JPH0621210B2 - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH0621210B2 JPH0621210B2 JP59274476A JP27447684A JPH0621210B2 JP H0621210 B2 JPH0621210 B2 JP H0621210B2 JP 59274476 A JP59274476 A JP 59274476A JP 27447684 A JP27447684 A JP 27447684A JP H0621210 B2 JPH0621210 B2 JP H0621210B2
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- monomer
- vinyl
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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、耐熱性に優れ、熱分解しにくく、且つ成形時
の着色劣化が少ない熱い可塑性樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a hot plastic resin composition having excellent heat resistance, being resistant to thermal decomposition, and having little color deterioration during molding.
［従来の技術］ 耐衝撃性に優れた熱可塑性樹脂として、今日、ABS樹
脂、AAS樹脂及びAES樹脂等で代表されるゴム変性熱可塑
性樹脂が広く利用されている。[Prior Art] As a thermoplastic resin having excellent impact resistance, a rubber-modified thermoplastic resin represented by ABS resin, AAS resin and AES resin is widely used today.
しかしながら、高い耐熱変形性を必要とする分野では、
これらの樹脂は耐熱性に欠けているため、比較的高温下
での使用に制限があった。そこで、これらの樹脂の耐熱
性を改良する方法が種々提案されており、例えば、α−
メチルスチレンとアクリロニトリルからなる共重合体を
ブレンドすると、優れた耐熱性を有する樹脂組成物が得
られることが特公昭45-33661号公報、特開昭55-78043号
公報、特開昭56-103211号公報及び特公昭57-60373号公
報等に述べられている。However, in fields requiring high heat distortion resistance,
Since these resins lack heat resistance, their use is limited at relatively high temperatures. Therefore, various methods for improving the heat resistance of these resins have been proposed, for example, α-
By blending a copolymer composed of methylstyrene and acrylonitrile, it is possible to obtain a resin composition having excellent heat resistance. JP-B-45-33661, JP-A-55-78043, JP-A-56-103211 And Japanese Patent Publication No. 57-60373.
［発明が解決しようとする問題点］ しかしながら、ゴム変性熱可塑性樹脂の耐熱性を向上さ
せる目的でα−アルキル置換芳香族ビニル共重合体を製
造しようとする場合、シアン化ビニルとα−アルキル置
換芳香族ビニル単量体との混合物を単純に重合させただ
けでは重合率が高くならず、しかも組成分布の広い共重
合体しか得られない。このため、この方法では耐熱性、
耐衝撃性が悪く、かつ熱分解し易い製品しか得ることが
できない。また、同単量体混合物を単に滴下重合させた
だけでも、やはり重合率が高くならず、組成分布の広い
共重合体しか得ることができない。一方、α−アルキル
置換芳香族ビニル単量体を先に仕込み、しかる後シアン
化ビニル単量体のみを滴下して重合させる方法がある
が、この方法では重合収率は高くなる傾向があるもの
の、組成分布の広い重量体しか得られない。以上の様な
共重合体を用いた場合は、α−アルキル置換芳香族ビニ
ル含有率の高い樹脂成分がが熱分解し易い性質を有して
いるため、高温成形時にシルバーストリークが多発する
傾向がみられる。また、シアン化ビニル含有率の高い
（α−アルキル置換芳香族ビニル含有率の低い）樹脂成
分は高温成形時に着色劣化を起こし易い性質を有してい
るため、かかる共重合体を用いた場合、製品の外観に著
しい黄変を生じる。[Problems to be Solved by the Invention] However, when an α-alkyl-substituted aromatic vinyl copolymer is produced for the purpose of improving the heat resistance of the rubber-modified thermoplastic resin, vinyl cyanide and α-alkyl-substituted are used. Simply polymerizing a mixture with an aromatic vinyl monomer does not increase the polymerization rate, and only a copolymer having a wide composition distribution can be obtained. Therefore, in this method, heat resistance,
Only products with poor impact resistance and easy thermal decomposition can be obtained. Further, even if the same monomer mixture is simply dropped and polymerized, the polymerization rate is not increased and only a copolymer having a wide composition distribution can be obtained. On the other hand, there is a method of preliminarily charging an α-alkyl-substituted aromatic vinyl monomer and then dropping only a vinyl cyanide monomer to perform polymerization, but this method tends to increase the polymerization yield. However, only a weight body having a wide composition distribution can be obtained. When a copolymer as described above is used, the resin component having a high α-alkyl-substituted aromatic vinyl content has a property of being easily thermally decomposed, so that silver streaks tend to occur frequently during high temperature molding. Seen. Further, since a resin component having a high vinyl cyanide content (low α-alkyl-substituted aromatic vinyl content) has a property of easily causing color deterioration during high temperature molding, when such a copolymer is used, Remarkable yellowing occurs on the appearance of the product.
したがって、本発明では、耐熱性が優れ、高温成形時の
着色性が少なく、かつ、熱分解しにくく、成形加工性が
優れ、しかも耐衝撃性の良好な樹脂組成物を提供するこ
とを目的とするものである。Therefore, in the present invention, it is an object of the present invention to provide a resin composition having excellent heat resistance, low colorability during high-temperature molding, and less likely to undergo thermal decomposition, excellent moldability, and good impact resistance. To do.
