JPH07145281A - Rubber-modified vinylaromatic resin composition - Google Patents
Rubber-modified vinylaromatic resin compositionInfo
- Publication number
- JPH07145281A JPH07145281A JP29343493A JP29343493A JPH07145281A JP H07145281 A JPH07145281 A JP H07145281A JP 29343493 A JP29343493 A JP 29343493A JP 29343493 A JP29343493 A JP 29343493A JP H07145281 A JPH07145281 A JP H07145281A
- Authority
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- Japan
- Prior art keywords
- rubber
- vinyl aromatic
- resin composition
- block copolymer
- polymer
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は衝撃性と流動性に優れた
樹脂組成物に関する。更に詳しくは、優れた衝撃性と流
動性とを有するゴム変性ビニル芳香族樹脂組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition excellent in impact resistance and fluidity. More specifically, it relates to a rubber-modified vinyl aromatic resin composition having excellent impact and fluidity.
【０００２】[0002]
【従来の技術】ＨＩＰＳに代表されるゴム変性ビニル芳
香族樹脂は、成形性、寸法安定性に加え、耐衝撃性にす
ぐれていることから、家電機器、ＯＡ機器をはじめ多岐
にわたり使用されている。近年これらの分野において、
衝撃性と流動性とに対する要望がさらに高まりつつあ
る。2. Description of the Related Art Rubber-modified vinyl aromatic resins typified by HIPS are used in a wide variety of fields such as home appliances and office automation equipment because they have excellent impact resistance in addition to moldability and dimensional stability. . In these fields in recent years,
The demand for impact and fluidity is increasing.
【０００３】このためＨＩＰＳ中のゴム量を増加させる
ことにより改良がなされたりするが流動性の低下をとも
なうという問題点があった。また衝撃強度の向上のため
にシリコンオイルなどの添加剤が用いられているが十分
な改良ではなかった。一方、流動性向上の方法としては
ＨＩＰＳマトリックス樹脂の分子量を低下させたり、鉱
油などの可塑剤をブレンドする方法があるが、衝撃強度
や耐熱性の低下を伴い満足のいく物性が得られないとい
う問題があった。For this reason, some improvements have been made by increasing the amount of rubber in HIPS, but there has been a problem that the fluidity is lowered. Further, additives such as silicone oil have been used to improve impact strength, but this is not a sufficient improvement. On the other hand, as a method for improving the fluidity, there is a method of lowering the molecular weight of the HIPS matrix resin or a method of blending a plasticizer such as mineral oil, but it is said that satisfactory physical properties cannot be obtained due to the reduction of impact strength and heat resistance. There was a problem.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、優れ
た衝撃強度と流動性とを有するゴム変性ビニル芳香族樹
脂組成物を提供することにある。An object of the present invention is to provide a rubber-modified vinyl aromatic resin composition having excellent impact strength and fluidity.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
鋭意検討を重ねた結果、本発明者らはある特定構造のブ
ロック共重合体を組成物として有することを特徴とする
ゴム変性ビニル芳香族樹脂組成物が上記課題を効果的に
解決することを見いだし、本発明を完成するに至った。As a result of extensive studies to solve the above problems, the present inventors have found that a rubber-modified vinyl aromatic compound having a block copolymer having a specific structure as a composition. They have found that a resin composition effectively solves the above problems, and completed the present invention.
【０００６】即ち、本発明は、ビニル芳香族重合体
（１）と、ビニル芳香族重合体ブロック及びジエン系重
合体であってかつ該ジエン系重合体を構成する単量体単
位の少なくとも５０モル％が水素添加された重合体ブロ
ックとより成るブロック共重合体（２）とからなり、上
記ビニル芳香族重合体（１）が７０〜９９重量部、上記
ブロック共重合体（２）が１〜３０重量部であるゴム変
性ビニル芳香族樹脂組成物において、上記ブロック共重
合体（２）がビニル芳香族重合体（１）を連続相として
分散体を形成しており、しかも、ルテニウム酸染色法に
より上記ゴム変性ビニル芳香族樹脂組成物中の上記ブロ
ック共重合体（２）を染色した透過型電子顕微鏡写真か
ら得られた、（ａ）上記ブロック共重合体（２）の分散
体の平均円相当径が０．２〜５μｍの範囲にあり、
（ｂ）染色された上記分散体の全面積（Ａ）と染色され
た上記分散体の円相当径が０．５μｍ以上である成分の
面積（Ｚ）との割合（Ｚ／Ａ）が少なくとも０．２であ
ることを特徴とするゴム変性ビニル芳香族樹脂組成物、
である。That is, the present invention provides a vinyl aromatic polymer (1), a vinyl aromatic polymer block and a diene-based polymer, and at least 50 mols of monomer units constituting the diene-based polymer. % Of the hydrogenated polymer block and the block copolymer (2), the vinyl aromatic polymer (1) is 70 to 99 parts by weight, and the block copolymer (2) is 1 to In the rubber-modified vinyl aromatic resin composition of 30 parts by weight, the block copolymer (2) forms a dispersion with the vinyl aromatic polymer (1) as a continuous phase, and the ruthenic acid dyeing method is used. The average circle of the dispersion of (a) the block copolymer (2) obtained from a transmission electron micrograph of the block copolymer (2) dyed in the rubber-modified vinyl aromatic resin composition according to Equivalent diameter is 0 It is in the range of 2~5μm,
(B) The ratio (Z / A) of the total area (A) of the dyed dispersion and the area (Z) of the component having a circle-equivalent diameter of 0.5 μm or more of the dyed dispersion (Z / A) is at least 0. 2. A rubber-modified vinyl aromatic resin composition, characterized in that
Is.
