JPH0737501B2 - Rubber-modified thermoplastic resin composition with good appearance - Google Patents
Rubber-modified thermoplastic resin composition with good appearanceInfo
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- JPH0737501B2 JPH0737501B2 JP61267726A JP26772686A JPH0737501B2 JP H0737501 B2 JPH0737501 B2 JP H0737501B2 JP 61267726 A JP61267726 A JP 61267726A JP 26772686 A JP26772686 A JP 26772686A JP H0737501 B2 JPH0737501 B2 JP H0737501B2
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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、優れた着色性と良好な外観及び機械的性質を
有するゴム変性熱可塑性樹脂組成物に関するものであ
る。TECHNICAL FIELD The present invention relates to a rubber-modified thermoplastic resin composition having excellent coloring properties and good appearance and mechanical properties.
ゴム変性熱可塑性樹脂、例えばゴム変性スチレン−アク
リロニトリル共重合体（一般にABS樹脂と呼称されてい
る）を製造するにあたり、連続塊状重合法または塊状−
懸濁二段重合法は、多量の乳化剤を用いる乳化重合法に
比して、水質汚濁の問題が少なく、また重合後処理に関
する問題も少ないので生産性の点で有利であり、経済性
が高い。しかしながら、連続塊状重合法または塊状−懸
濁二段重合法によるABS樹脂は乳化重合法によるものに
比べて、着色性や光沢等の外観及び機械的性質のバラン
スにおいて劣つていた。In producing a rubber-modified thermoplastic resin such as a rubber-modified styrene-acrylonitrile copolymer (generally referred to as ABS resin), a continuous bulk polymerization method or a bulk-
The suspension two-stage polymerization method is advantageous in terms of productivity because it has less problems of water pollution and less problems regarding post-polymerization treatment, as compared with the emulsion polymerization method using a large amount of emulsifier, and is highly economical. . However, the ABS resin produced by the continuous bulk polymerization method or the bulk-suspension two-stage polymerization method is inferior to the emulsion resin produced by the emulsion polymerization method in terms of balance of appearance and mechanical properties such as colorability and gloss.
本発明者らは、前記連続塊状重合法及び塊状−懸濁二段
重合法の利点を生かしつつ、優れた着色性、良好な光
沢、剛性、耐衝撃強度を有する総合的品質バランスに優
れたゴム変性熱可塑性樹脂組成物を得る目的で鋭意検討
した結果、樹脂相に分散したゴム状物質粒子及びその粒
子内部に内蔵される芳香族モノビニル単量体とシアン化
ビニル単量体との共重合体のミクロ構造を特性すること
により目的を達成し、本発明を成すに至つた。The present inventors have taken advantage of the continuous bulk polymerization method and the bulk-suspension two-stage polymerization method, and at the same time, have excellent colorability, good gloss, rigidity, and impact resistance and are excellent in a comprehensive quality balance. As a result of extensive studies aimed at obtaining a modified thermoplastic resin composition, as a result, particles of a rubber-like substance dispersed in a resin phase and a copolymer of an aromatic monovinyl monomer and a vinyl cyanide monomer incorporated inside the particles. The present invention has been accomplished by achieving the object by characterizing the microstructure of
即ち、本発明は、 （１） ゴム状物質を溶解した芳香族モノビニル単量体
及びシアン化ビニル単量体を、連続塊状重合法または塊
状−懸濁二段重合法により重合して得られるゴム変性熱
可塑性樹脂組成物において、 （ａ）共重合体樹脂相中の成分の割合が、芳香族モノビ
ニル単量体65〜95重量％、シアン化ビニル単量体５〜35
重量％であり、 （ｂ）ゴム状物質が共重合体樹脂相100重量部に対し２
〜20重量部含まれ、1,2ビニル結合を10〜25％、トラン
ス1,4結合を35〜65％、シス1,4結合を25〜40％含有する
ポリブタジエンであつて、スチレン中５重量％の溶液粘
度が10〜50センチポイズであり、 （ｃ）該ゴム状物質が樹脂組成物中において重量平均粒
子径0.2〜1.5ミクロンの粒子として分散しており、重量
平均粒子径と数平均粒子径の比が2.0以下であり、 （ｄ）該ゴム状物質粒子中に内蔵される芳香族モノビニ
ル単量体とシアン化ビニル単量体との共重合体の数平均
粒子径が0.13ミクロン以下であることを特徴とする外観
良好なゴム変性熱可塑性組成物に関するものである。That is, the present invention provides (1) a rubber obtained by polymerizing an aromatic monovinyl monomer and a vinyl cyanide monomer in which a rubber-like substance is dissolved by a continuous bulk polymerization method or a bulk-suspension two-stage polymerization method. In the modified thermoplastic resin composition, the proportion of the component (a) in the copolymer resin phase is 65 to 95% by weight of an aromatic monovinyl monomer and 5 to 35% of a vinyl cyanide monomer.
% By weight, and (b) the rubber-like substance is 2 per 100 parts by weight of the copolymer resin phase
Polybutadiene containing 20 to 20 parts by weight of 1,2 vinyl bonds 10 to 25%, trans 1,4 bonds 35 to 65%, and cis 1,4 bonds 25 to 40%. % Solution viscosity is 10 to 50 centipoise, and (c) the rubber-like substance is dispersed in the resin composition as particles having a weight average particle diameter of 0.2 to 1.5 microns, and the weight average particle diameter and number average particle diameter are Is 2.0 or less, and (d) the number average particle diameter of the copolymer of aromatic monovinyl monomer and vinyl cyanide monomer contained in the rubber-like substance particles is 0.13 micron or less. The present invention relates to a rubber-modified thermoplastic composition having good appearance.
本発明の樹脂組成物は、着色性、光沢、剛性、耐衝撃強
度のバランスに優れ、乳化重合法によるABS樹脂にも匹
敵し、射出成形品、押出成形品、押出真空成形品等を造
る上で有用であり、経済的価値は大である。The resin composition of the present invention has an excellent balance of colorability, gloss, rigidity, and impact strength, and is comparable to ABS resin produced by emulsion polymerization, and is suitable for producing injection molded products, extrusion molded products, extrusion vacuum molded products, etc. It is useful and has great economic value.
以下に本発明を具体的に説明する。The present invention will be specifically described below.
本発明における芳香族モノビニル単量体とは、スチレン
及びｏ−メチルスチレン、ｐ−メチルスチレン、ｍ−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−ブチルスチレン等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
チレン等のα−アルキル置換スチレン、ｏ−クロルスチ
レン、ｍ−クロルスチレン、ｐ−クロルスチレン、ｐ−
ブロモスチレン、２−メチル−1,4−クロルスチレン、
2,4−ジブロモスチレン等の核ハロゲン化スチレン、ビ
ニルナフタレンであり、単独又は、いずれか２種以上の
混合物として用いられる。特に好ましくはスチレン、α
−メチルスチレン、ｐ−メチルスチレン等であり、最も
好ましくはスチレンである。The aromatic monovinyl monomer in the present invention means a nuclear alkyl substitution such as styrene and o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene. Styrene, α-methylstyrene, α-alkyl-substituted styrene such as α-methyl-p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-
Bromostyrene, 2-methyl-1,4-chlorostyrene,
It is a nuclear halogenated styrene such as 2,4-dibromostyrene or vinylnaphthalene, and is used alone or as a mixture of any two or more thereof. Particularly preferably styrene, α
-Methylstyrene, p-methylstyrene and the like, most preferably styrene.
本発明におけるシアン化ビニル単量体とは、アクリロニ
トリル、メタクリロニトリル、α−クロルアクリロニト
リル等であり、単独又はいずれか２種以上の混合物とし
て用いられ、アクリロニトリルが特に好ましい。The vinyl cyanide monomer in the present invention is acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., which are used alone or as a mixture of any two or more thereof, and acrylonitrile is particularly preferable.
共重合体樹脂相中における芳香族モノビニル単量体成分
とシアン化ビニル単量体成分との割合は、両者の合計量
に対して芳香族モノビニル単量体が65〜95重量％、シア
ン化ビニル単量体が５〜35重量％であり、好ましくは芳
香族モノビニル単量体が70〜90重量％、シアン化ビニル
単量体が10〜30重量％である。シアン化ビニル単量体が
５重量％より少ないと強度が低下し、35重量％より多い
と熱安定性や流動性が低下する。The ratio of the aromatic monovinyl monomer component and the vinyl cyanide monomer component in the copolymer resin phase is 65 to 95% by weight of the aromatic monovinyl monomer and vinyl cyanide with respect to the total amount of both. The amount of the monomer is 5 to 35% by weight, preferably 70 to 90% by weight of the aromatic monovinyl monomer and 10 to 30% by weight of the vinyl cyanide monomer. If the amount of vinyl cyanide monomer is less than 5% by weight, the strength will be decreased, and if it is more than 35% by weight, the thermal stability and fluidity will be decreased.