［問題点を解決するための手段］ 本発明の熱可塑性樹脂組成物は、 [A]α−アルキル置換芳香族ビニル単量体60〜85重量
部；シアン化ビニル単量体15〜35重量部；及びこれらと
共重合可能なビニル系単量体０〜40重量部からなる共重
合体であって、 重合率０〜90％の各反応段階において、重合反応中の該
共重合体中に含まれるα−アルキル置換芳香族ビニルの
含有率の変動範囲を２％以内に保ち製造される共重合
体：50〜90重量％、並びに、 [B]ゴム状重合体30〜85重量部；モノビニル芳香族単量
体、シアン化ビニル単量体及びこれらと共重合可能な単
量体が85〜40：０〜40：０〜60の重量比で合わせて15〜
70重量部からなるグラフト共重合体：10〜50重量％、 から構成され、上記重合体[A]及び[B]の合計量が100重
量％であることを特徴とする。[Means for Solving Problems] The thermoplastic resin composition of the present invention comprises: [A] α-alkyl-substituted aromatic vinyl monomer 60 to 85 parts by weight; vinyl cyanide monomer 15 to 35 parts by weight. And a copolymer of 0 to 40 parts by weight of a vinyl-based monomer copolymerizable therewith, which is included in the copolymer during the polymerization reaction in each reaction step with a polymerization rate of 0 to 90%. Copolymer produced by keeping the variation range of the content of α-alkyl-substituted aromatic vinyl within 2%: 50 to 90% by weight, and [B] rubber-like polymer 30 to 85 parts by weight; monovinylaromatic Group monomer, vinyl cyanide monomer and monomer copolymerizable with them are combined in a weight ratio of 85 to 40: 0 to 40: 0 to 15 to 15 in total.
70 parts by weight of a graft copolymer: 10 to 50% by weight, wherein the total amount of the above polymers [A] and [B] is 100% by weight.
以下、本発明を更に詳細に説明する。Hereinafter, the present invention will be described in more detail.
本発明において特に重要なことは、α−アルキル置換芳
香族ビニル共重合体としてα−アルキル置換芳香族ビニ
ル含有率が一定で組成分布の狭い均一な共重合体[A]を
使用したことにある。即ち、高い耐熱性を保ち、熱分解
を小さくするために、重合率０〜90％（好ましくは０〜
95）の各反応段階において、重合反応中の該共重合体中
に含まれるα−アルキル置換芳香族ビニルの含有率の変
動範囲を２％以内に調節することにより得られた組成分
布の狭い共重合体[A]を使用したことである。更に本発
明では、上記共重合体[A]にグラフト共重合体[B]を混合
することにより、耐熱性が高く、熱分解性が少なく、且
つ、耐衝撃性及び流動性の良好な熱可塑性樹脂組成物と
したことを特徴とする。What is particularly important in the present invention is that a uniform copolymer [A] having a constant α-alkyl-substituted aromatic vinyl content and a narrow composition distribution is used as the α-alkyl-substituted aromatic vinyl copolymer. . That is, in order to maintain high heat resistance and reduce thermal decomposition, the polymerization rate is 0 to 90% (preferably 0 to
In each reaction step of 95), the copolymer having a narrow composition distribution obtained by adjusting the variation range of the content rate of the α-alkyl-substituted aromatic vinyl contained in the copolymer during the polymerization reaction to within 2% That is, the polymer [A] was used. Furthermore, in the present invention, by mixing the above-mentioned copolymer [A] with the graft copolymer [B], high heat resistance, low thermal decomposability, and good thermoplasticity with good impact resistance and fluidity It is characterized in that it is a resin composition.
本発明において使用される共重合体[A]は、α−アルキ
ル置換芳香族ビニル単量体、シアン化ビニル単量体及び
必要に応じて配合されるこれらと共重合可能なビニル系
単量体からなる。The copolymer [A] used in the present invention is an α-alkyl-substituted aromatic vinyl monomer, a vinyl cyanide monomer, and a vinyl-based monomer copolymerizable with these, which is blended as necessary. Consists of.
ここで、α−アルキル置換芳香族ビニル単量体として
は、例えばα−メチルスチレン、エチルスチレン又は更
にハロゲンもしくはアルキル核置換基を有するα−メチ
ルスチレン等が挙げられ、単独又は２種以上混合してい
られるが、好ましくはα−メチルスチレンである。ま
た、シアン化ビニル単量体としては、例えば、アクリロ
ニトリル、メタクリロニトリル等が挙げられ、単独又は
２種以上混合して使用されるが、好ましくはアクリロニ
トリルである。更に、これらと共重合可能なビニル系単
量体としては、例えば、N-フエニルマレイミド、マレイ
ミド等のマレイミド系単量体、メタクリル酸、アクリル
酸、メタクリル酸エステル、アクリル酸エステル等のア
クリル酸系単量体、及びフマロニトリル、アセナフチレ
ンが挙げられ、これらを単独又は２種以上混合して用い
ることができる。Here, as the α-alkyl-substituted aromatic vinyl monomer, for example, α-methylstyrene, ethylstyrene, or α-methylstyrene having a halogen or alkyl nucleus substituent, and the like can be mentioned. They may be used alone or in combination of two or more. However, α-methylstyrene is preferable. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more, and acrylonitrile is preferable. Further, as the vinyl-based monomer copolymerizable with these, for example, N-phenylmaleimide, maleimide-based monomer such as maleimide, methacrylic acid, acrylic acid, methacrylic acid ester, acrylic acid such as acrylic acid ester. Examples thereof include a system monomer, fumaronitrile, and acenaphthylene, and these can be used alone or in combination of two or more.
これらの単量体の配合割合は、α−アルキル置換芳香族
ビニル単量体が60〜85重量部、シアン化ビニル単量体が
15〜35重量部、これらと共重合可能なビニル系単量体が
０〜40重量部である。α−アルキル置換芳香族ビニル単
量体の配合割合が60重量部未満のときは、耐熱性が低下
する傾向があり、85重量部を超えると重合速度が高くな
らず、また耐衝撃性が低下し、熱分解し易い傾向がで
る。また、シアン化ビニル単量体の配合割合が15重量部
未満のとき、重合速度が低下する傾向がみられ、35重量
部を超えると高温成形時に着色劣化を起し易く、また耐
熱性が低下する傾向がある。一方、ビニル系単量体は任
意加成分であって、これを配合しなくとも格別問題は生
じないが、40重量部以内で配合した場合は耐熱性をさら
に向上せしめることができる利点が得られる。The mixing ratio of these monomers is 60 to 85 parts by weight of α-alkyl-substituted aromatic vinyl monomer and vinyl cyanide monomer.
