JP4530123B2 - Thermoplastic resin composition - Google Patents
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本発明は、耐衝撃性、特に、低温における耐衝撃性と流動性のバランスにすぐれると共に、耐薬品性と塗装性にもすぐれる熱可塑性樹脂組成物に関する。 The present invention relates to a thermoplastic resin composition having excellent impact resistance, in particular, good balance between impact resistance and fluidity at low temperatures, and excellent chemical resistance and paintability.
ポリアミド樹脂は、耐薬品性、機械的強度、耐熱性、耐磨耗性等にすぐれており、電気・電子部品、機械部品や自動車部品として広く用いられているが、耐衝撃性に劣る欠点を有している。他方、ゴム強化スチレン系樹脂であるＨＩＰＳ（ハイインパクトスチレン共重合体樹脂）、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン共重合体樹脂）、ＡＥＳ樹脂（アクリロニトリル−エチレン・プロピレン系ゴム−スチレン共重合体樹脂）、ＡＡＳ樹脂（アクリロニトリル−アクリル系ゴム−スチレン共重合体樹脂）等は、耐衝撃性や成形性にすぐれており、これらも自動車部品、事務機器部品、電気部品等として広く用いられているが、しかし、耐薬品性や耐磨耗性に劣るという欠点を有している。 Polyamide resins have excellent chemical resistance, mechanical strength, heat resistance, wear resistance, etc., and are widely used as electrical / electronic parts, mechanical parts, and automobile parts, but have the disadvantage of being inferior in impact resistance. Have. On the other hand, HIPS (high impact styrene copolymer resin), ABS resin (acrylonitrile-butadiene-styrene copolymer resin), and AES resin (acrylonitrile-ethylene / propylene rubber-styrene copolymer resin) which are rubber-reinforced styrene resins ), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer resin) and the like are excellent in impact resistance and moldability, and these are also widely used as automobile parts, office equipment parts, electrical parts, etc. However, it has the disadvantage of being inferior in chemical resistance and wear resistance.
そこで、これらの樹脂の相互の欠点を補うために、ポリアミド樹脂とＡＢＳ樹脂のブレンドが提案されている（特許文献１参照）。しかし、ポリアミド樹脂とＡＢＳ樹脂とは相溶性が乏しいので、不飽和カルボン酸をスチレンやアクリロニトリルと共重合してなる不飽和カルボン酸変性共重合体をポリアミド樹脂とＡＢＳ樹脂に相溶化剤として配合することが提案されており（特許文献２参照）、このような相溶性の改善に伴って、耐衝撃性についても、ある程度の改善が得られている。 Therefore, a blend of polyamide resin and ABS resin has been proposed in order to compensate for the mutual drawbacks of these resins (see Patent Document 1). However, since the compatibility between the polyamide resin and the ABS resin is poor, an unsaturated carboxylic acid-modified copolymer obtained by copolymerizing an unsaturated carboxylic acid with styrene or acrylonitrile is blended with the polyamide resin and the ABS resin as a compatibilizing agent. (Refer to Patent Document 2), and with such improved compatibility, some improvement in impact resistance has been obtained.
しかし、最近に至って、家電製品や自動車部品等の大型化や薄肉化が一層進展するなか、成形サイクルを向上して、その生産性を高めるべく、耐衝撃性と共に、流動性にすぐれたポリアミド樹脂／ゴム強化スチレン系樹脂組成物、特に、ポリアミド樹脂／ＡＢＳ樹脂組成物が求められるに至っている。 However, in recent years, polyamide resins with excellent impact resistance and fluidity have been developed in order to improve the molding cycle and increase the productivity, as household appliances and automobile parts are becoming larger and thinner. / Rubber-reinforced styrene-based resin compositions, in particular, polyamide resin / ABS resin compositions have been demanded.
