ましい混合装置は、一軸あるいは二軸押出機
であり、これにより連続的に効率よく混練りし、ペレッ
ト化することができる。得られたペレットを用い、押出
成形を行ない、成形品に加工することができる。本発明
の組成物を用いて得られる押出成形品としては、シー
ト、フィルム、チューブなどを挙げることができ、種々
の用途に使用することができる。
The composition of the present invention can be obtained by melt-kneading with an extruder, a kneader, a Banbury mixer or the like. To produce the composition of the present invention,
Each component may be mixed at once, or any component may be premixed in advance and then the remaining components may be added and mixed. The most preferable mixing device is a single-screw or twin-screw extruder, which allows efficient and continuous kneading and pelletization. By using the obtained pellets, extrusion molding can be performed and processed into a molded product. Examples of the extrusion-molded article obtained by using the composition of the present invention include a sheet, a film, a tube and the like, which can be used for various purposes.

【0015】[0015]

【実施例】以下、実施例を挙げて本発明をさらに具体的
に説明するが、本発明はこれらの実施例に限定されるも
のではない。なお、実施例中、部および%は特に断らな
い限り重量基準である。また、実施例中における各種の
測定は、下記の方法に拠った。 結合ビニル芳香族化合物含量 679cm-1のフェニル基の吸収を基に、赤外分析法に
より測定した。 共役ジエンのビニル結合含量 赤外分析法を用い、ハンプトン法により算出した。 水添率 四塩化エチレンを溶媒に用い、100MHz、1H−N
MRスペクトルから算出した。 重量平均分子量 トリクロルベンゼンを溶媒に用い、135℃におけるゲ
ルパーミエーションクロマトグラフィー(GPC)を用
いてポリスチレン換算で求めた。 アイゾット衝撃強度 JIS K7110に従って測定した。 成形外観 射出成形によって得られた成形品を目視評価した結果
を、下記基準に従って判定した。 ○ :全く問題の無い成形品である。 × :流動不良に起因するフローマークなどが見られ、
成形外観が劣る。 ××:シルバーストリークスなどが発生し、成形外観が
劣る。
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, various measurements in the examples were based on the following methods. Based on the absorption of a phenyl group having a content of a bound vinyl aromatic compound of 679 cm -1 , it was measured by an infrared analysis method. Vinyl bond content of conjugated diene Calculated by Hampton method using infrared analysis. Hydrogenation rate Using tetrachloroethylene as a solvent, 100 MHz, 1H-N
It was calculated from the MR spectrum. Weight average molecular weight Trichlorobenzene was used as a solvent, and it was determined in terms of polystyrene using gel permeation chromatography (GPC) at 135 ° C. Izod impact strength Measured according to JIS K7110. Molding appearance The results of visual evaluation of molded products obtained by injection molding were judged according to the following criteria. ◯: A molded product having no problem. ×: Flow marks and the like caused by poor flow are seen,
Molding appearance is inferior. XX: Silver streaks and the like occur, resulting in poor molding appearance.

【0016】実施例1〜8、比較例1〜11 表1および表2に示す組成の樹脂組成物の性能に評価
し、同表に結果を示した。表1に示す実施例1〜8の結
果から、本発明の樹脂組成物は、表2に示す比較例1〜
11に比べて耐衝撃性および成形外観のバランスに優れ
ることがわかる。比較例1〜7は水添ブロック共重合体
が本発明の範囲外であるため、耐衝撃性および成形外観
のバランスが劣る。比較例8〜10は配合比率が本発明
の範囲外であるため、耐衝撃性および成形外観のバラン
スが劣る。比較例11(ロ)成分の替りに市販SEBS
を使用しており、成形外観が劣り好ましくない。
Examples 1 to 8 and Comparative Examples 1 to 11 The resin compositions having the compositions shown in Tables 1 and 2 were evaluated, and the results are shown in the same table. From the results of Examples 1 to 8 shown in Table 1, the resin composition of the present invention was obtained by comparing Comparative Examples 1 to 1 shown in Table 2.
It can be seen that, as compared with No. 11, the impact resistance and the molding appearance have a better balance. Since the hydrogenated block copolymers of Comparative Examples 1 to 7 are out of the scope of the present invention, the balance of impact resistance and molding appearance is poor. In Comparative Examples 8 to 10, since the compounding ratio is outside the range of the present invention, the balance of impact resistance and molding appearance is poor. Comparative Example 11 (b) Commercially available SEBS instead of the component
Is not preferable because the molding appearance is inferior.