本発明においては、ゴム状物質として、1,2ビル結合を1
0〜25％、トランス1,4結合を35〜65％、シス1,4結合を2
5〜40％含有するポリブタジエンを用いるが、これは耐
衝撃性、特に低温時の耐衝撃強度に優れる為である。ス
チレン−ブタジエン共重合体（SBR）、アクリロニトリ
ル−ブタジエン共重合体（NBR）は低温時の耐衝撃強度
に劣り好ましくない。しかし、着色性及び光沢はポリブ
タジエンを用いるとSBRを用いた場合より従来は劣り好
ましくなかつた。本発明は、ポリブタジエンを用いる
が、特定のミクロ構造に制御することにより、剛性、耐
衝撃強度に優れるのみならず着色性、光沢にも優れた総
合的品質バランスを達成し得たものである。勿論、本発
明の目的を妨げない範囲内でSBR等の他のゴム状物質を
併用することは差支えない。In the present invention, as the rubber-like substance, 1,2 bill bonds are
0 to 25%, trans 1,4 bond 35 to 65%, cis 1,4 bond 2
Polybutadiene containing 5 to 40% is used because it is excellent in impact resistance, particularly impact resistance at low temperature. Styrene-butadiene copolymer (SBR) and acrylonitrile-butadiene copolymer (NBR) are inferior in impact strength at low temperature and are not preferred. However, the colorability and gloss of polybutadiene are inferior to those of SBR and are not preferable. The present invention uses polybutadiene, but by controlling it to have a specific microstructure, it is possible to achieve a comprehensive quality balance not only excellent in rigidity and impact resistance but also excellent in colorability and gloss. Of course, other rubber-like substances such as SBR may be used in combination within a range that does not impair the object of the present invention.
上記ポリブタジエンはｎ−ブチルリチウム、sec−ブチ
ルリチウム等の有機リチウムを含む触媒を用いて公知の
方法により製造される。本発明の特定されたミクロ構造
を得るためには、ポリブタジエンの５重量％スチレン溶
液の粘度が、25℃において10〜50センチポイズ（cp
s）、好ましくは20〜35cpsであり、ムーニー粘度が15〜
70、好ましくは20〜55の範囲のものが使用される。ポリ
ブタジエンの５重量％スチレン溶液の粘度が10cpsより
低いと耐衝撃強度が低下して好ましくない、また、50cp
sを超えると光沢が劣り好ましくない。The polybutadiene is produced by a known method using a catalyst containing organic lithium such as n-butyllithium and sec-butyllithium. To obtain the specified microstructure of the present invention, the viscosity of a 5 wt% solution of polybutadiene in styrene has a viscosity of 10-50 centipoise (cp) at 25 ° C.
s), preferably 20-35 cps, with a Mooney viscosity of 15-
Those in the range 70, preferably 20-55 are used. If the viscosity of a 5 wt% styrene solution of polybutadiene is lower than 10 cps, the impact strength is lowered, which is not preferable.
If it exceeds s, the gloss is inferior, which is not preferable.
芳香族モノビニル単量体とシアン化ビニル単量体の共重
合体樹脂相中に分散しているゴム状物質の重量平均粒子
径が0.2〜1.5ミクロン（μ）、好ましくは0.3〜1.0μで
あり、かつ重量平均粒子径／数平均粒子径で表わされる
粒子径分布が2.0以下であることが必要である。粒子径
0.2μより小さくなると耐衝撃強度が低く、1.5μより大
きくなると、光沢、剛性が低下し好ましくない。又、粒
子径分布が2.0より大きくなると特に射出成形品のゲー
ト部とゲート部からの距離の離れた個所との光沢の差が
大きくなり、色むら（色目が変化して見える）が出易く
外観が悪くなり好ましくない。更に本発明では、該分散
ゴム状物質の粒子中に内蔵される芳香族モノビニル単量
体とシアン化ビニル単量体との共重合体の数平均粒子径
が0.13μ以下、好ましくは0.11μ以下であり、微細で均
一なことが必要である。内蔵される芳香族モノビニル単
量体とシアン化ビニル単量体との共重合体の数平均粒子
径が0.13μを越える場合には、着色性が低下し本発明の
目的を達成できない。The weight average particle size of the rubber-like substance dispersed in the copolymer resin phase of the aromatic monovinyl monomer and the vinyl cyanide monomer is 0.2 to 1.5 μm (μ), preferably 0.3 to 1.0 μm. In addition, the particle size distribution represented by the weight average particle size / number average particle size must be 2.0 or less. Particle size
When it is less than 0.2 μ, the impact strength is low, and when it is more than 1.5 μ, the gloss and rigidity are deteriorated, which is not preferable. Also, if the particle size distribution is larger than 2.0, the difference in gloss between the gate part of the injection-molded product and the part distant from the gate part becomes large, and color unevenness (the appearance of changes in the color) is likely to occur. Is not good and is not preferable. Further, in the present invention, the number average particle size of the copolymer of the aromatic monovinyl monomer and the vinyl cyanide monomer contained in the particles of the dispersed rubber-like substance is 0.13 μm or less, preferably 0.11 μm or less. Therefore, it is necessary to be fine and uniform. When the number average particle diameter of the incorporated copolymer of aromatic monovinyl monomer and vinyl cyanide monomer exceeds 0.13 μ, the coloring property is deteriorated and the object of the present invention cannot be achieved.
又、本発明の目的を達成する上で、分散ゴム状物質粒子
の架橋化された状態も重要であり、トルエン50％、メチ
ルエチルケトン50％の混合溶倍中の膨潤指数が５〜７で
あることが好ましい。Further, in order to achieve the object of the present invention, the crosslinked state of the dispersed rubber-like substance particles is also important, and the swelling index is 5 to 7 in the mixed solution of toluene 50% and methyl ethyl ketone 50%. Is preferred.
さらに、芳香族モノビニル単量体とシアン化ビニル単量
体との共重合体の樹脂相部分の分子量も重要であり、該
樹脂相部分のメチルエチルケトン中で測定した還元比粘
度が0.6〜0.8であることが好ましい。Furthermore, the molecular weight of the resin phase portion of the copolymer of the aromatic monovinyl monomer and the vinyl cyanide monomer is also important, and the reduced specific viscosity of the resin phase portion measured in methyl ethyl ketone is 0.6 to 0.8. It is preferable.
本発明の樹脂組成物は、前記ゴム状物質を芳香族モノビ
ニル単量体及びシアン化ビニル単量体に溶解した後、ゴ
ム状物質が粒子化する重合転化率を越えない範囲まで重
合し、一方これと独立に芳香族モノビニル単量体及びシ
アン化ビニル単量体からの重合生成物を作り、この両者
を芳香族モノビニル単量体及びシアン化ビニル単量体の
重合生成物／ゴム状物質との重量比を3.0〜5.5、好まし
くは3.5〜4.5となるように混合撹拌し、強制的に粒子化
した後、更に塊状重合、溶剤塊状重合、懸濁重合のいず
れかの方法で重合を続ける。重合終了後に未重合の単量
体を除去及び加熱処理する。この加熱処理の温度、時間
等の条件を選定することにより、該分散ゴム状物質のト
ルエン，メチルエチルケトン混合溶媒中での膨潤指数を
制御することが出来る。The resin composition of the present invention is obtained by dissolving the rubber-like substance in an aromatic monovinyl monomer and a vinyl cyanide monomer, and then polymerizing the rubber-like substance into particles within a range not exceeding the polymerization conversion rate. Independently of this, a polymerization product from an aromatic monovinyl monomer and a vinyl cyanide monomer is prepared, and both are treated as a polymerization product of an aromatic monovinyl monomer and a vinyl cyanide monomer / a rubber-like substance. The mixture is mixed and stirred so that the weight ratio thereof is 3.0 to 5.5, preferably 3.5 to 4.5, and the particles are forcibly made into particles, and then the polymerization is further continued by any one of bulk polymerization, solvent bulk polymerization and suspension polymerization. After the polymerization is completed, unpolymerized monomers are removed and heat treatment is performed. The swelling index of the dispersed rubber-like substance in the mixed solvent of toluene and methyl ethyl ketone can be controlled by selecting the conditions such as temperature and time of this heat treatment.