そこで、相溶化剤として、限られた範囲の還元粘度を有する不飽和カルボン酸変性共重合体を用いることによって、耐衝撃性と流動性のバランスを図ることが提案されているが、未だ、十分とはいえない（特許文献３参照）。
本発明は、ポリアミド樹脂／ゴム強化スチレン系樹脂組成物における上述した問題を解決するためになされたものであって、耐衝撃性と流動性のバランスにすぐれ、更に、耐薬品性と塗装性にもすぐれるポリアミド樹脂／ゴム強化スチレン系樹脂組成物、特に、ポリアミド樹脂／ＡＢＳ樹脂組成物を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems in polyamide resin / rubber reinforced styrene resin compositions, and has a good balance between impact resistance and fluidity, and further has improved chemical resistance and paintability. An object of the present invention is to provide an excellent polyamide resin / rubber reinforced styrene resin composition, particularly a polyamide resin / ABS resin composition.
本発明によれば、
（Ａ）ポリアミド樹脂２０〜８０重量部と、
（Ｂ）膨潤度１５〜４５（但し、膨潤度は、ゴム状重合体を１ｇ精秤し、これを５０ｇのトルエン中に温度２３℃で４８時間浸漬して、ポリマーを膨潤させた後、トルエンをデカンテーションにて除き、ここで、膨潤したポリマーを精秤した後、８０℃で２４時間減圧乾燥して、ポリマーが吸収したトルエンを蒸発、除去し、再び、精秤して、Ｗ S を膨潤したポリマーの重量とし、Ｗ 0 を乾燥したポリマーの重量とするとき、式（Ｗ S −Ｗ 0 )／Ｗ 0 により算出される値である。）、重量平均粒子径１００〜６００ｎｍのゴム状重合体４０〜８０重量％の存在下に、芳香族ビニル系単量体５０〜９０重量％、シアン化ビニル系単量体１０〜５０重量％及び上記単量体に共重合性を有するその他のビニル単量体０〜３０重量％からなる単量体混合物２０〜６０重量％をグラフト重合してなり、アセトン可溶分の数平均分子量が２００００〜１０００００のグラフト重合体２０〜８０重量部と、
（Ｃ）メタクリル酸０．８〜７重量％、スチレン６０〜８５．２重量％及びアクリロニトリル１４〜３３重量％を共重合してなる数平均分子量２６０００〜４６０００の不飽和カルボン酸変性共重合体１０〜２４重量部と、
（Ｄ）スチレン５０〜９０重量％及びアクリロニトリル１０〜５０重量％を共重合してなる共重合体５〜２９重量部（但し、上記（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）の合計を１００重量部とする。）とからなることを特徴とする熱可塑性樹脂組成物が提供される。
According to the present invention,
(A) 20-80 parts by weight of polyamide resin;
(B) Swelling degree 15 to 45 (however, the swelling degree is determined by weighing 1 g of a rubbery polymer and immersing it in 50 g of toluene at a temperature of 23 ° C. for 48 hours to swell the polymer. except by decantation, wherein, after precisely weighed swollen polymer, and dried under reduced pressure for 24 hours at 80 ° C., the polymer has absorbed toluene evaporated to remove again, and precisely weighed, and W S When the weight of the swollen polymer is used and W 0 is the weight of the dried polymer, it is a value calculated by the formula (W S −W 0 ) / W 0. ) , Rubber-like having a weight average particle diameter of 100 to 600 nm In the presence of 40 to 80% by weight of polymer, 50 to 90% by weight of aromatic vinyl monomer, 10 to 50% by weight of vinyl cyanide monomer, and other monomers having copolymerizability with the above monomer Monomer mix consisting of 0-30 wt% vinyl monomer 20 to 60% by weight will by graft-polymerizing a graft polymer 20 to 80 parts by weight of the number average molecular weight of the acetone-soluble fraction is 20000-100000,
(C) Unsaturated carboxylic acid-modified copolymer 10 having a number average molecular weight of 26000 to 46000 , obtained by copolymerizing methacrylic acid 0.8 to 7 % by weight, styrene 60 to 85.2 % by weight, and acrylonitrile 14 to 33 % by weight. ~ 24 parts by weight;
(D) 5 to 29 parts by weight of a copolymer obtained by copolymerizing 50 to 90% by weight of styrene and 10 to 50 % by weight of acrylonitrile (however, the above (A), (B), (C) and (D) The total amount is 100 parts by weight.) A thermoplastic resin composition is provided.