15 to 35 parts by weight, and 0 to 40 parts by weight of the vinyl-based monomer copolymerizable therewith. When the blending ratio of the α-alkyl-substituted aromatic vinyl monomer is less than 60 parts by weight, the heat resistance tends to decrease, and when it exceeds 85 parts by weight, the polymerization rate does not increase and the impact resistance decreases. However, it tends to be easily thermally decomposed. Further, when the mixing ratio of the vinyl cyanide monomer is less than 15 parts by weight, the polymerization rate tends to decrease, and when it exceeds 35 parts by weight, color deterioration is likely to occur during high temperature molding, and heat resistance is deteriorated. Tend to do. On the other hand, the vinyl-based monomer is an optional additive component, and no particular problem occurs even if it is not blended, but when blended within 40 parts by weight, the advantage that the heat resistance can be further improved can be obtained. .
上記共重合体[A]は、該共重合体中のα−アルキル置換
芳香族ビニル含有率を重合率０〜90％（好ましくは０〜
95％）の重合反応段階において２％以内の変動範囲に制
御することにより得られたものである。かかる共重合体
[A]を製造する方法は、例えば、まずα−アルキル置換
芳香族ビニル単量体全量とシアン化ビニル単量体及びビ
ニル系単量体の一部を先に仕込み、十分に乳化状態にす
る。次にシアン化ビニル単量体及びビニル系単量体の反
応消失速度にほぼ一致するように、滴下速度を適宜選択
して、残りのシアン化ビニル単量体及びビニル系単量体
を連続滴下することにより、重合反応中のモノマー組成
を常に仕込組成とほぼ等しい一定の狭い範囲内に保ちつ
つ重合させるものである。重合率０〜90％の反応段階
で、重合反応中の該共重合体中に含まれるα−アルキル
置換芳香族ビニル含有率の変動範囲が２％を超える場合
は、組成分布が狭く、かつ耐熱性の優れた共重合体が得
られにくい傾向がある。The copolymer [A] has a polymerization rate of 0 to 90% (preferably 0 to 90%, based on the α-alkyl-substituted aromatic vinyl content of the copolymer).
It was obtained by controlling the fluctuation range within 2% in the polymerization reaction stage of (95%). Such a copolymer
The method for producing [A] is, for example, to first charge the entire amount of α-alkyl-substituted aromatic vinyl monomer, vinyl cyanide monomer and a part of vinyl-based monomer in advance to sufficiently emulsify the state. . Next, the dropping speed is appropriately selected so that the reaction disappearance speed of the vinyl cyanide monomer and the vinyl monomer is almost the same, and the remaining vinyl cyanide monomer and the vinyl monomer are continuously dropped. By doing so, polymerization is carried out while always maintaining the monomer composition during the polymerization reaction within a certain narrow range substantially equal to the charged composition. When the variation range of the α-alkyl-substituted aromatic vinyl content contained in the copolymer during the polymerization reaction exceeds 2% in the reaction step of the polymerization rate of 0 to 90%, the composition distribution is narrow and the heat resistance is high. It tends to be difficult to obtain a copolymer having excellent properties.
一方、本発明において使用されるグラフト共重合体[B]
は、ゴム状重合体、モノビニル芳香族単量体、シアン化
ビニル単量体及び必要に応じて配合されるこれらと共重
合可能な単量体からなる。On the other hand, the graft copolymer [B] used in the present invention
Is a rubber-like polymer, a monovinyl aromatic monomer, a vinyl cyanide monomer, and a monomer copolymerizable with these, which is blended as necessary.
ここでゴム状重合体とは、例えば、ジエン系単量体を主
成分とするジエン系ゴム（例えば、ポリブタジエン、ポ
リイソプレン、ブタジエン−スチレン共重合体等）、ア
クリル酸エステルを主成分とするアクリル系ゴム（例え
ば、ブチルアクリレートを主成分とするアクリルゴム
等）及びエチレン−プロピレン−ジエン（EPDM）系ゴム
等をいうが、格別にこれらに限定されるものではない。
これらのゴム状重合体は単独又は２種以上混合して使用
することができる。また、モノビニル芳香族単量体とし
ては、例えばスチレンの外にα−メチルスチレン、クロ
ルスチレン、tert−ブチルスチレン等が挙げられ、単独
又は２種以上混合して用いられる。Here, the rubber-like polymer means, for example, a diene rubber containing a diene monomer as a main component (for example, polybutadiene, polyisoprene, butadiene-styrene copolymer, etc.), an acrylic resin containing an acrylic ester as a main component. A rubber (for example, an acrylic rubber containing butyl acrylate as a main component) and an ethylene-propylene-diene (EPDM) rubber are referred to, but are not particularly limited thereto.
These rubber-like polymers can be used alone or in combination of two or more. Examples of the monovinyl aromatic monomer include styrene, α-methylstyrene, chlorostyrene, tert-butylstyrene, etc., which may be used alone or in combination of two or more.
シアン化ビニル単量体としては、例えば、アクリロニト
リル、メタクリロニトリル等が挙げられ、単独又は２種
以上混合して使用される。更にこれらと共重合可能な単
量体としては、例えばＮ−フエニルマレイミド、マレイ
ミド等のマレイミド系単量体、メタクリル酸、アクリル
酸、メタクリル酸エステル、アクリル酸エステル等のア
クリル酸系単量体、及びフマロニトリル、アセナフチレ
ン等が挙げられるが、これらは単独又は２種以上混合し
て用いられる。Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Further, examples of monomers copolymerizable with these include maleimide-based monomers such as N-phenylmaleimide and maleimide, acrylic acid-based monomers such as methacrylic acid, acrylic acid, methacrylic acid ester, and acrylic acid ester. , And fumaronitrile, acenaphthylene, and the like. These may be used alone or in combination of two or more.