【０００７】本発明のゴム変性ビニル芳香族樹脂組成物
中では、ブロック共重合体（２）はビニル芳香族重合体
（１）をマトリックスとして分散相を形成しており、５
００個以上の上記ブロック共重合体（２）の分散体が撮
影されている５千〜５万倍の透過型電子顕微鏡写真にお
いて、画像解析装置（商品名 ＩＰ１０００：旭化成工
業（株）社製）を用い求めた、ルテニウム酸染色された
上記ブロック共重合体（２）部分の平均円相当径は０．
２〜５μｍの範囲にあることが必要である。平均円相当
径が０．２μｍより小さいと衝撃強度に劣り、５μｍよ
り大きいと剛性が低下するなどの欠点が生じ好ましくな
い。平均円相当径の好ましい範囲は０．３〜３．５μｍ
であり、さらに好ましい範囲は０．５〜２．５μｍであ
る。In the rubber-modified vinyl aromatic resin composition of the present invention, the block copolymer (2) forms a dispersed phase using the vinyl aromatic polymer (1) as a matrix.
An image analysis device (trade name IP1000: manufactured by Asahi Kasei Co., Ltd.) in a transmission electron micrograph of 5,000 to 50,000 times in which 00 or more dispersions of the block copolymer (2) were photographed The average circle-equivalent diameter of the ruthenium acid-stained block copolymer (2) portion obtained using
It is necessary to be in the range of 2 to 5 μm. If the average equivalent circle diameter is smaller than 0.2 μm, the impact strength is poor, and if it is larger than 5 μm, the rigidity is lowered, which is not preferable. A preferable range of the average equivalent circle diameter is 0.3 to 3.5 μm
And a more preferable range is 0.5 to 2.5 μm.
【０００８】また、上記写真中に占める上記ブロック共
重合体（２）部分のうち、円相当径が０．５μｍ以上で
ある成分の面積（Ｚ）と染色部分面積（Ａ）の割合（Ｚ
／Ａ）は少なくとも０．２であることが必要である。
０．２に満たない場合は衝撃強度に劣るが、上記要件を
満たす限り円相当径分布については特に制約はなく、二
峰分布性のものであってもよい。Ｚ／Ａはより好ましく
は０．３以上である。Further, in the block copolymer (2) portion occupied in the photograph, the ratio (Z) of the area (Z) of the component having a circle-equivalent diameter of 0.5 μm or more and the dyed portion area (A) (Z
/ A) must be at least 0.2.
When it is less than 0.2, the impact strength is poor, but as long as the above requirements are satisfied, there is no particular limitation on the equivalent circle diameter distribution, and bimodal distribution may be used. Z / A is more preferably 0.3 or more.
【０００９】以下、本発明の詳細を説明する。まず、上
記ビニル芳香族重合体（１）を構成する単量体とは、ス
チレンのほかｏ−メチルスチレン、ｍ−メチルスチレ
ン、ｐ−メチルスチレン、２，４−ジメチルスチレン、
エチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレンなどの
核アルキル置換スチレン、α−メチルスチレン、α−メ
チル−ｐ−メチルスチレンなどのα−アルキル置換スチ
レンなどであるが、代表的なものは、スチレンの単独も
しくは、その一部をスチレン以外の上記ビニル芳香族単
量体で置き換えた単量体混合物であり、公知の塊状、懸
濁、乳化または溶液重合方法により上記（１）のビニル
芳香族重合体を得ることができる。The details of the present invention will be described below. First, the monomers constituting the vinyl aromatic polymer (1) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,
Nuclear alkyl-substituted styrenes such as ethyl styrene and p-tert-butyl styrene, α-alkyl substituted styrenes such as α-methyl styrene and α-methyl-p-methyl styrene, and the like, but typical ones include styrene alone. Alternatively, it is a monomer mixture in which a part thereof is replaced with the above vinyl aromatic monomer other than styrene, and the vinyl aromatic polymer of (1) above is prepared by a known bulk, suspension, emulsion or solution polymerization method. Obtainable.