特に、本発明によれば、好ましい態様として、
（Ａ）ポリアミド樹脂１００重量部と、
（Ｂ）膨潤度１５〜４５（但し、膨潤度は、ゴム状重合体を１ｇ精秤し、これを５０ｇのトルエン中に温度２３℃で４８時間浸漬して、ポリマーを膨潤させた後、トルエンをデカンテーションにて除き、ここで、膨潤したポリマーを精秤した後、８０℃で２４時間減圧乾燥して、ポリマーが吸収したトルエンを蒸発、除去し、再び、精秤して、ＷS を膨潤したポリマーの重量とし、Ｗ0 を乾燥したポリマーの重量とするとき、式（ＷS−Ｗ0)／Ｗ0 により算出される値である。）、重量平均粒子径１００〜６００ｎｍのゴム状重合体４０〜８０重量％の存在下に、芳香族ビニル系単量体４０〜９０重量部、シアン化ビニル系単量体１０〜４０重量部及び上記単量体に共重合性を有するその他のビニル単量体０〜２０重量部からなる単量体混合物（但し、上記芳香族ビニル系単量体、シアン化ビニル系単量体及びその他のビニル単量体の合計は１００重量部である。）２０〜６０重量％をグラフト重合してなり、アセトン可溶分の数平均分子量が２００００〜１０００００のグラフト重合体３０〜３００重量部と、
（Ｃ）メタクリル酸０．８〜７重量％、スチレン６０〜８５．２重量％及びアクリロニトリル１４〜３３重量％を共重合してなる数平均分子量２６０００〜４６０００の不飽和カルボン酸変性共重合体１７〜８０重量部と、
（Ｄ）スチレン５０〜９０重量％及びアクリロニトリル１０〜５０重量％を共重合してなる共重合体８〜９７重量部とからなることを特徴とする熱可塑性樹脂組成物が提供される。
In particular, according to the present invention, as a preferred embodiment,
(A) 100 parts by weight of a polyamide resin;
(B) Swelling degree 15 to 45 (however, the swelling degree is determined by weighing 1 g of a rubbery polymer and immersing it in 50 g of toluene at a temperature of 23 ° C. for 48 hours to swell the polymer. except by decantation, wherein, after precisely weighed swollen polymer, and dried under reduced pressure for 24 hours at 80 ° C., the polymer has absorbed toluene evaporated to remove again, and precisely weighed, and W S The weight of the swollen polymer, where W 0 is the weight of the dried polymer, and is a value calculated by the formula (W S −W 0 ) / W 0. ), Rubber-like having a weight average particle diameter of 100 to 600 nm In the presence of 40 to 80% by weight of polymer, 40 to 90 parts by weight of aromatic vinyl monomer, 10 to 40 parts by weight of vinyl cyanide monomer, and other monomers having copolymerizability with the above monomer Monomer mixture comprising 0 to 20 parts by weight of vinyl monomer (However, the total of the above aromatic vinyl monomer, vinyl cyanide monomer and other vinyl monomers is 100 parts by weight.) 20-60% by weight is graft-polymerized and acetone is acceptable. 30 to 300 parts by weight of a graft polymer having a number average molecular weight of a solute of 20,000 to 100,000,
(C) Unsaturated carboxylic acid-modified copolymer 17 having a number average molecular weight of 2600 to 46000, which is obtained by copolymerizing 0.8 to 7% by weight of methacrylic acid, 60 to 85.2% by weight of styrene and 14 to 33% by weight of acrylonitrile. ~ 80 parts by weight,
(D) A thermoplastic resin composition comprising 8 to 97 parts by weight of a copolymer obtained by copolymerizing 50 to 90% by weight of styrene and 10 to 50 % by weight of acrylonitrile is provided.