これらの配合割合は、ゴム状重合体が30〜85重量部、モ
ノビニル芳香族単量体、シアン化ビニル単量体及びこれ
らと共重合可能な単量体が85〜40：０〜40：０〜60の重
量比で合わせて15〜70重量部である。ゴム状重合体の配
合割合が30重量部未満のときは、耐衝撃性が低下する傾
向があり、85重量部を超えると良好な耐熱性が得られに
くく、また成形性が低下する傾向がある。また、モノビ
ニル芳香族単量体、シアン化ビニル単量体及びこれらと
共重合可能な単量体とを合わせた配合割合が15重量部未
満のとき、成形性が低下する傾向があり、70重量部を超
えると耐衝撃性が低下する傾向がある。これらの単量体
の配合比が上記範囲外となる場合は、本発明の目的とす
る熱可塑性樹脂組成物が得られにくい傾向がある。The mixing ratio of these is such that the rubber-like polymer is 30 to 85 parts by weight, the monovinyl aromatic monomer, the vinyl cyanide monomer and the monomer copolymerizable therewith are 85 to 40: 0 to 40: 0. 15 to 70 parts by weight in total in a weight ratio of -60. When the compounding ratio of the rubber-like polymer is less than 30 parts by weight, impact resistance tends to decrease, and when it exceeds 85 parts by weight, good heat resistance is difficult to obtain, and moldability tends to decrease. . Further, when the blending ratio of the monovinyl aromatic monomer, the vinyl cyanide monomer and the monomer copolymerizable therewith is less than 15 parts by weight, the moldability tends to decrease, and 70 parts by weight If it exceeds the range, the impact resistance tends to decrease. If the compounding ratio of these monomers is out of the above range, it tends to be difficult to obtain the thermoplastic resin composition of the present invention.
上記の如き成分からなるグラフト重合は通常の方法によ
り既知の反応条件下で行われる。Graft polymerization comprising the above components is carried out by a conventional method under known reaction conditions.
さて、以上に説明してきた共重合体[A]及びグラフト共
重合体[B]は、いずれも乳化重合により得られるが、そ
れらの製造方法は格別乳化重合のみに限定されるもので
はない。Both the copolymer [A] and the graft copolymer [B] described above can be obtained by emulsion polymerization, but their production method is not limited to particular emulsion polymerization.
乳化重合は通常の方法によって実施することができる。
例えば、前記単量体混合物に、水性分散媒中、重合開始
剤、連鎖移動剤、乳化剤などの従来公知のものを適宜添
加することにより、上記共重合体が得られる。重合終了
後、常法により凝固させると共重合体粉を得ることがで
きる。Emulsion polymerization can be carried out by a usual method.
For example, the above copolymer can be obtained by appropriately adding conventionally known compounds such as a polymerization initiator, a chain transfer agent and an emulsifier in an aqueous dispersion medium to the monomer mixture. After the completion of the polymerization, the copolymer powder can be obtained by coagulating by a conventional method.
本発明においては、このようにして得られた共重合体
[A]とグラフト共重合体[B]の両乾固粉をヘンシェルミキ
サーで混合した後、ベント付混練押出機やバンバリ、ロ
ール等により混練しペレット化することにより、目的と
する耐熱性に優れ、熱分解性が少なく、成形時の着色劣
化が少なく、耐衝撃性にも優れ、且つ流動性が優れた熱
可塑性樹脂組成物が得られる。In the present invention, the copolymer thus obtained
After mixing both dry solid powders of [A] and graft copolymer [B] with a Henschel mixer, kneading with a venting kneading extruder, Banbury, rolls, etc. to form pellets, excellent heat resistance as desired A thermoplastic resin composition having low thermal decomposability, little color deterioration during molding, excellent impact resistance, and excellent fluidity can be obtained.
［実施例］ 以上に実施例を挙げて本発明を具体的に説明する。な
お、実施例中「部」とあるのはいずれも「重量部」を表
わす。また、熱分解性、成形時の着色、ポリマー中のα
−メチルスチレン含有量については、次のように測定し
た。[Examples] The present invention will be specifically described with reference to Examples. In the examples, "parts" means "parts by weight". In addition, thermal decomposability, coloring during molding, α in the polymer
-Methylstyrene content was measured as follows.
熱分解性、成形時の着色 １ozの射出成形機を用い、230及び290℃で射出成形して
得られたそれぞれの成形板中に残存するα−メチルスチ
レンの含量（重量％）をガスクロマトグラフィーにより
測定し、290℃と230℃における含量の差（重量％差）の
大小により、熱分解性の程度を判定した。また、射出成
形時の着色変化を290℃で射出成形した成形板の黄色度
（ＹＩ値、JIS K-7103により測定）により測定し、着色
劣化の有無を調べた。Pyrolysis, coloring at the time of molding Using a 1 oz injection molding machine, the content (% by weight) of α-methylstyrene remaining in each molded plate obtained by injection molding at 230 and 290 ° C was analyzed by gas chromatography. The degree of thermal decomposability was judged by the difference in content (difference in weight%) between 290 ° C and 230 ° C. Further, the change in coloration during injection molding was measured by the yellowness (YI value, measured according to JIS K-7103) of the molded plate injection-molded at 290 ° C., and the presence or absence of color deterioration was examined.
共重合体中のα−メチルスチレン含量 イソプロピルアルコールを用いて凝固回収したポリマー
について、ミクロケルダール法によりそのアクリロニト
リル含量を含め、残余をα−メチルスチレン含量とし
た。Α-Methylstyrene content in the copolymer Regarding the polymer coagulated and recovered using isopropyl alcohol, the acrylonitrile content was included by the Micro-Kjeldahl method, and the balance was taken as the α-methylstyrene content.