【００１０】本発明のゴム変性ビニル芳香族樹脂組成物
は、メチルエチルケトン可溶分のゲルパーミッションク
ロマトグラフにより求めた重量平均分子量が７万〜３０
万の範囲にあることが好ましい。次に、ブロック共重合
体（２）は、ビニル芳香族重合体ブロック（以後重合体
ブロックＳと略称する）と、ジエン系重合体であって、
かつジエン系重合体を構成する単量体の少なくとも５０
モル％が水素添加された重合体ブロック（以後重合体ブ
ロックＤと略称する）よりなるブロック共重合体である
ことが必要である。重合体ブロックＤを構成する単量体
の水素添加率が５０モル％に満たない場合には、最終的
に得られるゴム変性ビニル芳香族樹脂組成物にフローマ
ークが発生しやすくかつ高温成形時に光沢が低下するな
どの欠点が生じる。The rubber-modified vinyl aromatic resin composition of the present invention has a weight average molecular weight of 70,000 to 30 as determined by gel permeation chromatography of a methyl ethyl ketone soluble component.
It is preferably in the range of 10,000. Next, the block copolymer (2) is a vinyl aromatic polymer block (hereinafter abbreviated as polymer block S) and a diene polymer,
And at least 50 monomers constituting the diene polymer
It is necessary that the mol% is a block copolymer composed of hydrogenated polymer blocks (hereinafter abbreviated as polymer block D). When the hydrogenation rate of the monomer constituting the polymer block D is less than 50 mol%, the rubber-modified vinyl aromatic resin composition finally obtained tends to have flow marks and has a gloss during high temperature molding. However, there are drawbacks such as a decrease in
【００１１】上記重合体ブロックＳを構成するビニル芳
香族単量体とは、スチレンのほかｏ−メチルスチレン、
ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジ
メチルスチレン、エチルスチレン、ｐ−ｔｅｒｔ−ブチ
ルスチレンなどの核アルキル置換スチレン、α−メチル
スチレン、α−メチル−ｐ−メチルスチレンなどのα−
アルキル置換スチレンなどであるが、代表的なものは、
スチレンの単独もしくは、その一部をスチレン以外の上
記ビニル芳香族単量体で置き換えた単量体混合物であ
る。The vinyl aromatic monomer constituting the polymer block S includes styrene, o-methylstyrene,
Nuclear alkyl-substituted styrenes such as m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene and other α-
Alkyl-substituted styrene etc., but the typical ones are
It is a monomer mixture in which styrene is used alone or a part thereof is replaced with the above vinyl aromatic monomer other than styrene.
【００１２】また、上記重合体ブロックＤの水素添加さ
れる前の単量体単位としては、１，３−ブタジエン、イ
ソプレンなどを挙げることができ、上記ブロック共重合
体中のジエン系重合体を構成する単量体の水素添加率
は、好ましくは６０モル％以上、より好ましくは８０モ
ル％以上である。以上の要件を満たすブロック共重合体
は公知のスチレン−共役ジエンブロック共重合体に、公
知の水素添加処理たとえば特開昭５９−１３３２０３号
公報に開示の方法の水素添加処理をすることにより得る
ことができる。As the monomer unit of the polymer block D before hydrogenation, 1,3-butadiene, isoprene and the like can be mentioned, and the diene polymer in the block copolymer can be used. The hydrogenation rate of the constituent monomers is preferably 60 mol% or more, more preferably 80 mol% or more. The block copolymer satisfying the above requirements can be obtained by subjecting a known styrene-conjugated diene block copolymer to a known hydrogenation treatment, for example, the hydrogenation treatment according to the method disclosed in JP-A-59-133203. You can
【００１３】上記ブロック共重合体中の重合体ブロック
Ｓの含量は、５〜５０重量％の範囲にある。また、ブロ
ック共重合体のブロック構造は、重合体ブロックＳを単
にＳ、重合体ブロックＤを単にＤで表示する場合、Ｓ
Ｄ、Ｓ（ＤＳ）n （但し、ｎは１〜３の整数）、Ｓ（Ｄ
ＳＤ）n （但し、ｎは１〜２の整数）のリニアーブロッ
ク共重合体及び（ＳＤ）n Ｘ（但し、ｎは３〜６の整
数。Ｘは四塩化ケイ素、四塩化スズ、ポリエポキシ化合
物などのカップリング剤残基。）で表示される、Ｄ部分
を結合中心とする星状（スター）ブロック共重合体であ
ることが好ましい。The content of the polymer block S in the above block copolymer is in the range of 5 to 50% by weight. Further, the block structure of the block copolymer is S when the polymer block S is simply represented by S and the polymer block D is simply represented by S.
D, S (DS) n (where n is an integer of 1 to 3), S (D
SD) n (where n is an integer of 1-2) and (SD) n X (where n is an integer of 3-6. X is silicon tetrachloride, tin tetrachloride, a polyepoxy compound) It is preferably a star block copolymer having a D portion as a bond center, which is represented by a coupling agent residue such as.