本発明の特定のミクロ構造とする上で、前記条件下で行
う混合撹拌は、混合撹拌機壁と撹拌翼の間隔が１〜20mm
好ましくは１〜15mmである装置内で高速回転下に行うこ
とが必要である。かかる特定の条件下で初めて本発明の
ミクロ構造を得ることが可能であり、従来の如き芳香族
モノビニル単量体及びシアン化ビニル単量体をゴム状物
質存在下に重合し、ゴム状物質を粒子化させる方法、粒
子化時期を早めるために芳香族モノビニル単量体とシア
ン化ビニル単量体の共重合物を添加する方法等では得ら
れない。In the specific microstructure of the present invention, the mixing and stirring performed under the above conditions, the distance between the mixing stirrer wall and the stirring blade is 1 to 20 mm.
It is necessary to carry out under high speed rotation in a device which is preferably 1 to 15 mm. It is possible to obtain the microstructure of the present invention for the first time under such specific conditions, and a conventional aromatic monovinyl monomer and vinyl cyanide monomer are polymerized in the presence of a rubber-like substance to give a rubber-like substance. It cannot be obtained by a method of making particles, a method of adding a copolymer of an aromatic monovinyl monomer and a vinyl cyanide monomer in order to accelerate the time of making particles, and the like.
本発明では重合時に溶剤を存在させることも出来る。そ
の溶剤としては、芳香族炭化水素類、例えば、トルエ
ン、キシレン、エチルベンゼンの単独又は２種以上の混
合物がある。更にゴム状物質及び芳香族モノビニル単量
体及びシアン化ビニル単量体からの重合生成物の溶解を
損ねない範囲で、他の溶剤、例えば脂肪族炭化水素類、
ジアルキルケトン類を芳香族炭化水素類と併用すること
が出来る。In the present invention, a solvent may be present during the polymerization. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, which may be used alone or as a mixture of two or more kinds. Further, other solvents, for example, aliphatic hydrocarbons, within a range that does not impair the dissolution of the polymerization product from the rubber-like substance and aromatic monovinyl monomer and vinyl cyanide monomer,
Dialkyl ketones can be used in combination with aromatic hydrocarbons.
溶剤は０〜25重量％の範囲で使用される。25重量％を越
えると重合速度が著しく低下し、かつ得られる樹脂の耐
衝撃強度の低下が大きくなる。又、溶剤の回収エネルギ
ーが大となり経済性も劣つてくる。溶剤は比較的高粘度
となる重合転化率となつてから添加しても良く、重合前
から添加しておいても良い。ゴム状物質を粒子化する重
合転化率を越えない範囲まで重合するに当たり、重合開
始剤不存在下に100〜180℃の温度範囲で重合し得るが、
着色性を高め耐衝撃強度を向上させるために重合開始剤
が使用される。重合開始剤としてはラジカルを発生する
有機過酸化物が本発明では使用出来る。温度50〜150℃
好ましくは70〜135℃の温度範囲で、一定温度或いは漸
次昇温して前記のゴム状物質未粒子化範囲で重合する。
有機過酸化物は、着色性、耐衝撃強度の点で優れた樹脂
とする上でゴム状物質と共に存在させて重合する方が好
ましい。The solvent is used in the range of 0 to 25% by weight. If it exceeds 25% by weight, the polymerization rate will be remarkably reduced, and the impact strength of the resulting resin will be greatly reduced. In addition, the recovery energy of the solvent is large and the economy is poor. The solvent may be added after the polymerization conversion rate becomes relatively high, or may be added before the polymerization. In polymerizing to a range not exceeding the polymerization conversion rate for granulating the rubber-like substance, it can be polymerized in the temperature range of 100 to 180 ° C in the absence of a polymerization initiator,
A polymerization initiator is used to enhance the colorability and the impact strength. Organic peroxides that generate radicals can be used as the polymerization initiator in the present invention. Temperature 50-150 ℃
Preferably, it is polymerized in the temperature range of 70 to 135 [deg.] C. at a constant temperature or gradually increasing the temperature in the range where the above-mentioned rubbery substance is not made into particles.
The organic peroxide is preferably polymerized by being present together with a rubber-like substance in order to form a resin excellent in colorability and impact resistance.
重合転化率をゴム状物質が粒子化するまでの高めてしま
うと、最終の樹脂の着色性が著しく低下してしまい、本
発明の目的を達成することが出来ない。If the polymerization conversion rate is increased until the rubber-like substance is made into particles, the colorability of the final resin is significantly lowered, and the object of the present invention cannot be achieved.
独立に芳香族モノビニル単量体及びシアン化ビニル単量
体からの重合生成物を造るにあたり、芳香族モノビニル
単量体及びシアン化ビニル単量体75〜100重量％、溶剤
０〜25重量％を110〜180℃の温度範囲で重合開始剤不存
在下で重合するか前記有機過酸化物を用いて50〜180
℃、好ましくは70〜160℃、更に好ましくは80〜140℃の
温度範囲で重合する。When independently producing a polymerization product from an aromatic monovinyl monomer and a cyanide vinyl monomer, 75 to 100% by weight of the aromatic monovinyl monomer and the vinyl cyanide monomer and 0 to 25% by weight of the solvent are used. Polymerize in the absence of a polymerization initiator in the temperature range of 110 to 180 ° C or 50 to 180 using the organic peroxide.
Polymerization is carried out in the temperature range of ℃, preferably 70 to 160 ℃, more preferably 80 to 140 ℃.
本発明に使用される有機過酸化物は、1,1−ビス（ｔ−
ブチルパーオキシ）シクロヘキサン、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
等のパーオキシケタール類、ジ−ｔ−ブチルパーオキサ
イド、2,5−ジメチル−2,5−ジ（ｔ−ブチルパーオキ
シ）ヘキサン等のジアルキルパーオキサイド類、ベンゾ
イルパーオキサイド、ｍ−トルオイルパーオキサイド等
のジアシルパーオキサイド類、ジミリスチルパーオキシ
ジカーボネート等のパーオキシジカーボネート類、ｔ−
ブチルパーオキシイソプロピルカーボネート等のパーオ
キシエステル類、シクロヘキサノンパーオキサイド等の
ケトンパーオキサイド類、ｐ−メンタハイドロパーオキ
サイド等のハイドロパーオキサイド類がある。The organic peroxide used in the present invention is 1,1-bis (t-
Butyl peroxy) cyclohexane, 1,1-bis (t-
Butylperoxy) 3,3,5-trimethylcyclohexane and other peroxyketals, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and other dialkyl peroxides Diacyl peroxides such as oxides, benzoyl peroxide, m-toluoyl peroxide, peroxydicarbonates such as dimyristyl peroxydicarbonate, t-
There are peroxyesters such as butylperoxyisopropyl carbonate, ketone peroxides such as cyclohexanone peroxide, and hydroperoxides such as p-mentor hydroperoxide.
芳香族モノビニル単量体とシアン化ビニル単量体との共
重合体樹脂相部分の分子量は、重合温度、使用する有機
過酸化物の種類と量、溶剤の種類と量によつて調整され
るが、一般には連鎖移動剤によつて調整される。連鎖移
動剤としては、例えばｎ−ドデシルメルカプタン、ｔ−
ドデシルメルカプタンのようなメルカプタン類、α−メ
チルスチレンリニアダイマー、テルピノーレン等があ
る。The molecular weight of the copolymer resin phase portion of the aromatic monovinyl monomer and the vinyl cyanide monomer is adjusted according to the polymerization temperature, the type and amount of the organic peroxide used, and the type and amount of the solvent. However, it is generally adjusted by a chain transfer agent. Examples of chain transfer agents include n-dodecyl mercaptan and t-
Examples include mercaptans such as dodecyl mercaptan, α-methylstyrene linear dimer, and terpinolene.
又、酸化防止剤として、ヒンダードフエノール類、ヒン
ダードビスフエノール類、ヒンダードトリスフエノール
類等例えば2,6−ジ−ｔ−ブチル−４−メチルフエノー
ル、ステアリル−β−（3,5−ジ−ｔ−ブチル−４−ヒ
ドロキシフエニル）ピロピネオートを添加することが出
来る。As antioxidants, hindered phenols, hindered bisphenols, hindered trisphenols, etc., such as 2,6-di-t-butyl-4-methylphenol, stearyl-β- (3,5-diphenol -T-Butyl-4-hydroxyphenyl) pyropineone can be added.