実施例１〜５ 共重合体[A]の製造 容量５の撹拌機付き反応器に次の物質を仕込んだ。Examples 1 to 5 Preparation of copolymer [A] The following substances were charged in a reactor equipped with a stirrer and having a capacity of 5.
水 250部 デキストローズ 0.5部 硫酸第一鉄（FeSO4・7H2O） 0.003部 ピロ燐酸ナトリウム 0.1部 パルミチン酸カリウム 3部 上記物質を窒素気流中で60℃に加熱撹拌した後、後述す
る表に記載した単量体(I)をそれぞれ仕込んだ。それら
を十分に乳化させた後、クメンヒドロペルオキシド0.3
部を添加し、続いて、表に示した単量体(II)をそれぞれ
連続的に３時間滴下した。滴下終了後、更に１時間半撹
拌を続けた後、重合を終了した。生成した共重合体ラテ
ックスを１％硫酸マグネシウム水溶液で凝固し、洗浄、
乾燥し白色粉末を得た。After the water 250 parts Dextrose 0.5 part of ferrous sulfate (FeSO 4 · 7H 2 O) 0.003 parts sodium pyrophosphate 0.1 parts palmitic acid potassium 3 parts The above materials were stirred and heated to 60 ° C. in a nitrogen stream, the table to be described later Each of the listed monomers (I) was charged. After fully emulsifying them, cumene hydroperoxide 0.3
Then, the monomers (II) shown in the table were continuously added dropwise for 3 hours. After the dropwise addition was completed, stirring was continued for another one and a half hours, and then the polymerization was completed. The copolymer latex produced is coagulated with a 1% magnesium sulfate aqueous solution, washed,
A white powder was obtained after drying.
一方、反応途中のラテックスを逐次サンプリングし、組
成分析と重合率を経時的に測定した。結果を図に示し
た。図より明らかなように、上記反応で得られた共重合
体はいずれも共重合体中のα−メチルスチレン(MS)含有
率が一定であり、組成分布が狭いことがわかる。On the other hand, the latex during the reaction was sequentially sampled, and the composition analysis and the polymerization rate were measured with time. The results are shown in the figure. As is clear from the figure, all of the copolymers obtained by the above reaction have a constant α-methylstyrene (MS) content in the copolymer and have a narrow composition distribution.
共重合体[B]の製造 (B-1)ジエン系ゴム変性樹脂 撹拌機付き反応器に次の物質を仕込んだ。Production of Copolymer [B] (B-1) Diene Rubber Modified Resin The following substances were charged in a reactor equipped with a stirrer.
水 140部 デキストローズ 0.3部 硫酸第一鉄（FeSO4・7H2O） 0.005部 ピロ燐酸ナトリウム 0.2部 ポリブタジエン 60部 上記物質を窒素気流中60℃で加熱撹拌した後、スチレン
28部、アクリロニトリル12部及びクメンヒドロペルオキ
シド0.3部を同時に連続的に２時間滴下した。滴下終了
後、更に１時間撹拌した後、重合を終了した。得られた
ラテックスに抗酸化剤としてブチル化ヒドロキシトルエ
ン２部を加え、５％硫酸水溶液で凝固し、洗浄、乾燥し
て白色粉末のグラフト共重合体(B-1)を得た。After the water 140 parts Dextrose 0.3 part of ferrous sulfate (FeSO 4 · 7H 2 O) 0.005 parts sodium pyrophosphate 0.2 parts of polybutadiene 60 parts The above materials were stirred and heated at 60 ° C. in a nitrogen stream, a styrene
28 parts, acrylonitrile 12 parts and cumene hydroperoxide 0.3 parts were simultaneously added dropwise continuously for 2 hours. After the dropwise addition was completed, the mixture was stirred for 1 hour, and then the polymerization was completed. 2 parts of butylated hydroxytoluene was added to the obtained latex as an antioxidant, coagulated with a 5% sulfuric acid aqueous solution, washed and dried to obtain a white powder of the graft copolymer (B-1).
(B-2)アクリル系ゴム変性樹脂 (A)架橋樹脂ラテックスの製法 反応容器中にイオン交換水200部を入れ、窒素置換を行
った後、昇温して内温を80℃にした。この容器内に過硫
酸カリウム0.06部を加えて下記混合物を30分間に旦り連
続的に注入した。(B-2) Method for producing acrylic rubber-modified resin (A) cross-linked resin latex 200 parts of ion-exchanged water was put into a reaction vessel, nitrogen substitution was performed, and then the temperature was raised to 80 ° C. 0.06 part of potassium persulfate was added to this container, and the following mixture was continuously injected for 30 minutes.
メチルメタクリレート（MMA） 24部 アクリロニトリル（AN） 24部 スチレン（St） 7.2部 トリアリルイソシアヌレート（TAIC） 0.06部 ペレックスOTP 0.3部 注入後１時間程で発熱反応は終了した。得られた架橋樹
脂ラテックスの粒子径は0.26μであった。Methyl methacrylate (MMA) 24 parts Acrylonitrile (AN) 24 parts Styrene (St) 7.2 parts Triallyl isocyanurate (TAIC) 0.06 parts Perex OTP 0.3 parts The exothermic reaction was completed about 1 hour after injection. The particle diameter of the obtained crosslinked resin latex was 0.26μ.