【００１４】なかでも、ＳＤ２型、ＳＤＳ３型、ＳＤＳ
Ｄ４型のリニアーブロック共重合体が好ましい。ブロッ
ク共重合体の分子量は数平均分子量で２万〜３５万の範
囲にあることが好ましく、８万〜２５万の範囲にあるこ
とがより好ましい。本発明のゴム変性ビニル芳香族樹脂
組成物は、上記ブロック共重合体の割合が１〜３０重量
部であり、２〜２０重量部であることが好ましく、１０
〜１５重量部が更に好ましい。ブロック共重合体の割合
が１重量部に満たない場合は、強度に劣り、３０重量部
を越える場合は流動性に劣るようになる。Among them, SD2 type, SDS3 type, SDS
A D4 type linear block copolymer is preferred. The number average molecular weight of the block copolymer is preferably in the range of 20,000 to 350,000, more preferably in the range of 80,000 to 250,000. In the rubber-modified vinyl aromatic resin composition of the present invention, the ratio of the block copolymer is 1 to 30 parts by weight, preferably 2 to 20 parts by weight.
-15 parts by weight is more preferable. When the proportion of the block copolymer is less than 1 part by weight, the strength is poor, and when it exceeds 30 parts by weight, the fluidity is poor.
【００１５】また、上記ゴム変性ビニル芳香族樹脂組成
物に、更に鉱油（３）を加えたゴム変性ビニル芳香族樹
脂組成物は衝撃強度が向上したものとなり、鉱油の平均
分子量が４００以上、及び／または、ｎ−ｄ−Ｍ環分析
法によるナフテン成分の割合が３３％以下であるとその
効果が更に著しい。上記鉱油のゴム変性ビニル芳香族樹
脂組成物１００重量部に対する割合は２０重量部以下で
あり、１〜１５重量部が好ましい。鉱油の割合が２０重
量部を越える場合は耐熱性に劣る。またブロック共重合
体（２）に対する上記鉱油の割合は、５重量％〜５００
重量％が好ましく１０重量％〜４００重量％がより好ま
しい。鉱油の平均分子量が４００以下で、ナフテン成分
の割合が３３％を越える樹脂組成物は流動性に優れるが
耐熱性、衝撃強度に劣る。またナフテン成分量を求める
前記ｎ−ｄ−Ｍ環分析法とは高沸点石油留分の分析方法
であり、芳香環中の炭素原子の含量、ナフテン環中の炭
素原子の含量、パラフィン鎖中の炭素原子の含量を求め
るものである。また、平均分子量は試料の粘度及び粘度
指数を石油製品の動粘度試験方法並びに石油製品粘度指
数算出方法に規定する方法で測定し算出する。Further, the rubber-modified vinyl aromatic resin composition obtained by further adding mineral oil (3) to the rubber-modified vinyl aromatic resin composition has improved impact strength, and the average molecular weight of the mineral oil is 400 or more, and If the ratio of the naphthene component by the ndM ring analysis method is 33% or less, the effect is more remarkable. The ratio of the mineral oil to 100 parts by weight of the rubber-modified vinyl aromatic resin composition is 20 parts by weight or less, preferably 1 to 15 parts by weight. When the proportion of mineral oil exceeds 20 parts by weight, the heat resistance is poor. The ratio of the mineral oil to the block copolymer (2) is 5% by weight to 500%.
Weight% is preferable, and 10 weight% to 400 weight% is more preferable. A resin composition in which the average molecular weight of mineral oil is 400 or less and the proportion of the naphthene component exceeds 33% is excellent in fluidity but inferior in heat resistance and impact strength. The n-d-M ring analysis method for determining the amount of naphthene components is a method for analyzing high boiling point petroleum fractions, including the content of carbon atoms in aromatic rings, the content of carbon atoms in naphthene rings, and the content of paraffin chains. The content of carbon atoms is determined. The average molecular weight is calculated by measuring the viscosity and viscosity index of the sample by the method specified in the kinematic viscosity test method for petroleum products and the method for calculating petroleum product viscosity index.
【００１６】本発明のゴム変性ビニル芳香族樹脂組成物
の製造方法は、（イ）ビニル芳香族単量体を公知の方法
により、塊状、塊状・懸濁、乳化または溶液重合を行
い、ビニル芳香族単量体の重合終了後、脱揮回収したビ
ニル芳香族重合体（１）とブロック共重合体（２）を溶
融混合する方法、（ロ）ブロック共重合体（２）を溶解
したビニル芳香族単量体を公知の方法により、せん断力
の存在下に塊状、塊状・懸濁、溶液重合を行い、重合終
了後、脱揮回収する方法、などがある。The method for producing the rubber-modified vinyl aromatic resin composition of the present invention comprises: (a) vinyl aromatic monomer is subjected to bulk, bulk / suspension, emulsion or solution polymerization by a known method to obtain vinyl aromatic After completion of the polymerization of the group monomer, a method of melt-mixing the volatilized and recovered vinyl aromatic polymer (1) and the block copolymer (2), and (b) a vinyl aromatic in which the block copolymer (2) is dissolved. For example, there is a method in which a group monomer is subjected to bulk, bulk / suspension, or solution polymerization by a known method in the presence of shearing force, and then devolatilized and recovered after completion of the polymerization.