更に本発明の樹脂に洗顔料、滑剤、充填剤、離型剤、可
塑剤、帯電防止剤の添加剤を必要に応じて添加すること
ができる。Further, additives such as a face wash, a lubricant, a filler, a release agent, a plasticizer and an antistatic agent can be added to the resin of the present invention as required.
又、本発明の樹脂と、ビーズ、ペレツト状の他のABS樹
脂、ポリカーボネート樹脂、塩化ビニル樹脂等とを混合
あるいは溶融混練した樹脂組成物として用いることもで
きる。Further, it can be used as a resin composition obtained by mixing or melt-kneading the resin of the present invention with beads, other ABS resin in pellet form, polycarbonate resin, vinyl chloride resin and the like.
本発明で特定されたゴム粒子径と，ゴム状物質中に内蔵
された芳香族モノビニル単量体とシアン化ビニル単量体
との共重合体の微細さのミクロ構造を共に有するゴム変
性熱可塑性樹脂組成物は、着色性に優れ、良好な光沢、
剛性と耐衝撃強度とのバランス等の総合的品質に優れて
いる。A rubber-modified thermoplastic having both a rubber particle size specified in the present invention and a fine microstructure of a copolymer of an aromatic monovinyl monomer and a vinyl cyanide monomer embedded in a rubber-like substance. The resin composition has excellent coloring properties and good gloss,
Excellent overall quality such as balance between rigidity and impact strength.
本発明の樹脂組成物は、弱電機器、雑貨等の分野におい
て成形品として有用である。着色性が良好であること
は、着色時に使用する染顔料コストが大巾に安くなり特
に鮮やかな色調が要求される成形品において好ましい結
果を得ることができる。INDUSTRIAL APPLICABILITY The resin composition of the present invention is useful as a molded article in the fields of light electric appliances, sundries and the like. Good colorability makes it possible to obtain a favorable result in a molded article which requires a particularly vivid color tone because the cost of dyeing and pigment used for coloring is significantly reduced.
このように、連続塊状重合法または塊状−懸濁二段重合
法により得られるものでありながら、優れた特性を有す
るゴム変性熱可塑性樹脂諸生物は工業的に非常に大きな
意味を持つのである。As described above, the rubber-modified thermoplastic resin organisms having excellent properties, which are obtained by the continuous bulk polymerization method or the bulk-suspension two-step polymerization method, have a very great industrial significance.
次に、本発明において用いた分析法と試験法について説
明する。Next, the analysis method and test method used in the present invention will be described.
ゴム状物質のミクロ構造：モレロ法（D.Moreroet al.:C
him.e Ind.,41 758（1959）により赤外分光光度計を使
用して、シス−1,4、トランス1,4、1,2−ビニルの含有
率を求めた。Microstructure of rubbery material: Morero method (D. Morero et al .: C
The content of cis-1,4, trans 1,4,1,2-vinyl was determined using an infrared spectrophotometer according to him.e Ind., 41 758 (1959).
ゴム状物質の溶液粘度：ポリブタジエン2gをスチレン38
gに溶解して５重量％の溶液を用意し、キヤノン−フエ
ンスケ粘度計100番を用いて25℃にて測定する。Solution viscosity of rubber-like substance: Polybutadiene 2g styrene 38
Dissolve in g to prepare a 5% by weight solution, and measure at 25 ° C. using a Canon-Fenske viscometer No. 100.
樹脂中のゴム状物質の粒子径及び粒子径分布：ビーズ又
はペレツトを四酸化オスミウム染色し、超薄切片を作成
し電子顕微鏡写真をとる。写真中に拡大されたゴム状物
質粒子の200〜500個の粒子径を測定し、重量平均粒子径
を求める。楕円形をしている場合は、長径ａと短径ｂと
の平均即ち（ａ＋ｂ）/2をもつて粒子径とする。Particle size and particle size distribution of rubber-like substance in resin: Beads or pellets are stained with osmium tetroxide, ultrathin sections are prepared and electron micrographs are taken. The particle size of 200 to 500 particles of the rubber-like substance expanded in the photograph is measured, and the weight average particle size is obtained. In the case of an elliptical shape, the average of the major axis a and the minor axis b, that is, (a + b) / 2, is used as the particle size.
粒子径分布は、重量平均粒子径を求めたのと同様にして
数平均粒子径を求め、重量平均粒子径／数平均粒子径で
粒子粒分布を計算する。For the particle size distribution, the number average particle size is calculated in the same manner as the weight average particle size is calculated, and the particle size distribution is calculated by weight average particle size / number average particle size.
内蔵された芳香族モノビニル単量体とシアン化ビニル単
量体との共重合体（ネクルージヨン）の粒子径：ビース
又はペレツトを四酸化オスミウム染色し、超薄切片を作
成し電子顕微鏡写真をとる。写真中に拡大された分散ゴ
ム状物質の粒子内に内蔵された芳香族モノビニル単量体
とシアン化ビニル単量体との共重合体の粒子径を0.01μ
まで測定し、数平均粒子径として表す。楕円形をしてい
る場合は、長径ａと短径ｂとの平均即ち（ａ＋ｂ）/2を
もつて粒子径とする。Particle size of the incorporated copolymer of aromatic monovinyl monomer and vinyl cyanide monomer (Necurgeon): Bees or pellets are stained with osmium tetroxide, ultrathin sections are prepared and electron micrographs are taken. The particle size of the copolymer of aromatic monovinyl monomer and vinyl cyanide monomer embedded in the dispersed rubber-like substance particles enlarged in the photograph is 0.01μ.
Measured up to and expressed as a number average particle size. In the case of an elliptical shape, the average of the major axis a and the minor axis b, that is, (a + b) / 2, is used as the particle size.
ゲル含有量及び膨潤指数:1gの樹脂に10mlのトルエン及
び10mlのメチルエチルケトンを加えて１時間激しく震盪
し、溶解或いは膨潤させる。次に遠心分離機にてゲルを
沈降させた後、デカンテーシヨンで上澄液を捨て、沈降
したゲルを秤量する。このようにして得られたトルエン
／メチルエチルケトン膨潤ゲルを160℃、常圧で45分間
続いて３〜5mmHgの減圧下で15分間乾燥させ、デシケー
タ中で冷却後秤量する。ゲル含有量は、乾燥ゲルの重量
を樹脂重量で除して重量％で示す。膨潤指数はトルエン
／メチルエチルケトン膨潤ゲルの重量を乾燥ゲル重量で
除した商の数値で示す。Gel content and swelling index: Add 1 ml of resin to 10 ml of toluene and 10 ml of methyl ethyl ketone and shake vigorously for 1 hour to dissolve or swell. Next, the gel is settled by a centrifuge, the supernatant is discarded by decantation, and the settled gel is weighed. The toluene / methylethylketone swollen gel thus obtained is dried at 160 ° C. for 45 minutes under normal pressure, then under reduced pressure of 3-5 mmHg for 15 minutes, cooled in a desiccator, and then weighed. The gel content is given in wt% by dividing the weight of dry gel by the weight of resin. The swelling index is represented by the quotient of the weight of the toluene / methyl ethyl ketone swelling gel divided by the weight of the dry gel.
共重合体樹脂相部分の還元比粘度：樹脂1gにアセトンを
20ml加え１時間激しくしんとうし、溶解あるいは膨潤さ
せる。次に遠心分離機にてゲルを沈降させた後、デカン
テーシヨンで上澄液をメタノール200ml中に入れ、共重
合体樹脂相部分を析出させる。析出した樹脂相部分をと
り出し、160℃にて常圧で15分、減圧で15分乾燥させ
る。乾燥した樹脂相部分は0.1g静秤しメチルエチルケト
ン20mlに溶解し、キヤノン−フエンスケ型粘度計100番
で30℃で還元比粘度（単位:dl/g）を測定する。Reduced specific viscosity of copolymer resin phase part: Acetone to 1 g of resin
Add 20 ml and stir vigorously for 1 hour to dissolve or swell. Next, after the gel is settled by a centrifuge, the supernatant is put into 200 ml of methanol by decantation to precipitate a copolymer resin phase portion. The precipitated resin phase portion is taken out and dried at 160 ° C. under normal pressure for 15 minutes and under reduced pressure for 15 minutes. The dried resin phase portion is statically weighed at 0.1 g, dissolved in 20 ml of methyl ethyl ketone, and the reduced specific viscosity (unit: dl / g) is measured with a Canon-Fenske viscometer No. 100 at 30 ° C.
メルトフローレート:JIS K72.0（220℃、10kg）によつ
た。Melt flow rate: Measured according to JIS K72.0 (220 ° C, 10 kg).