【0017】[0017]

【表1】 [Table 1]

【0018】[0018]

【表2】 [Table 2]

【0019】[0019]

【発明の効果】従来、オレフィン系重合体およびスチレ
ン系重合体からなる組成物を改良するため種々の相溶化
剤が検討されてきたが、耐衝撃性および成形外観のバラ
ンスに優れれた組成物を得るのは困難であった。本発明
は、特定の構造を有する水添ブロック共重合体を用いる
ことにより、耐衝撃性と成形外観のバランスに優れた熱
可塑性樹脂組成物を得たものであり、各種射出成形品の
材料として好適であり、工業的価値は大きい。
Various compatibilizers have been investigated in order to improve the composition comprising an olefin polymer and a styrene polymer, but a composition having an excellent balance of impact resistance and molding appearance. Was hard to get. The present invention is to obtain a thermoplastic resin composition having an excellent balance between impact resistance and molding appearance by using a hydrogenated block copolymer having a specific structure, and as a material for various injection molded products. It is suitable and has great industrial value.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 (イ)オレフィン系重合体2〜98重量
%、およびスチレン系重合体98〜2重量%を含む重合
体混合物100重量部に対して、 (ロ)重量平均分子量が1.5万以上のビニル芳香族化
合物重合体ブロック(A1)と、重量平均分子量が0.
9万以下のビニル芳香族化合物重合体ブロック(A
2)、およびビニル芳香族化合物と共役ジエン化合物と
のランダム共重合体ブロック(B)からなり、 全ビニル芳香族化合物/全共役ジエン化合物の重量
比率は15/85〜60/40。 (B)成分中の共役ジエン化合物部分のビニル結合
含量が60%を超える。 の条件を満たす(A1)−(B)−(A2)ブロック共
重合体の共役ジエン部分の二重結合が80%以上飽和さ
れた、重量平均分子量が20万〜50万の水添ブロック
共重合体2〜50重量部、を含有してなる熱可塑性樹脂
組成物。
1. (b) A weight average molecular weight of 1.5 relative to 100 parts by weight of a polymer mixture containing 2 to 98% by weight of an olefin polymer and 98 to 2% by weight of a styrene polymer. 10,000 or more vinyl aromatic compound polymer block (A1) and a weight average molecular weight of 0.
90,000 or less vinyl aromatic compound polymer block (A
2) and a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene compound, and the weight ratio of total vinyl aromatic compound / total conjugated diene compound is 15/85 to 60/40. The vinyl bond content of the conjugated diene compound portion in the component (B) exceeds 60%. Of the (A1)-(B)-(A2) block copolymer satisfying the condition of 80% or more of the double bond of the conjugated diene moiety of the hydrogenated block copolymer having a weight average molecular weight of 200,000 to 500,000. A thermoplastic resin composition containing 2 to 50 parts by weight of the combined product.
JP08673093A 1993-03-22 1993-03-22 Thermoplastic resin composition Expired - Lifetime JP3367136B2 (en)

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Application Number Priority Date Filing Date Title
JP08673093A JP3367136B2 (en) 1993-03-22 1993-03-22 Thermoplastic resin composition

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JPH06271717A true JPH06271717A (en) 1994-09-27
JP3367136B2 JP3367136B2 (en) 2003-01-14

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JP2002284944A (en) * 2001-03-23 2002-10-03 Asahi Kasei Corp Thermoplastic flexible resin composition
US6759454B2 (en) 2002-02-07 2004-07-06 Kraton Polymers U.S. Llc Polymer modified bitumen compositions
US6797776B1 (en) * 1999-12-21 2004-09-28 Asahi Kasei Kabushiki Kaisha Thermoplastic resin composition
US7267855B2 (en) 2002-02-07 2007-09-11 Kraton Polymers U.S. Llc Articles prepared from hydrogenated controlled distribution block copolymers
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6797776B1 (en) * 1999-12-21 2004-09-28 Asahi Kasei Kabushiki Kaisha Thermoplastic resin composition
JP2002234974A (en) * 2001-02-08 2002-08-23 Asahi Kasei Corp Ethylene resin composition and extruded article using the same
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US7169848B2 (en) 2002-02-07 2007-01-30 Kraton Polymers U.S. Llc Block copolymers and method for making same
US7223816B2 (en) 2002-02-07 2007-05-29 Handlin Jr Dale L Solvent-free, hot melt adhesive composition comprising a controlled distribution block copolymer
US7067589B2 (en) 2002-02-07 2006-06-27 Kraton Polymers U.S. Llc Block copolymers and method for making same
US7138456B2 (en) 2002-02-07 2006-11-21 Bening Robert C Block copolymers and method for making same
US7141621B2 (en) 2002-02-07 2006-11-28 Kraton Polymers U.S. Llc Gels from controlled distribution block copolymers
US6759454B2 (en) 2002-02-07 2004-07-06 Kraton Polymers U.S. Llc Polymer modified bitumen compositions
US7169850B2 (en) 2002-02-07 2007-01-30 Kraton Polymers U.S. Llc Block copolymers and method for making same
US6987142B2 (en) 2002-02-07 2006-01-17 Kraton Polymers U.S. Llc Adhesives and sealants from controlled distribution block copolymers
US7244785B2 (en) 2002-02-07 2007-07-17 Bening Robert C Block copolymers and method for making same
US7267855B2 (en) 2002-02-07 2007-09-11 Kraton Polymers U.S. Llc Articles prepared from hydrogenated controlled distribution block copolymers
US7282536B2 (en) 2002-02-07 2007-10-16 Kraton Polymers Llc Block copolymers and method for making same
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JP2014141540A (en) * 2013-01-22 2014-08-07 Toyo Ink Sc Holdings Co Ltd Resin composition

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