【００１７】ブロック共重合体（２）の分散状態の調整
は、ブロック共重合体の分子量、ブロック共重合体
（２）に結合するビニル芳香族重合体ブロックＳの分子
量、重合時のせん断力、溶融混合時の押し出し機などの
フィード量、及びスクリュウ回転数を制御するなどの方
法で行える。ブロック共重合体の分子量を大きく、ブロ
ック共重合体（２）に結合するビニル芳香族重合体ブロ
ックＳの分子量を小さくすると分散相の平均円相当径が
大きい上記ゴム変性ビニル芳香族樹脂組成物が得られ
る。The dispersion state of the block copolymer (2) can be adjusted by adjusting the molecular weight of the block copolymer, the molecular weight of the vinyl aromatic polymer block S bonded to the block copolymer (2), the shearing force during polymerization, It can be performed by a method such as controlling the feed amount of an extruder or the like at the time of melt mixing and the screw rotation speed. When the molecular weight of the block copolymer is large and the molecular weight of the vinyl aromatic polymer block S bonded to the block copolymer (2) is small, the above rubber-modified vinyl aromatic resin composition has a large average circle equivalent diameter of the dispersed phase. can get.
【００１８】溶融混合の方法については特に制約はな
く、バンバリーミキサー、単軸押し出し機、２軸押し出
し機などの公知の混練装置により溶融混合すればよい。
また、鉱油（３）は、ブロック共重合体と予め混合して
おく、前記（イ）、（ロ）の方法で得られたゴム変性樹
脂組成物と溶融混合する、あるいは、前記（イ）、
（ロ）の方法において重合液または重合途中の液に混合
する、こともできる。The method of melt mixing is not particularly limited, and melt mixing may be performed by a known kneading device such as a Banbury mixer, a single-screw extruder or a twin-screw extruder.
Further, the mineral oil (3) is mixed with the block copolymer in advance, melt-mixed with the rubber-modified resin composition obtained by the method of (a) or (b), or (a),
In the method (b), it can be mixed with the polymerization liquid or the liquid in the process of polymerization.
【００１９】本発明のゴム変性ビニル芳香族系樹脂組成
物には、有機シロキサン、高級脂肪酸、高級脂肪酸の金
属塩、高級脂肪酸のアミド類を添加することにより衝撃
強度を一段と高めることができる。また本発明のゴム変
性ビニル芳香族樹脂組成物には、染顔料、滑剤、充填
剤、離型剤、可塑剤、帯電防止剤、難燃剤、酸化防止
剤、紫外線吸収剤、熱安定剤などの添加剤を必要に応じ
て添加することができる。Impact strength can be further enhanced by adding an organosiloxane, a higher fatty acid, a metal salt of a higher fatty acid, or an amide of a higher fatty acid to the rubber-modified vinyl aromatic resin composition of the present invention. The rubber-modified vinyl aromatic resin composition of the present invention includes dyes and pigments, lubricants, fillers, release agents, plasticizers, antistatic agents, flame retardants, antioxidants, ultraviolet absorbers, heat stabilizers, and the like. Additives can be added as needed.
【００２０】[0020]
【実施例】以下、実施例により本発明を具体的に説明す
る。なお物性測定は、下記方法によった。 （１）アイゾット衝撃強度は、ＡＳＴＭ Ｄ２５６に準
拠。 （２）メルトフローレートは、ＩＳＯ−Ｒ１１３３に準
拠。EXAMPLES The present invention will be specifically described below with reference to examples. The physical properties were measured by the following methods. (1) Izod impact strength complies with ASTM D256. (2) The melt flow rate complies with ISO-R1133.
【００２１】（３）ビカット軟化点は、ＡＳＴＭ Ｄ１
５２５に準拠。 （４）平均円相当径と（Ｚ／Ａ）とは、試料をクライオ
ミクロトームを用いて、液体窒素下ー１６０℃で切削し
た厚さ５０〜１００ｎｍの超薄切片をＲｕＯ4 蒸気で５
分染色後撮影した透過型電子顕微鏡写真について画像解
析を行い、（Ｚ／Ａ）を求めた。 以下の実施例、比較例において、下記の参考例１〜５に
示す重合体を用いた。(3) Vicat softening point is ASTM D1
Compliant with 525. (4) The average equivalent circle diameter and (Z / A) are the values obtained by cutting a sample with a cryomicrotome at −160 ° C. under liquid nitrogen at an ultrathin section of 50 to 100 nm in thickness with RuO 4 vapor.
Image analysis was performed on transmission electron micrographs taken after minute staining to determine (Z / A). In the following examples and comparative examples, the polymers shown in the following reference examples 1 to 5 were used.