以下の各試験では、ペレツトを射出成形し試験片を作成
して測定に供した。In each of the following tests, a pellet was injection-molded to prepare a test piece, and the test piece was subjected to the measurement.
ビカツト軟化点:ASTM D1525によった。Bicatus softening point: According to ASTM D1525.
アイゾツド衝撃強度:ASTM D256によつた。Izod impact strength: According to ASTM D256.
引張強度:ASTM D638によつた。Tensile strength: According to ASTM D638.
曲げ強度及び曲げ弾性率:ASTM D790によつた。Flexural strength and flexural modulus: According to ASTM D790.
光沢:ASTM D638のダンベル試験片をシリンダー温度240
℃、金型温度45℃、射出圧力はシヨートシヨツトの圧力
＋5kg/cm2にて射出成形し、試験片のゲート端から40mm
の位置の中央部及び反ゲート端から40mmの位置の中央部
の光沢度（入射角60゜）をグロスメーターで測定する。
３本の試験片について測定してそれぞれの平均値を求
め、さらにゲート部の平均値と反ゲート部の平均値を加
えて２で割り、光沢の測定値とする。Gloss: ASTM D638 dumbbell specimen with cylinder temperature 240
℃, mold temperature 45 ℃, injection pressure injection molding at the pressure of the short shot + 5kg / cm 2 , 40mm from the gate end of the test piece
Measure the glossiness (incident angle 60 °) at the center of the position and at the position 40 mm from the opposite gate end with a gloss meter.
The three test pieces are measured and the respective average values are obtained, and the average value of the gate portion and the average value of the anti-gate portion are added and divided by 2 to obtain a gloss measurement value.
着色性：樹脂100重量部に黒系の染顔料計0.02重量部の
一定量を添加して、黒着色品として、成形片（縦89mm、
横50mm、厚み2.5mm）をつくり色調を比較してランク付
けする。一定量の染顔料添加で評価し、ランク１より５
まで相対比較する。数値が大きいほど着色性に優れてい
ることを示す。Colorability: A fixed amount of 0.02 parts by weight of black dye / pigment was added to 100 parts by weight of resin to give a black colored product.
Create a width of 50 mm and a thickness of 2.5 mm) and compare the colors to rank. Evaluated by adding a certain amount of dyes and pigments, and rank 1 to 5
Compare relative to. The larger the value, the more excellent the coloring property.
以下に実施例を示す。 Examples will be shown below.
実施例１ 第１の流として２／時間の供給速度にて次の混合物
（ａ）を2.4の第１重合機に連続的に送入する。Example 1 The following mixture (a) is continuously fed as a first stream at a feed rate of 2 / h into the first polymerizer at 2.4.
混合物（ａ） ポリブタジエンゴム 11.6重量％ スチレン 53.43重量％ アクリロニトリル 17.8 重量％ エチルベンゼン 15.0 重量％ 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 0.03重量％ ステアリル−β−（3,5−ジ−ｔ−ブチル−４−ヒドロ
キシフエニル）プロピオネート 0.34重量％ α−メチルスチレンリニアダイマー 0.15重量％ ミネラルオイル 1.65重量％ 第１重合機は温度108℃であり、出口の固体物質濃度は2
3重量％であつた。差顕微鏡観察では白いゴムの連続相
に黒いスチレン−アクリロニトリル共重合体の粒子が見
られ、未だゴム相は粒子化していなかつた。Mixture (a) Polybutadiene rubber 11.6% by weight Styrene 53.43 wt% Acrylonitrile 17.8 wt% Ethylbenzene 15.0 wt% 1,1-Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 0.03 wt% Stearyl-β- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate 0.34% by weight α-methylstyrene linear dimer 0.15% by weight mineral oil 1.65% by weight The temperature of the first polymerization machine is 108 ° C, and the solid substance concentration at the outlet is 2
It was 3% by weight. Under a differential microscope, black styrene-acrylonitrile copolymer particles were found in the white rubber continuous phase, and the rubber phase was not yet formed into particles.
第２の流として１／時間の供給速度にて次の混合物
（ｂ）を6.2の第２重合機に連続的に送入する。The following mixture (b) is continuously fed into the second polymerizer at 6.2 as a second stream at a feed rate of 1 / h.
混合物（ｂ） スチレン 59.85重量％ アクリロニトリル 20.0 重量％ エチルベンゼン 20.0 重量％ α−メチルスチレンリニアダイマー 0.15重量％ 第２重合機は温度118〜128℃であり、出口の固体物質濃
度は52重量％であつた。Mixture (b) Styrene 59.85% by weight Acrylonitrile 20.0% by weight Ethylbenzene 20.0% by weight α-Methylstyrene linear dimer 0.15% by weight The temperature of the second polymerization machine was 118 to 128 ° C, and the solid substance concentration at the outlet was 52% by weight. .
これらの第１の流と第２の流は0.5の容量を持ち、撹
拌翼先端と混合機壁との間隙が5mmであり、軸方向に15
段の撹拌棒が装着し機壁にはピンが撹拌棒間に出ている
混合撹拌機内に導入され、200rpmの回転で混合される。The first flow and the second flow have a volume of 0.5, the gap between the tip of the stirring blade and the mixer wall is 5 mm, and the axial direction is 15 mm.
A stir bar is attached to the stage, and pins are introduced into the stirrer on the wall of the machine. The pin is introduced into the stirrer and mixed at 200 rpm.
更に6.2の第３重合機に送入され、温度108〜118℃で
重合され、ペレツト中のゴム状物質の平均粒子径が0.87
μとなるように撹拌された。出口の固体物質は55重量％
であつた。このものは更に6.2の第４重合機に送入さ
れ、温度135〜160℃で重合された。出口の固体物質濃度
は70重量％であつた。Further, it was fed into a third polymerization machine of 6.2 and polymerized at a temperature of 108 to 118 ° C., and the average particle size of the rubber-like substance in the pellet was 0.87.
The mixture was stirred so as to have μ. 55% by weight of solid matter at the outlet
It was. This product was further fed to a fourth polymerization machine of 6.2 and polymerized at a temperature of 135 to 160 ° C. The solid substance concentration at the outlet was 70% by weight.
得られた重合物を２ベント付押出機に供給して250℃、
−735mmHgの減圧下に揮発性成分を除去し、ダイスから
溶融ストランドを引出し水冷し、カツターにて切断し、
シリンダー状のペレツトを連続的に得た。得られたペレ
ツトの諸物性を測定し、その結果を表１に示す。The obtained polymer was fed to an extruder with 2 vents,
Remove the volatile components under reduced pressure of -735mmHg, pull out the molten strand from the die, cool with water, cut with a cutter,
Cylindrical pellets were continuously obtained. Various physical properties of the obtained pellets were measured, and the results are shown in Table 1.
実施例２ 第１の流として1.8／時間の供給速度にて次の混合物
（ａ）を2.4の第１重合機に連続的に送入する。Example 2 The following mixture (a) is continuously fed as a first stream into the first polymerizer at 2.4 at a feed rate of 1.8 / hour.
混合物（ａ） ポリブタジエン（実施例１と同じ） 7.9 重量％ スチレン 58.25重量％ アクリロニトリル 19.4 重量％ エチルベンゼン 14.0 重量％ 1,1−ビス（ｔ−ブチルパーオキシ）シクロヘキサン 0.03重量％ ステアリル−β−（3,5−ジ−ｔ−ブチル−４−ヒドロ
キシフエニル）プロピオネート 0.32重量％ α−メチルスチレンリニアダイマー 0.10重量％ 第１重合機は温度102℃であり、出口の固体物質濃度は1
5重量％であつた。位相差顕微鏡観察では白いゴムの連
続相に黒いスチレン−アクリロニトリル共重合体の粒子
が見られ、未だゴム相は粒子化していなかつた。Mixture (a) Polybutadiene (same as in Example 1) 7.9 wt% styrene 58.25 wt% acrylonitrile 19.4 wt% ethylbenzene 14.0 wt% 1,1-bis (t-butylperoxy) cyclohexane 0.03 wt% stearyl-β- (3,3 5-di-t-butyl-4-hydroxyphenyl) propionate 0.32% by weight α-methylstyrene linear dimer 0.10% by weight The temperature of the first polymerization machine is 102 ° C, and the solid substance concentration at the outlet is 1
It was 5% by weight. Observation with a phase-contrast microscope showed particles of black styrene-acrylonitrile copolymer in the continuous phase of white rubber, and the rubber phase was not yet formed into particles.