本発明による熱可塑性樹脂組成物は、ポリアミド樹脂とゴム強化スチレン系樹脂と相溶化剤としての不飽和カルボン酸変性共重合体と、必要に応じて、芳香族ビニル系単量体−シアン化ビニル系単量体共重合体とからなり、ここに、ゴム強化スチレン系樹脂におけるグラフト重合体としてアセトン可溶分が限られた範囲の数平均分子量を有せしめると共に、不飽和カルボン酸変性共重合体が限られた範囲の数平均分子量を有せしめることによって、耐衝撃性と流動性のバランにすぐれ、更に、耐薬品性と塗装性にもすぐれている。 The thermoplastic resin composition according to the present invention comprises a polyamide resin, a rubber-reinforced styrene resin, an unsaturated carboxylic acid-modified copolymer as a compatibilizing agent, and, if necessary, an aromatic vinyl monomer-vinyl cyanide. And a monomer having a number-average molecular weight of a limited acetone-soluble component as a graft polymer in a rubber-reinforced styrene resin, and an unsaturated carboxylic acid-modified copolymer. By having a number average molecular weight in a limited range, it is excellent in impact resistance and fluidity balun, and also in chemical resistance and paintability.
本発明において、ポリアミド樹脂（Ａ）としては、例えば、ナイロン６、ナイロン４６、ナイロン６６、ナイロン６９、ナイロン６１０、ナイロン６１２、ナイロン１１６、ナイロン４、ナイロン７、ナイロン８、ナイロン１１、ナイロン１２、ナイロン６Ｉ、ナイロン６／６６、ナイロン６Ｔ／６Ｉ、ナイロン６／６Ｔ、ナイロン６６／６Ｔ、ポリトリメチルヘキサメチレンテレフタルアミド、ポリビス（４−アミノシクロヘキシル）メタンドデカミド、ポリビス（３−メチル−４−アミノシクロヘキシル）メタンドデカミド、ポリメタキシリレンアジパミド、ナイロン１１Ｔ、ポリウンデカメチレンヘキサヒドロテレフタルアミド、ポリアミドエラストマー等を挙げることができる。上記において、Ｉはイソフタル酸成分、Ｔはテレフタル酸成分を示す。 In the present invention, examples of the polyamide resin (A) include nylon 6, nylon 46, nylon 66, nylon 69, nylon 610, nylon 612, nylon 116, nylon 4, nylon 7, nylon 8, nylon 11, nylon 12, Nylon 6I, Nylon 6/66, Nylon 6T / 6I, Nylon 6 / 6T, Nylon 66 / 6T, Polytrimethylhexamethylene terephthalamide, Polybis (4-aminocyclohexyl) methane dodecamide, Polybis (3-methyl-4-amino (Cyclohexyl) methandecamide, polymetaxylylene adipamide, nylon 11T, polyundecamethylene hexahydroterephthalamide, polyamide elastomer and the like. In the above, I represents an isophthalic acid component, and T represents a terephthalic acid component.
本発明によれば、これらのうち、特にナイロン６、ナイロン４６、ナイロン６６、ナイロン１２、ナイロン６Ｔ／６Ｉ、ナイロン６／６Ｔ、ナイロン６６／６Ｔが好ましく用いられる。 Of these, nylon 6, nylon 46, nylon 66, nylon 12, nylon 6T / 6I, nylon 6 / 6T, and nylon 66 / 6T are preferably used among these.