【００２２】［参考例１］ ブロック共重合体Ｄ１、Ｄ２の調整 オートクレーブ中にシクロヘキサン４００ｇ、スチレン
２０ｇ、ｎ−ブチルリチウム０．０９ｇ、及びテトラヒ
ドロフランをｎ−ブチルリチウム／テトラヒドロフラン
＝４０の割合で加え、６０度Ｃで３時間重合した。次い
で１，３−ブタジエンを８０ｇ加えて６０度Ｃで３時間
重合し、ブロックスチレン含有量２０重量％、ブタジエ
ン単位の１，２−ビニル結合含有量３５モル％、数平均
分子量１００，０００のスチレン−ブタジエン型ブロッ
ク共重合体を得た。Reference Example 1 Preparation of Block Copolymers D1 and D2 400 g of cyclohexane, 20 g of styrene, 0.09 g of n-butyllithium, and tetrahydrofuran were added to an autoclave at a ratio of n-butyllithium / tetrahydrofuran = 40, Polymerization was carried out at 60 ° C for 3 hours. Then, 80 g of 1,3-butadiene was added and the mixture was polymerized at 60 ° C. for 3 hours to give a styrene having a block styrene content of 20% by weight, a 1,2-vinyl bond content of a butadiene unit of 35 mol% and a number average molecular weight of 100,000. A butadiene type block copolymer was obtained.
【００２３】次いで、特開昭５９−１３３２０３号公報
に開示の方法の水素添加処理を行い、ブタジエン単位の
水素添加率９５モル％のブロック共重合体（Ｄ１）を得
た。また、上記方法に準拠し、重合温度、重合時間、単
体量の量を変更して、ブロックスチレン含有量３７重量
％、ブタジエン単位の１，２−ビニル結合含有量３５モ
ル％、数平均分子量１３０，０００のスチレン−ブタジ
エン型ブロック共重合体を得た。次いで上記と同様の水
素添加処理を行い、ブタジエン単位の水素添加率９５モ
ル％のブロック共重合体（Ｄ２）を得た。Then, hydrogenation treatment according to the method disclosed in JP-A-59-133203 was carried out to obtain a block copolymer (D1) having a hydrogenation rate of 95 mol% of butadiene units. Further, according to the above method, the polymerization temperature, the polymerization time, and the amount of the simple substance are changed, and the block styrene content is 37% by weight, the 1,2-vinyl bond content of the butadiene unit is 35 mol%, and the number average molecular weight is 130. , Styrene-butadiene type block copolymer was obtained. Then, the same hydrogenation treatment as above was performed to obtain a block copolymer (D2) having a butadiene unit hydrogenation rate of 95 mol%.
【００２４】［参考例２］ ブロック共重合体Ｄ３、Ｄ４の調整 オートクレーブ中にシクロヘキサン４００ｇ、１，３−
ブタジエン９ｇ、ｎ−ブチルリチウム０．０８ｇおよび
テトラヒドロフランをモル比でｎ−ブチルリチウム／テ
トラヒドロフラン＝４０の割合で加え、７０度Ｃで１時
間重合し、次いでスチレン１９ｇを加えて３０分、次い
で１，３−ブタジエン５６ｇを加えて７５分、そして最
後にスチレンを１６ｇ加えて３０分重合し、ブロックス
チレン含有量３５重量％、ブタジエン単位の１，２−ビ
ニル結合含有量３５モル％、数平均分子量１２０，００
０のスチレン−ブタジエン−スチレン−ブタジエン型ブ
ロック共重合体を得た。Reference Example 2 Preparation of Block Copolymers D3 and D4 Cyclohexane 400 g, 1,3-in an autoclave
Butadiene 9 g, n-butyllithium 0.08 g and tetrahydrofuran were added at a molar ratio of n-butyllithium / tetrahydrofuran = 40 and polymerized at 70 ° C. for 1 hour, then 19 g of styrene was added for 30 minutes, then 1 ,. 3-Butadiene (56 g) was added for 75 minutes, and finally styrene (16 g) was added for 30 minutes for polymerization, and the block styrene content was 35% by weight, the 1,2-vinyl bond content of the butadiene unit was 35 mol%, and the number average molecular weight was 120. , 00
A styrene-butadiene-styrene-butadiene type block copolymer of 0 was obtained.
【００２５】次いで参考例１と同様の水素添加処理を行
い、ブタジエン単位の水素添加率９５モル％のブロック
共重合体（Ｄ３）を得た。 また、上記方法に準拠し、
重合温度、重合時間、単量体の量を変更して、ブロック
スチレン含有量３２重量％、ブタジエン単位の１，２−
ビニル結合含有量３５モル％、数平均分子量４８，００
０のスチレン−ブタジエン−スチレン−ブタジエン型ブ
ロック共重合体を得た。次いで参考例１と同様の水素添
加処理を行い、ブタジエン単位の水素添加率９５モル％
のブロック共重合体（Ｄ４）を得た。Then, the same hydrogenation treatment as in Reference Example 1 was carried out to obtain a block copolymer (D3) having a hydrogenation rate of 95 mol% of butadiene units. Also, in accordance with the above method,
By changing the polymerization temperature, the polymerization time, and the amount of the monomer, the block styrene content is 32% by weight, and the butadiene unit 1,2-
Vinyl bond content 35 mol%, number average molecular weight 48,000
A styrene-butadiene-styrene-butadiene type block copolymer of 0 was obtained. Then, the same hydrogenation treatment as in Reference Example 1 was performed, and the hydrogenation rate of the butadiene unit was 95 mol%.
The block copolymer (D4) of was obtained.