第２の流として0.9／時間の供給速度にて次の混合物
（ｂ）を6.2の第２重合機に連続的に送入する。The following mixture (b) is continuously fed into a second polymerizer of 6.2 at a feed rate of 0.9 / hour as a second stream.
混合物（ｂ） スチレン 57.8重量％ アクリロニトリル 19.2重量％ エチルベンゼン 18.0重量％ α−メチルスチレンリニアダイマー 0.2重量％ ミネラルオイル 4.8重量％ 第２重合機は温度115〜125℃であり、出口の固体物質濃
度は49重量％であつた。Mixture (b) Styrene 57.8% by weight Acrylonitrile 19.2% by weight Ethylbenzene 18.0% by weight α-Methylstyrene linear dimer 0.2% by weight Mineral oil 4.8% by weight The second polymerizer has a temperature of 115-125 ° C and a solid substance concentration of 49 at the outlet. % By weight.
これらの第１の流と第２の流は0.5の容量を持ち、撹
拌翼先端と混合機質との間隙が2.5mmであり、軸方向に
６段の撹拌棒が装着し機壁には伝熱管が撹拌棒間に出て
いる混合撹拌機内に導入され、150rpmの回転で混合され
る。The first flow and the second flow have a volume of 0.5, the gap between the tip of the agitating blade and the mixing material is 2.5 mm, and six agitating rods are attached in the axial direction to the machine wall. A hot tube is introduced into the mixing stirrer between the stirring rods and mixed at a rotation of 150 rpm.
更に、6.2の第３重合機に送入され、温度105〜120℃
で重合され、ペレツト中のゴム状物質の平均粒子径が0.
41μとなるように撹拌された。出口の固体物質は54重量
％であつた。このものに更に6.2の第４重合機に送入
され、温度140〜155℃で重合された。出口の固体物質濃
度は70重量％であつた。Furthermore, it was fed into the third polymerization machine of 6.2 and the temperature was 105-120 ℃.
The average particle diameter of the rubber-like substance in the pellets is 0.
The mixture was agitated to 41 μm. The solid material at the outlet was 54% by weight. This product was further fed into a fourth polymerization machine of 6.2 and polymerized at a temperature of 140 to 155 ° C. The solid substance concentration at the outlet was 70% by weight.
得られた重合物を２ベント付押出機に供給して250℃、
−735mmHgの減圧下に揮発性成分を除去し、ダイスから
溶融ストランドを引出し水冷し、カツターにて切断し、
シリンダー状のペレツトを連続的に得た。得られたペレ
ツトの諸特性を測定し、結果を表１に示す。The obtained polymer was fed to an extruder with 2 vents,
Remove the volatile components under reduced pressure of -735mmHg, pull out the molten strand from the die, cool with water, cut with a cutter,
Cylindrical pellets were continuously obtained. Various properties of the obtained pellet were measured, and the results are shown in Table 1.
実施例３ 第１の流として２／時間の供給速度にて次の混合物
（ａ）を2.4の第１混合機に連続的に送入する。Example 3 The following mixture (a) is continuously fed as a first stream at a feed rate of 2 / h into a first mixer of 2.4.
混合物（ａ） ポリブタジエン（実施例１と同じ） 11.6 重量％ スチレン 60.515重量％ アクリロニトリル 10.7 重量％ エチルベンゼン 15.0 重量％ 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 0.045重量％ ステアリル−β−（3,5−ジ−ｔ−ブチル−４−ヒドロ
キシフエニル）プロピオネート 0.34 重量％ α−メチルスチレンリニアダイマー 0.15 重量％ ミネラルオイル 1.65 重量％ 第１重合機は温度110℃であり、出口の固体物質濃度は2
4重量％であつた。位相差顕微鏡観察では白いゴムの連
続相に黒いスチレン−アクリロニトリル共重合体の粒子
が見られ、未だゴム相は粒子化していないかつた。Mixture (a) Polybutadiene (same as Example 1) 11.6 wt% Styrene 60.515 wt% Acrylonitrile 10.7 wt% Ethylbenzene 15.0 wt% 1,1-Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 0.045 wt% Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.34% by weight α-methylstyrene linear dimer 0.15% by weight mineral oil 1.65% by weight The first polymerizer has a temperature of 110 ° C. The solid substance concentration at the outlet is 2
It was 4% by weight. Observation with a phase-contrast microscope showed particles of black styrene-acrylonitrile copolymer in the continuous phase of white rubber, and the rubber phase was not yet formed into particles.
第２の流として１／時間の供給速度にて次の混合物
（ｂ）を6.2の第２重合機に連続的に送入する。The following mixture (b) is continuously fed into the second polymerizer at 6.2 as a second stream at a feed rate of 1 / h.
混合物（ｂ） スチレン 67.8重量％ アクリロニトリル 12.0重量％ エチルベンゼン 20.0重量％ α−メチルスチレンリニアダイマー 0.2重量％ 第２重合機は温度124〜132℃であり、出口の固体物質濃
度は50重量％であつた。Mixture (b) Styrene 67.8% by weight Acrylonitrile 12.0% by weight Ethylbenzene 20.0% by weight α-Methylstyrene linear dimer 0.2% by weight The temperature of the second polymerization machine was 124 to 132 ° C, and the solid substance concentration at the outlet was 50% by weight. .
これらの第１の流と第２の流は0.5の容量を持ち、撹
拌翼先端と混合機質との間隙が5mmであり、軸方向に15
段の撹拌棒が装着し、機壁にはピンが撹拌棒間に出てい
る混合撹拌機内に導入され、250rpmの回転で混合され
る。The first flow and the second flow have a volume of 0.5, the gap between the stirring blade tip and the mixing material is 5 mm, and the axial direction is 15 mm.
A stir bar is attached to the stage, and a pin is introduced into the mixing stirrer between the stirrers on the machine wall, and mixing is performed at a rotation of 250 rpm.
更に6.2の第３重合機に送入され、温度118〜128℃で
重合され、ペレツト中のゴム状物質の平均粒子径が0.55
μとなるように撹拌された。出口の固体物質は53重量％
であつた。このものは更に6.2の第４重合機に送入さ
れ、温度145〜165℃で重合された。出口の固体物質濃度
は69重量％であつた。Further, it was fed into the third polymerization machine of 6.2 and polymerized at a temperature of 118 to 128 ° C, and the average particle size of the rubber-like substance in the pellet was 0.55.
The mixture was stirred so as to have μ. 53% by weight of solid matter at the outlet
It was. This product was further fed to a fourth polymerization machine of 6.2 and polymerized at a temperature of 145-165 ° C. The solid substance concentration at the outlet was 69% by weight.
得られた重合物を２ベント付押出機に供給して250℃、
−735mmHgの減圧下に揮発性成分を除去し、ダイスから
溶融ストランドを引出し水冷し、カツターにて切断し、
シリンダー状のペレツトを連続的に得た。得られたペレ
ツトの諸特性を測定し、結果を表１に示す。The obtained polymer was fed to an extruder with 2 vents,
Remove the volatile components under reduced pressure of -735mmHg, pull out the molten strand from the die, cool with water, cut with a cutter,
Cylindrical pellets were continuously obtained. Various properties of the obtained pellet were measured, and the results are shown in Table 1.
実施例４ 第１の流として1.8／時間の供給速度にて次の混合物
（ａ）を2.4の第１混合機に連続的に送入する。Example 4 The following mixture (a) is continuously fed into the first mixer of 2.4 as a first stream at a feed rate of 1.8 / hour.
混合物（ａ） ポリブタジエン（実施例１と同じ） 11.3 重量％ スチレン 54.9 重量％ アクリロニトリル 18.3 重量％ エチルベンゼン 15.0 重量％ 1,1−ビス（ｔ−ブチルパーオキシ）シクロヘキサン 0.03重量％ ステアリル−β−（3,5−ジ−ｔ−ブチル−４−ヒドロ
キシフエニル）プロピオネート 0.32重量％ α−メチルスチレンリニアダイマー 0.15重量％ 第１重合機は温度105℃であり、出口の固体物質濃度は2
5重量％であつた。位相差顕微鏡観察では白いゴムの連
続相に黒いスチレン−アクリロニトリル共重合体の粒子
が見られ、未だゴム相は粒子化していないかつた。Mixture (a) Polybutadiene (same as Example 1) 11.3 wt% Styrene 54.9 wt% Acrylonitrile 18.3 wt% Ethylbenzene 15.0 wt% 1,1-Bis (t-butylperoxy) cyclohexane 0.03 wt% Stearyl-β- (3,3 5-di-t-butyl-4-hydroxyphenyl) propionate 0.32% by weight α-methylstyrene linear dimer 0.15% by weight The temperature of the first polymerization machine was 105 ° C, and the solid substance concentration at the outlet was 2
It was 5% by weight. Observation with a phase-contrast microscope showed particles of black styrene-acrylonitrile copolymer in the continuous phase of white rubber, and the rubber phase was not yet formed into particles.