(B)多相構造架橋アクリル系ゴムの製造 (A)で得た架橋樹脂ラテックスに0.24部の過硫酸カリウ
ムを追加添加し、下記混合物を２時間に旦って連続的に
注入した。(B) Production of cross-linked acrylic rubber with multi-phase structure To the cross-linked resin latex obtained in (A), 0.24 parts of potassium persulfate was additionally added, and the following mixture was continuously injected for 2 hours.
n-ブチルアクリレート（BuA） 43.2部 AN 4.8部 TAIC 0.24部 ペレックスOTP 0.30部 このようにして得られた架橋樹脂を芯部とする架橋アク
リル系ゴムの膨潤度は80、ゲル含有部は90％、粒子径は
0.30μであった。ここで膨潤度（ＤＳ）とは、試料0.5
ｇ（Ｗ１ｇ）をトルエン50mlに室温にて48時間浸漬後10
0メッシュですくった重さ（Ｗ２ｇ）とすると、ＤＳ＝
Ｗ２／Ｗ１で算出したものをいう。またゲル含有量（Ｇ
Ｃ）とは、前記Ｗ２ｇの試料を一昼夜真空乾燥した重さ
（Ｗ３ｇ）とするとＧＣ＝Ｗ３／Ｗ１×100％で算出し
たものをいう。n-Butyl acrylate (BuA) 43.2 parts AN 4.8 parts TAIC 0.24 parts Perex OTP 0.30 parts The swelling degree of the crosslinked acrylic rubber having the crosslinked resin thus obtained as the core is 80, and the gel content is 90%, Particle size
It was 0.30μ. Here, the degree of swelling (DS) means sample 0.5
g (W 1 g) in 50 ml of toluene at room temperature for 48 hours and then 10
Assuming a weight of 0 mesh (W 2 g), DS =
It refers to the value calculated by W 2 / W 1 . The gel content (G
C) means a value calculated by GC = W 3 / W 1 × 100% when the weight of the W 2 g sample is vacuum-dried all day and night (W 3 g).
(C)グラフト共重合体の製造 引続き(B)の架橋アクリル系ゴムラテックスに下記の混
合物を２時間に亘って連続的に注入した。(C) Preparation of Graft Copolymer Subsequently, the following mixture was continuously injected into the crosslinked acrylic rubber latex of (B) over 2 hours.
MMA 8部 AN 8部 St 24部 n-オクチルメルカプタン 0.04部 過硫化ベンゾイル 0.20部 このようにして得られたラテックスを５倍量の塩化カル
シウム水溶液に撹拌しながら投入し凝固させた後、脱
液、洗浄を行ない乾燥することによって高ゴム含量のグ
ラフト共重合体(B-2)を得た。MMA 8 parts AN 8 parts St 24 parts n-octyl mercaptan 0.04 parts Benzoyl persulfate 0.20 parts The latex thus obtained is poured into a 5-fold amount of calcium chloride aqueous solution with stirring to coagulate, followed by deliquoring, After washing and drying, a graft copolymer (B-2) having a high rubber content was obtained.
得られたグラフト共重合体(B-1)又は(B-2)を夫々、前記
した５種の共重合体[A]と表に示した重量比で混合し、
ヘンシェルミキサーで混合した後、樹脂温270℃で押出
し、ペレット化して耐熱性、耐衝撃性、流動性等の基本
物性及び熱分解性、成形時の着色劣化の評価に供した。
その結果を表に併記した。The resulting graft copolymer (B-1) or (B-2) was mixed with the above-mentioned five copolymers [A] at the weight ratios shown in the table,
After mixing with a Henschel mixer, the resin was extruded at a resin temperature of 270 ° C., pelletized and subjected to evaluation of basic physical properties such as heat resistance, impact resistance, fluidity and thermal decomposability, and color deterioration during molding.
The results are also shown in the table.
表から明らかなように、本発明により製造された共重合
体は、耐熱性、耐熱分解性、流動性、耐衝撃性、成形時
の着色劣化に優れていることが判明する。As is clear from the table, it is clear that the copolymer produced according to the present invention is excellent in heat resistance, thermal decomposition resistance, fluidity, impact resistance and color deterioration during molding.
比較例１ 容量５の撹拌器付き反応器に次の物質を仕込んだ。Comparative Example 1 The following substances were charged into a reactor equipped with a stirrer and having a volume of 5.
水 250部 デキストローズ 0.5部 硫酸第一鉄（FeSO4・7H2O） 0.003部 ピロ燐酸ナトリウム 0.1部 パルミチン酸カリウム 3部 上記物質の窒素気流中で60℃に加熱撹拌した後、α−メ
チルスチレンを80部仕込んだ。十分に乳化させた後、ア
クリロニトリル20部及びクメンヒドロペルオキシド0.5
部を一定の滴下速度で連続的に４時間滴下した。滴下終
了後、更に２時間撹拌を続けた後、重合を終了した。生
成した共重合体ラテックスを１％硫酸マグネシウム水溶
液で凝固し、洗浄乾燥し白色粉末を得た。Water 250 parts Dextrose 0.5 part of ferrous sulfate (FeSO 4 · 7H 2 O) was heated with stirring to 60 ° C. with 0.003 parts of a stream of nitrogen of sodium pyrophosphate 0.1 parts potassium palmitate 3 parts The above substances, alpha-methyl styrene I prepared 80 copies. After fully emulsified, 20 parts of acrylonitrile and 0.5 of cumene hydroperoxide are added.
A part was continuously dropped at a constant dropping rate for 4 hours. After the dropwise addition was completed, stirring was continued for another 2 hours, and then the polymerization was completed. The produced copolymer latex was coagulated with a 1% magnesium sulfate aqueous solution, washed and dried to obtain a white powder.
一方、反応途中のラテックスをサンプリングし、組成分
析と重合率を測定した。結果を図に併記した。また、前
記実施例で得られたグラフト共重合体(B-1)と、上記比
較例の共重合体とを25：75の重量比でブレンドし、ヘン
シェルミキサーにより混合した後、樹脂温270℃で押し
出しペレット化し、基本物性、熱分解性及び熱着色性の
評価に供した。その結果を表に併記した。On the other hand, the latex during the reaction was sampled, and the composition analysis and the polymerization rate were measured. The results are also shown in the figure. Further, the graft copolymer (B-1) obtained in the above example, and the copolymer of the comparative example were blended at a weight ratio of 25:75, and after mixing with a Henschel mixer, the resin temperature was 270 ° C. It was extruded into pellets and evaluated for basic physical properties, thermal decomposability and thermal colorability. The results are also shown in the table.