【００２６】なお、上記Ｄ１〜Ｄ４のブタジエン単量体
単位部分の水素添加率の測定は、ＮＭＲにて測定した。
（測定の詳細は、特開昭６４−９０２０８号公報に記載
の手順に依った。） ［参考例３］ ゴム変性ポリスチレンＨ１の調整 ポリブタジエンゴム（日本ゼオン株式会社製、商品名
ニポール１２２０ＳＬ）をスチレンに溶解し、次いでエ
チルベンゼン及び、１，１−ビス（ｔ−ブチルパーオキ
シ）３，３，５−トリメチルシクロヘキサンの少量を加
え、最終的に下記の組成より成る重合原液を調整した
（単位は重量部数）。The hydrogenation rate of the butadiene monomer unit portion of the above D1 to D4 was measured by NMR.
(Details of the measurement were based on the procedure described in JP-A-64-90208.) [Reference Example 3] Preparation of rubber-modified polystyrene H1 Polybutadiene rubber (manufactured by Nippon Zeon Co., Ltd., trade name
Nipol 1220SL) is dissolved in styrene, and then ethylbenzene and a small amount of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane are added to finally prepare a polymerization stock solution having the following composition. Yes (unit is parts by weight).
【００２７】・ポリブタジエンゴム−−−−−１０．０ ・スチレン−−−−−−−−−−７８．０ ・エチルベンゼン−−−−−−−１２．０ ・１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−
トリメチルシクロヘキサン−−−−−−−−−−−−−
−０．０１ 上記の重合原液を、各々の内容積が６．２リットルの撹
拌機付きの３槽式反応機に連続的に送液した。第一槽反
応機出口の固形分濃度が３０重量％となるように反応機
内温度を制御した。最終槽反応機出口の固形分濃度が８
０重量％となるように反応機内温度を調整した。次いで
２３０度Ｃ、真空下の脱揮装置に送り込み、未反応のス
チレン及びエチルベンゼンを除去し、押出機にて造粒し
ペレット状のゴム変性ビニル芳香族樹脂、Ｈ１を得た。-Polybutadiene rubber ---- 10.0-Styrene -------- 78.0-Ethylbenzene--1-2.0-1, 1-bis (t- Butyl peroxy) 3,3,5-
Trimethylcyclohexane ---------------
-0.01 The above-mentioned polymerization stock solution was continuously fed to a 3-tank reactor equipped with a stirrer and having an internal volume of 6.2 liters. The temperature inside the reactor was controlled so that the solid content concentration at the outlet of the first tank reactor was 30% by weight. Solids concentration at the outlet of the final tank is 8
The temperature inside the reactor was adjusted so as to be 0% by weight. Next, it was sent to a devolatilizer under vacuum at 230 ° C. to remove unreacted styrene and ethylbenzene, and granulated with an extruder to obtain pelletized rubber-modified vinyl aromatic resin, H1.
【００２８】ゴム変性ビニル芳香族樹脂中のポリブタジ
エンゴムの含量は、１２．５重量％、ゲル含量は３０重
量％、分散相の平均粒子径は１．４ミクロン、トルエン
に対する膨潤指数は９．８であり、メチルエチルケトン
可溶分より求めたマトリックス相の重量平均分子量は２
０１，０００であった。 ［参考例４］ ビニル芳香族重合体Ｖ１の調整 塊状重合方法により、重量平均分子量１８２，０００の
ポリスチレンを調整した。The content of polybutadiene rubber in the rubber-modified vinyl aromatic resin was 12.5% by weight, the gel content was 30% by weight, the average particle size of the dispersed phase was 1.4 microns, and the swelling index in toluene was 9.8. And the weight average molecular weight of the matrix phase determined from the methyl ethyl ketone soluble content is 2
It was 01,000. [Reference Example 4] Preparation of vinyl aromatic polymer V1 Polystyrene having a weight average molecular weight of 182,000 was prepared by a bulk polymerization method.
【００２９】［参考例５］ ビニル芳香族重合体Ｖ２の調整 塊状重合方法により、重量平均分子量１３１，０００の
ポリスチレンを調整した。[Reference Example 5] Preparation of vinyl aromatic polymer V2 Polystyrene having a weight average molecular weight of 131,000 was prepared by a bulk polymerization method.
【００３０】[0030]
【実施例１〜８、比較例１〜２、参考例１〜２】前記参
考例１、２で得たブロック共重合体Ｄ１、Ｄ２、Ｄ３、
Ｄ４、参考例３で得たゴム変性ビニル芳香族樹脂Ｈ１、
参考例４、５で得たビニル芳香族重合体Ｖ１、Ｖ２、と
鉱油を表１〜３に示す比率にて配合し、押し出し機にて
溶融・混練し、ゴム変性ビニル芳香族樹脂組成物のペレ
ットを得た。次いで得られたゴム変性ビニル芳香族樹脂
組成物のペレットより射出成形機にて、２２０℃の成形
温度にて試験片を作成し物性を測定した。 結果を表１
〜３に示す。Examples 1-8, Comparative Examples 1-2, Reference Examples 1-2 The block copolymers D1, D2, D3 obtained in Reference Examples 1 and 2 above.