第２の流として0.9／時間の供給速度にて次の混合物
（ｂ）を6.2の第２重合機に連続的に送入する。The following mixture (b) is continuously fed into a second polymerizer of 6.2 at a feed rate of 0.9 / hour as a second stream.
混合物（ｂ） スチレン 54.7重量％ アクリロニトリル 17.5重量％ エチルベンゼン 18.0重量％ α−メチルスチレンリニアダイマー 0.2重量％ ミネラルオイル 4.8重量％ アジピン酸とブタンジオールとのポリエステル（アデカ
サイザーPN400） 4.8重量％ 第２重合機は温度104〜113℃であり、出口の固体物質濃
度は52重量％であつた。Mixture (b) Styrene 54.7% by weight Acrylonitrile 17.5% by weight Ethylbenzene 18.0% by weight α-Methylstyrene linear dimer 0.2% by weight Mineral oil 4.8% by weight Polyester of adipic acid and butanediol (Adekaizer PN400) 4.8% by weight Second polymerization machine Was at a temperature of 104 to 113 ° C, and the solid substance concentration at the outlet was 52% by weight.
これらの第１の流と第２の流は0.5の容量を持ち、撹
拌翼先端と混合機壁との間隙が2.5mmであり、軸方向に
６段の撹拌棒が装着し機壁には伝熱管が撹拌棒間に出て
いる混合撹拌機内に導入され、120rpmの回転で混合され
る。The first flow and the second flow have a capacity of 0.5, the gap between the tip of the stirring blade and the wall of the mixer is 2.5 mm, and a 6-stage stirring rod is installed in the axial direction to transmit to the wall of the machine. A hot tube is introduced into the mixing stirrer between the stirring rods and mixed at 120 rpm.
更に6.2の第３重合機に送入され、温度104〜113℃で
重合され、ペレツト中のゴム状物質の平均粒子径が0.92
μとなるように撹拌された。出口の固体物質は52重量％
であつた。このものは更に6.2の第４重合機に送入さ
れ、温度140〜155℃で重合された。出口の固体物質濃度
は69重量％であつた。Further, it was fed into a third polymerization machine of 6.2 and polymerized at a temperature of 104 to 113 ° C., and the average particle size of the rubber-like substance in the pellet was 0.92.
The mixture was stirred so as to have μ. 52% by weight of solid matter at the outlet
It was. This product was further fed into a fourth polymerization machine of 6.2 and polymerized at a temperature of 140 to 155 ° C. The solid substance concentration at the outlet was 69% by weight.
得られた重合物を２ベント付押出機に供給して250℃、
−735mmHgの減圧下に揮発性成分を除去し、ダイスから
溶融ストランドを引出し水冷し、カツターにて切断し、
シリンダー状のペレツトを連続的に得た。得られたペレ
ツトの諸特性を測定し、結果を表１に示す。The obtained polymer was fed to an extruder with 2 vents,
Remove the volatile components under reduced pressure of -735mmHg, pull out the molten strand from the die, cool with water, cut with a cutter,
Cylindrical pellets were continuously obtained. Various properties of the obtained pellet were measured, and the results are shown in Table 1.
比較例１ 混合物（ａ）に含まれるポリブタジンエンゴムを、 にした以外は実施例１と同様に行つた。得られたペレツ
トの諸物性を測定し、その結果を表１に示す。Comparative Example 1 Polybutadiene rubber contained in the mixture (a) Example 1 was repeated except that Various physical properties of the obtained pellets were measured, and the results are shown in Table 1.
比較例２ 次の混合物を2.4／時間の供給速度にて6.2の第１重
合機（実施例１の第３重合機と同一の装置）に連続的に
送入する。Comparative Example 2 The following mixture is continuously fed at a feed rate of 2.4 / hour into the first polymerizer of 6.2 (same equipment as the third polymerizer of Example 1).
ポリブタジエンゴム（実施例１と同じ） 7.35重量％ スチレン 56.78重量％ アクリロニトリル 18.9 重量％ エチルベンゼン 15.0 重量％ 1,1−ビス（ｔ−ブチルパーオキシ）ヘキサン 0.03重量
％ ステアリル−β−（3,5−ジ−ｔ−ブチル−４−ヒドロ
キシフエニル）プロピオネート 0.21重量％ α−メチルスチレンリニアダイマー 0.15重量％ ミネラルオイル 1.58重量％ 第１重合機は温度103〜107℃であり、ペレツト中のゴム
状物質の平均粒子径が1.21μとなるように撹拌された。
出口の固体物質濃度は33重量％であつた。位相差顕微鏡
観察では黒いスチレン−アクリロニトリル共重合体の連
続相に白いゴムの粒子が分散相として存在しているのが
確認された。続いて6.2の第２重合機（実施例１の第
２重合機と同一の装置）で温度115〜125℃で重合し、更
に6.2の第３重合機（実施例１の第４重合機と同一の
装置）で温度140〜160℃で重合した。出口の固体物質の
濃度は75重量％であつた。次いで重合物を２ベント付押
出機に供給して250℃、−735mmHgの減圧下に揮発性成分
を除去し、ダイスから溶融ストランドを引出し水冷し、
カツターにて切断し、シリンダー状のペレツトを連続的
に得た。このペレツトの測定結果を表１に示す。Polybutadiene rubber (same as in Example 1) 7.35 wt% Styrene 56.78 wt% Acrylonitrile 18.9 wt% Ethylbenzene 15.0 wt% 1,1-Bis (t-butylperoxy) hexane 0.03 wt% Stearyl-β- (3,5-di) -T-Butyl-4-hydroxyphenyl) propionate 0.21% by weight α-methylstyrene linear dimer 0.15% by weight Mineral oil 1.58% by weight The first polymerizer has a temperature of 103 to 107 ° C, and the average of the rubber-like substance in the pellet. The mixture was stirred so that the particle size was 1.21μ.
The solid substance concentration at the outlet was 33% by weight. Observation with a phase-contrast microscope confirmed that white rubber particles were present as a dispersed phase in the continuous phase of the black styrene-acrylonitrile copolymer. Subsequently, polymerization was carried out at a temperature of 115 to 125 ° C. in a second polymerization machine of 6.2 (the same apparatus as the second polymerization machine of Example 1), and further, a third polymerization machine of 6.2 (same as the fourth polymerization machine of Example 1). The apparatus was used for the polymerization at a temperature of 140 to 160 ° C. The concentration of solid matter at the outlet was 75% by weight. Then, the polymer was fed to an extruder with 2 vents to remove volatile components under reduced pressure of 250 ° C. and −735 mmHg, and the molten strand was drawn out from the die and water-cooled,
It was cut with a cutter to continuously obtain cylindrical pellets. The measurement results of this pellet are shown in Table 1.
比較例３ 得られた重合物を２ベント付押出機に供給して220℃、
−735mmHgの減圧下に揮発性成分を除去した他は、実施
例１と同様に行つた。得られたペレツトの諸特性を測定
し、その結果を表１に示す。Comparative Example 3 The polymer obtained was fed to an extruder with 2 vents and heated at 220 ° C.
Example 1 was repeated except that the volatile components were removed under a reduced pressure of -735 mmHg. Various properties of the obtained pellet were measured, and the results are shown in Table 1.
比較例４ 第１の流として２／時間の供給速度にて次の混合物
（ａ）を2.4の第１重合機に連続的に送入する。Comparative Example 4 The following mixture (a) is continuously fed as a first stream at a feed rate of 2 / h into the first polymerizer at 2.4.
混合物（ａ） ポリブタジエン（実施例１と同じ） 11.6 重量％ スチレン 54.93重量％ アクリロニトリル 17.8 重量％ エチルベンゼン 15.0 重量％ 1,1−ビス（ｔ−ブチルパーオキシ）シクロヘキサン 0.03重量％ ステアリル−β−（3,5−ジ−ｔ−ブチル−４−ヒドロ
キシフエニル）プロピオネート 0.34重量％ α−メチルスチレンリニアダイマー 0.3 重量％ 第１重合機は温度105℃であり、出口の固体物質濃度は1
8重量％であつた。位相差顕微鏡観察では白いゴムの連
続相に黒いスチレン−アクリロニトリル共重合体の粒子
が見られ、未だゴム相は粒子化していないかつた。Mixture (a) Polybutadiene (same as Example 1) 11.6 wt% Styrene 54.93 wt% Acrylonitrile 17.8 wt% Ethylbenzene 15.0 wt% 1,1-Bis (t-butylperoxy) cyclohexane 0.03 wt% Stearyl-β- (3,3 5-di-t-butyl-4-hydroxyphenyl) propionate 0.34% by weight α-methylstyrene linear dimer 0.3% by weight The temperature of the first polymerization machine was 105 ° C, and the solid substance concentration at the outlet was 1
It was 8% by weight. Observation with a phase-contrast microscope showed particles of black styrene-acrylonitrile copolymer in the continuous phase of white rubber, and the rubber phase was not yet formed into particles.