比較例２ 容量５の撹拌機付き反応器に次の物質を仕込んだ。Comparative Example 2 The following substances were charged in a reactor equipped with a stirrer and having a volume of 5.
水 250部 デキストローズ 0.5部 硫酸第一鉄（FeSO4・7H2O） 0.003部 ピロ燐酸ナトリウム 0.1部 パルミチン酸カリウム 5部 上記物質を窒素気流中で60℃に加熱撹拌した後、α−メ
チルスチレン及びアクリロニトリルをそれぞれ24部、2.
4部仕込んだ。この反応系にクメンヒドロペルオキシド
0.3部を添加し、１時間重合を行った後、α−メチルス
チレン56部及びアクリロニトリル5.6部を３時間連続滴
下した。その後、収率を上げる目的でアクリロニトリル
12部を１時間連続滴下した。滴下終了後、更に３時間撹
拌した後、重合を終了した。生成した共重合体ラテック
スを１％硫酸マグネシウム水溶液で凝固した後、洗浄乾
燥し白色粉末を得た。After the water 250 parts Dextrose 0.5 part of ferrous sulfate (FeSO 4 · 7H 2 O) 0.003 parts sodium pyrophosphate 0.1 parts palmitic acid potassium 5 parts The above materials were stirred and heated to 60 ° C. in a nitrogen stream, alpha-methyl styrene And 24 parts of acrylonitrile, 2.
4 copies were prepared. Cumene hydroperoxide was added to this reaction system.
After 0.3 part was added and polymerization was carried out for 1 hour, 56 parts of α-methylstyrene and 5.6 parts of acrylonitrile were continuously added dropwise for 3 hours. Then, for the purpose of increasing the yield, acrylonitrile
12 parts was continuously dropped for 1 hour. After the dropping was completed, the mixture was further stirred for 3 hours, and then the polymerization was finished. The produced copolymer latex was coagulated with a 1% aqueous magnesium sulfate solution, washed and dried to obtain a white powder.
一方、反応途中のラテックスをサンプリングし、組成分
析と重合率を測定した。結果を図に示した。また、前記
実施例で得た。グラフト共重合体(B-1)と、上記比較例
の共重合体とを25：75の重量比でブレンドし、ヘンシェ
ルミキサーにより混合した後、樹脂温270℃で押し出し
ペレット化し、基本物性、熱分解性及び着色性の評価に
供した。その結果を表に示した。On the other hand, the latex during the reaction was sampled, and the composition analysis and the polymerization rate were measured. The results are shown in the figure. In addition, it was obtained in the above example. The graft copolymer (B-1) and the copolymer of the comparative example were blended at a weight ratio of 25:75, mixed with a Henschel mixer, and then extruded into pellets at a resin temperature of 270 ° C. to obtain basic physical properties and heat. It was used for evaluation of degradability and colorability. The results are shown in the table.
比較例３ 容量５の撹拌器付き反応器に次の物質を仕込んだ。Comparative Example 3 The following substances were charged in a reactor equipped with a stirrer and having a volume of 5.
水 250部 デキストローズ 0.5部 硫酸第一鉄（FeSO4・7H2O） 0.003部 ピロ燐酸ナトリウム 0.1部 パルミチン酸カリウム 5部 上記物質を窒素気流中で60℃に加熱撹拌した後、α−メ
チルスチレン80部、アクリロニトリル8部及びクメンヒ
ドロペルオキシド0.4部を６時間連続滴下し、続いて収
率を上げる目的で、アクリロニトリル12部を１時間滴下
した。滴下終了後、更に３時間撹拌を続けて重合を終了
した。生成した共重合体ラテックスを１％硫酸マグネシ
ウム水溶液で凝固した後、洗浄、乾燥し白色粉末を得
た。After the water 250 parts Dextrose 0.5 part of ferrous sulfate (FeSO 4 · 7H 2 O) 0.003 parts sodium pyrophosphate 0.1 parts palmitic acid potassium 5 parts The above materials were stirred and heated to 60 ° C. in a nitrogen stream, alpha-methyl styrene 80 parts, 8 parts of acrylonitrile and 0.4 parts of cumene hydroperoxide were continuously added dropwise for 6 hours, and then 12 parts of acrylonitrile were added dropwise for 1 hour for the purpose of increasing the yield. After completion of the dropping, stirring was continued for further 3 hours to complete the polymerization. The produced copolymer latex was coagulated with a 1% aqueous magnesium sulfate solution, washed and dried to obtain a white powder.
一方、反応途中のラテックスをサンプリングし組成分析
と重合率を測定した。結果を図に示した。また、前記実
施例で得たグラフト共重合体(B-1)と本比較例の共重合
体と25：75の重量比でブレンドし、ヘンシェルミキサー
にて混合した後、樹脂温270℃で押し出しペレット化、
基本物性、熱分解性及び熱着色性の評価に供した。その
結果を表に示した。On the other hand, the latex in the middle of the reaction was sampled to analyze the composition and measure the polymerization rate. The results are shown in the figure. Further, the graft copolymer obtained in the above example (B-1) and the copolymer of the present comparative example were blended at a weight ratio of 25:75, mixed with a Henschel mixer, and then extruded at a resin temperature of 270 ° C. Pelletizing,
It was used for evaluation of basic physical properties, thermal decomposability, and thermal colorability. The results are shown in the table.