D4, rubber-modified vinyl aromatic resin H1 obtained in Reference Example 3,
Vinyl aromatic polymers V1 and V2 obtained in Reference Examples 4 and 5 and mineral oil were blended in the ratios shown in Tables 1 to 3 and melted and kneaded with an extruder to obtain a rubber-modified vinyl aromatic resin composition. Pellets were obtained. Then, a test piece was prepared from the obtained rubber-modified vinyl aromatic resin composition pellets at a molding temperature of 220 ° C. by an injection molding machine, and the physical properties were measured. The results are shown in Table 1.
~ 3.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【発明の効果】本発明のゴム変性ビニル芳香族樹脂組成
物は、従来のものに比較して、衝撃強度と流動性とのバ
ランスに優れる。また、鉱油を第３の成分として用いた
ゴム変性ビニル芳香族樹脂組成物は、より一層衝撃強度
に優れたものである。The rubber-modified vinyl aromatic resin composition of the present invention has an excellent balance between impact strength and fluidity as compared with the conventional ones. Further, the rubber-modified vinyl aromatic resin composition using mineral oil as the third component is more excellent in impact strength.
【図１】実施例３のゴム変性ビニル芳香族樹脂組成物中
において分散体を形成するブロック共重合体の粒子構造
を示す透過型電子顕微鏡写真。FIG. 1 is a transmission electron micrograph showing the particle structure of a block copolymer forming a dispersion in the rubber-modified vinyl aromatic resin composition of Example 3.
Claims (3)
重合体ブロック及びジエン系重合体であってかつ該ジエ
ン系重合体を構成する単量体単位の少なくとも５０モル
％が水素添加された重合体ブロックとより成るブロック
共重合体（２）とからなり、上記ビニル芳香族重合体
（１）が７０〜９９重量部、上記ブロック共重合体
（２）が１〜３０重量部であるゴム変性ビニル芳香族樹
脂組成物において、上記ブロック共重合体（２）がビニ
ル芳香族重合体（１）を連続相として分散体を形成して
おり、しかも、ルテニウム酸染色法により上記ゴム変性
ビニル芳香族樹脂組成物中の上記ブロック共重合体
（２）を染色した透過型電子顕微鏡写真から得られた、
（ａ）上記ブロック共重合体（２）の分散体の平均円相
当径が０．２〜５μｍの範囲にあり、（ｂ）染色された
上記分散体の全面積（Ａ）と染色された上記分散体の円
相当径が０．５μｍ以上である成分の面積（Ｚ）との割
合（Ｚ／Ａ）が少なくとも０．２であることを特徴とす
るゴム変性ビニル芳香族樹脂組成物。1. A vinyl aromatic polymer (1), a vinyl aromatic polymer block and a diene polymer, wherein at least 50 mol% of the monomer units constituting the diene polymer are hydrogenated. And a block copolymer (2) comprising a polymer block, the vinyl aromatic polymer (1) is 70 to 99 parts by weight, and the block copolymer (2) is 1 to 30 parts by weight. In the rubber-modified vinyl aromatic resin composition, the block copolymer (2) forms a dispersion with the vinyl aromatic polymer (1) as a continuous phase, and the rubber-modified vinyl is dyed by a ruthenium acid dyeing method. Obtained from a transmission electron micrograph of the block copolymer (2) dyed in the aromatic resin composition,
(A) The average circle equivalent diameter of the dispersion of the block copolymer (2) is in the range of 0.2 to 5 μm, and (b) the total area (A) of the dyed dispersion is dyed. A rubber-modified vinyl aromatic resin composition, characterized in that the ratio (Z / A) to the area (Z) of a component having a circle-equivalent diameter of 0.5 μm or more in the dispersion is at least 0.2.
物が１００重量部と鉱油（３）が２０重量部以下とより
なることを特徴とするゴム変性ビニル芳香族樹脂組成
物。2. A rubber-modified vinyl aromatic resin composition comprising 100 parts by weight of the rubber-modified vinyl aromatic resin composition of claim 1 and 20 parts by weight or less of mineral oil (3).
び／または、ｎ−ｄ−Ｍ環分析法によって求まるナフテ
ン成分の割合が３３％以下であることを特徴とする請求
項２のゴム変性ビニル芳香族樹脂組成物。3. The rubber according to claim 2, wherein the average molecular weight of the mineral oil (3) is 400 or more, and / or the proportion of the naphthene component obtained by the ndM ring analysis method is 33% or less. Modified vinyl aromatic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29343493A JP3290012B2 (en) | 1993-11-24 | 1993-11-24 | Rubber-modified vinyl aromatic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29343493A JP3290012B2 (en) | 1993-11-24 | 1993-11-24 | Rubber-modified vinyl aromatic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07145281A true JPH07145281A (en) | 1995-06-06 |
| JP3290012B2 JP3290012B2 (en) | 2002-06-10 |
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ID=17794714
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29343493A Expired - Fee Related JP3290012B2 (en) | 1993-11-24 | 1993-11-24 | Rubber-modified vinyl aromatic resin composition |
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| Country | Link |
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