第２の流として１／時間の供給速度にて次の混合物
（ｂ）を6.2の第２重合機に連続的に送入する。The following mixture (b) is continuously fed into the second polymerizer at 6.2 as a second stream at a feed rate of 1 / h.
混合物（ｂ） スチレン 58.1重量％ アクリロニトリル 18.5重量％ エチルベンゼン 20.0重量％ ミネラルオイル 3.1重量％ α−メチルスチレンリニアダイマー 0.3重量％ 第２重合機は温度118〜128℃であり、出口の固体物質濃
度は51重量％であつた。Mixture (b) Styrene 58.1% by weight Acrylonitrile 18.5% by weight Ethylbenzene 20.0% by weight Mineral oil 3.1% by weight α-Methylstyrene linear dimer 0.3% by weight The temperature of the second polymerization machine is 118 to 128 ° C and the solid substance concentration at the outlet is 51%. % By weight.
これらの第１の流と第２の流は0.5の容量を持ち、撹
拌翼先端と混合機壁との間隙が2.5mmであり、軸方向に
６段の撹拌棒が装着し機壁には伝熱管が撹拌棒間に出て
いる混合撹拌機内に導入され、150rpmの回転で混合され
る。The first flow and the second flow have a capacity of 0.5, the gap between the tip of the stirring blade and the wall of the mixer is 2.5 mm, and a 6-stage stirring rod is installed in the axial direction to transmit to the wall of the machine. A hot tube is introduced into the mixing stirrer between the stirring rods and mixed at a rotation of 150 rpm.
更に6.2の第３重合機に送入され、温度108〜118℃で
重合され、ペレツト中のゴム状物質の平均粒子径が0.98
μとなるように撹拌された。出口の固体物質は54重量％
であつた。このものは更に6.2の第４重合機に送入さ
れ、温度140〜160℃で重合された。出口の固体物質濃度
は72重量％であつた。Further, it was fed into a third polymerization machine of 6.2 and polymerized at a temperature of 108 to 118 ° C., and the average particle size of the rubber-like substance in the pellet was 0.98.
The mixture was stirred so as to have μ. 54% by weight of solid matter at the outlet
It was. This product was further fed into a fourth polymerization machine of 6.2 and polymerized at a temperature of 140 to 160 ° C. The solid substance concentration at the outlet was 72% by weight.
得られた重合物を２ベント付押出機に供給して250℃、
−735mmHgの減圧下に揮発性成分を除去し、ダイスから
溶融ストランドを引出し水冷し、カツターにて切断し、
シリンダー状のペレツトを連続的に得た。得られたペレ
ツトの諸特性を測定し、結果を表１に示す。The obtained polymer was fed to an extruder with 2 vents,
Remove the volatile components under reduced pressure of -735mmHg, pull out the molten strand from the die, cool with water, cut with a cutter,
Cylindrical pellets were continuously obtained. Various properties of the obtained pellet were measured, and the results are shown in Table 1.
Claims (2)
量体及びシアン化ビニル単量体を、連続塊状重合法また
は塊状−懸濁二段重合法により重合して得られるゴム変
性熱可塑性樹脂組成物において、 （ａ）共重合体樹脂相中の成分の割合が、芳香族モノビ
ニル単量体65〜95重量％、シアン化ビニル単量体５〜35
重量％であり、 （ｂ）ゴム状物質が共重合体樹脂相100重量部に対し２
〜20重量部含まれ、1,2ビニル結合を10〜25％、トラン
ス1,4結合を35〜65％、シス1,4結合を25〜40％含有する
ポリブタジエンであつて、スチレン中５重量％の溶液粘
度が10〜50センチポイズであり、 （ｃ）該ゴム状物質が樹脂組成物中において重量平均粒
子径0.2〜1.5ミクロンの粒子として分散しており、重量
平均粒子径と数平均粒子径の比が2.0以下であり、 （ｄ）該ゴム状物質粒子中に内蔵される芳香族モノビニ
ル単量体とシアン化ビニル単量体との共重合体の数平均
粒子径が0.13ミクロン以下であることを特徴とする外観
良好なゴム変性熱可塑性樹脂組成物1. A rubber-modified thermoplastic resin obtained by polymerizing an aromatic monovinyl monomer and a vinyl cyanide monomer in which a rubber-like substance is dissolved by a continuous bulk polymerization method or a bulk-suspension two-step polymerization method. In the composition, (a) the proportion of the components in the copolymer resin phase is 65 to 95% by weight of the aromatic monovinyl monomer and 5 to 35% of the vinyl cyanide monomer.
% By weight, and (b) the rubber-like substance is 2 with respect to 100 parts by weight of the copolymer resin phase.
Polybutadiene containing 20 to 20 parts by weight of 1,2 vinyl bonds 10 to 25%, trans 1,4 bonds 35 to 65%, and cis 1,4 bonds 25 to 40%. % Solution viscosity is 10 to 50 centipoise, and (c) the rubber-like substance is dispersed in the resin composition as particles having a weight average particle diameter of 0.2 to 1.5 microns, and the weight average particle diameter and number average particle diameter are Is 2.0 or less, and (d) the number average particle diameter of the copolymer of aromatic monovinyl monomer and vinyl cyanide monomer contained in the rubber-like substance particles is 0.13 micron or less. A rubber-modified thermoplastic resin composition having a good appearance characterized by
度が、20〜35センチポイスであることを特徴とする特許
請求の範囲第１項記載の樹脂組成物2. The resin composition according to claim 1, wherein a solution viscosity of the rubber-like substance in styrene at 5% by weight is 20 to 35 centipoise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61267726A JPH0737501B2 (en) | 1986-11-12 | 1986-11-12 | Rubber-modified thermoplastic resin composition with good appearance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61267726A JPH0737501B2 (en) | 1986-11-12 | 1986-11-12 | Rubber-modified thermoplastic resin composition with good appearance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63122720A JPS63122720A (en) | 1988-05-26 |
| JPH0737501B2 true JPH0737501B2 (en) | 1995-04-26 |
Family
ID=17448712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61267726A Expired - Lifetime JPH0737501B2 (en) | 1986-11-12 | 1986-11-12 | Rubber-modified thermoplastic resin composition with good appearance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0737501B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216139A (en) * | 1988-07-05 | 1990-01-19 | Mitsui Toatsu Chem Inc | Styrene copolymer modified with anionically polymerized rubber |
| JP5436517B2 (en) * | 2011-08-01 | 2014-03-05 | 日本エイアンドエル株式会社 | Graft copolymer and thermoplastic resin composition |
| CN115057971B (en) * | 2022-07-01 | 2023-11-07 | 北方华锦化学工业股份有限公司 | High-fluidity impact-resistant polystyrene composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59179611A (en) * | 1983-03-31 | 1984-10-12 | Mitsui Toatsu Chem Inc | Rubber-modified styrene/acrylonitrile copolymer resin composition |
| JPS59217712A (en) * | 1983-05-26 | 1984-12-07 | Nippon Erasutomaa Kk | Impact-resistant styrene resin |
| JPS60233116A (en) * | 1984-05-04 | 1985-11-19 | Asahi Chem Ind Co Ltd | Rubber-reinforced aromatic monovinyl resin composition |
-
1986
- 1986-11-12 JP JP61267726A patent/JPH0737501B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59179611A (en) * | 1983-03-31 | 1984-10-12 | Mitsui Toatsu Chem Inc | Rubber-modified styrene/acrylonitrile copolymer resin composition |
| JPS59217712A (en) * | 1983-05-26 | 1984-12-07 | Nippon Erasutomaa Kk | Impact-resistant styrene resin |
| JPS60233116A (en) * | 1984-05-04 | 1985-11-19 | Asahi Chem Ind Co Ltd | Rubber-reinforced aromatic monovinyl resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63122720A (en) | 1988-05-26 |
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