［発明の効果］ 本発明の最大の特徴は、α−アルキル置換芳香族ビニル
共重合体として、α−アルキル置換芳香族ビニル含有率
が一定で組成分布の狭い均一な共重合体を使用したこと
にある。したがって、かかかる共重合体をブレンドした
本発明の樹脂組成物を用いれば、極めて優れた耐熱性及
び耐熱分解性を有し、かつ、高温成形時の着色性が少な
い成形品を得ることができる。また、本発明の樹脂組成
物はこの他に、成形加工性及び耐衝撃性についても良好
な性質を有している。 EFFECTS OF THE INVENTION The greatest feature of the present invention is that a uniform copolymer having a constant α-alkyl-substituted aromatic vinyl content and a narrow composition distribution is used as the α-alkyl-substituted aromatic vinyl copolymer. It is in. Therefore, by using the resin composition of the present invention in which such a copolymer is blended, it is possible to obtain a molded product having extremely excellent heat resistance and thermal decomposition resistance, and having little coloring during high temperature molding. . In addition to the above, the resin composition of the present invention has good properties such as moldability and impact resistance.
図は各実施例及び比較例の反応途中におけるラテックス
について測定した共重合体中のα−メチルスチレン含有
量と重合率との関係を示したものである。The figure shows the relationship between the content of α-methylstyrene in the copolymer and the polymerization rate, which was measured for the latex during the reaction in each Example and Comparative Example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中田 章 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社内 (72)発明者 山本 直己 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社内 (56)参考文献 特開 昭59−80455（ＪＰ，Ａ) 特開 昭58−13649（ＪＰ，Ａ) 特開 昭57−147534（ＪＰ，Ａ) 特開 昭60−231750（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Nakata 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon Co., Ltd. (72) Inventor Naoki Yamamoto 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon (56) References JP 59-80455 (JP, A) JP 58-13649 (JP, A) JP 57-147534 (JP, A) JP 60-231750 (JP, A)
Claims (1)
体60〜85重量部；シアン化ビニル単量体15〜35重量部；
及びこれらと共重合可能なビニル系単量体０〜40重量部
からなる共重合体であって、 重合率０〜90％の各反応段階において、重合反応中の該
共重合体中に含まれるα−アルキル置換芳香族ビニルの
含有率の変動範囲を２％以内に保ち製造される共重合
体：50〜90重量％、並びに、 〔Ｂ〕ゴム状重合体30〜85重量部；モノビニル芳香族単
量体、シアン化ビニル単量体及びこれらと共重合可能な
単量体が85〜40：０〜40：０〜60の重量比で合わせて15
〜70重量部からなるグラフト共重合体：10〜50重量％、 から構成され、上記重合体〔Ａ〕及び〔Ｂ〕の合計量が
100重量％である熱可塑性樹脂組成物。1. [A] 60-85 parts by weight of an α-alkyl-substituted aromatic vinyl monomer; 15-35 parts by weight of a vinyl cyanide monomer;
And a copolymer comprising 0 to 40 parts by weight of a vinyl-based monomer copolymerizable therewith, which is contained in the copolymer during the polymerization reaction in each reaction step having a polymerization rate of 0 to 90%. Copolymer produced by keeping the content range of α-alkyl-substituted aromatic vinyl within 2%: 50 to 90% by weight, and [B] rubber-like polymer 30 to 85 parts by weight; monovinylaromatic Monomers, vinyl cyanide monomers and monomers copolymerizable with them are combined in a weight ratio of 85 to 40: 0 to 40: 0 to 15 in total.
To 70 parts by weight of the graft copolymer: 10 to 50% by weight, and the total amount of the above polymers [A] and [B] is
A thermoplastic resin composition which is 100% by weight.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59274476A JPH0621210B2 (en) | 1984-12-28 | 1984-12-28 | Thermoplastic resin composition |
| CA000498335A CA1273147A (en) | 1984-12-28 | 1985-12-20 | PROCESS FOR PRODUCING AN .alpha.-ALKYL-SUBSTITUTED AROMATIC VINYL COPOLYMER AND A THERMOPLASTIC RESIN COMPOSITION COMPRISING THE COPOLYMER |
| DE8585116572T DE3572499D1 (en) | 1984-12-28 | 1985-12-24 | A process for producing an alpha-alkyl-substituted aromatic vinyl copolymer and a thermoplastic resin composition comprising the copolymer |
| EP85116572A EP0188814B1 (en) | 1984-12-28 | 1985-12-24 | A process for producing an alpha-alkyl-substituted aromatic vinyl copolymer and a thermoplastic resin composition comprising the copolymer |
| US07/523,269 US5057574A (en) | 1984-12-28 | 1990-05-14 | Process for producing an α-alkyl-substituted aromatic vinyl copolymer and a thermoplastic resin composition comprising the copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59274476A JPH0621210B2 (en) | 1984-12-28 | 1984-12-28 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61155439A JPS61155439A (en) | 1986-07-15 |
| JPH0621210B2 true JPH0621210B2 (en) | 1994-03-23 |
Family
ID=17542219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59274476A Expired - Lifetime JPH0621210B2 (en) | 1984-12-28 | 1984-12-28 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621210B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0742386B2 (en) * | 1989-10-06 | 1995-05-10 | 住友ダウ株式会社 | Weather resistant resin composition |
| KR101743816B1 (en) * | 2014-04-25 | 2017-06-07 | 주식회사 엘지화학 | Heat-resistant styrene copolymer and styrene resin composition comprising the same |
| JP6210255B2 (en) * | 2014-04-25 | 2017-10-11 | エルジー・ケム・リミテッド | Heat resistant styrene copolymer and styrene resin composition containing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57147534A (en) * | 1981-03-06 | 1982-09-11 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JP2634396B2 (en) * | 1981-07-17 | 1997-07-23 | 電気化学工業株式会社 | Method for producing thermoplastic resin composition |
| JPS5980455A (en) * | 1982-10-28 | 1984-05-09 | Sumitomo Naugatuck Co Ltd | Heat-resistant, impact-resistant resin composition |
| JPS60231750A (en) * | 1984-05-02 | 1985-11-18 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
-
1984
- 1984-12-28 JP JP59274476A patent/JPH0621210B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61155439A (en) | 1986-07-15 |
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| Date | Code | Title | Description |
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| EXPY | Cancellation because of completion of term |