本発明において、グラフト重合体（Ｂ）とは、膨潤度１０〜８０、重量平均粒子径１００〜６００ｎｍのゴム状重合体４０〜８０重量％の存在下に、芳香族ビニル系単量体５０〜９０重量％、シアン化ビニル系単量体１０〜５０重量％及び上記単量体に共重合性を有するその他のビニル単量体０〜３０重量％からなる単量体混合物２０〜６０重量％をグラフト重合してなり、アセトン可溶分の数平均分子量が２００００〜２０００００の範囲にあるものをいう。 In the present invention, the graft polymer (B) is an aromatic vinyl monomer 50 to 50% in the presence of 40 to 80% by weight of a rubbery polymer having a degree of swelling of 10 to 80 and a weight average particle size of 100 to 600 nm. 90-60% by weight of a monomer mixture consisting of 90% by weight, 10-50% by weight of vinyl cyanide monomer and 0-30% by weight of other vinyl monomers copolymerizable with the above monomers It is obtained by graft polymerization and has a number-average molecular weight in the range of 20000 to 200000, which is soluble in acetone.
好ましい態様によれば、グラフト重合体（Ｂ）は、膨潤度１０〜８０、重量平均粒子径１００〜６００ｎｍのゴム状重合体４０〜８０重量％の存在下に、芳香族ビニル系単量体４０〜９０重量部、シアン化ビニル系単量体１０〜４０重量部及び上記単量体に共重合性を有するその他のビニル単量体０〜２０重量部からなる単量体混合物（但し、上記芳香族ビニル系単量体、シアン化ビニル系単量体及びその他のビニル単量体の合計は１００重量部である。）２０〜６０重量％をグラフト重合してなり、アセトン可溶分の数平均分子量が２００００〜２０００００の範囲にあるものをいう。 According to a preferred embodiment, the graft polymer (B) contains an aromatic vinyl monomer 40 in the presence of 40 to 80% by weight of a rubbery polymer having a degree of swelling of 10 to 80 and a weight average particle size of 100 to 600 nm. ~ 90 parts by weight, a monomer mixture comprising 10 to 40 parts by weight of vinyl cyanide monomer and 0 to 20 parts by weight of other vinyl monomers copolymerizable with the above monomers The total of the vinyl group monomer, vinyl cyanide monomer and other vinyl monomers is 100 parts by weight.) Graft polymerization of 20 to 60% by weight, number average of acetone solubles The molecular weight is in the range of 20,000 to 200,000.
本発明において、グラフト重合体の製造に用いる上記ゴム状重合体としては、例えば１，３−ポリブタジエン、ポリイソプレン等に代表される共役ジエンゴムや、また、共役ジエンとこれに共重合可能な単量体を共重合してなる共役ジエン共重合体ゴムが好ましく用いられる。上記共役ジエン系単量体と共重合可能な単量体としては、スチレン、α−メチルスチレン等の芳香族ビニル系単量体、アクリロニトリル、メタクリロニトリル等のシアン化ビニル系単量体、メチルアクリレート、エチルアクリレート、メチルメタアクリレート等の不飽和カルボン酸アルキルエステル系単量体等を挙げることができる。従って、上記ゴム状重合体の具体例として、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、ブタジエン−アクリロニトリル共重合体、ブタジエン−メチルメタアクリレート共重合体等を挙げることができる。 In the present invention, the rubbery polymer used for the production of the graft polymer may be, for example, a conjugated diene rubber represented by 1,3-polybutadiene, polyisoprene or the like, or a conjugated diene and a monomer copolymerizable therewith. A conjugated diene copolymer rubber obtained by copolymerizing a polymer is preferably used. Examples of the monomer copolymerizable with the conjugated diene monomer include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and methyl. Examples thereof include unsaturated carboxylic acid alkyl ester monomers such as acrylate, ethyl acrylate, and methyl methacrylate. Therefore, specific examples of the rubbery polymer include polybutadiene, polyisoprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-methyl methacrylate copolymer, and the like.
本発明によれば、グラフト重合体（Ｂ）は、このようなゴム状重合体に芳香族ビニル系単量体とシアン化ビニル系単量体と、必要に応じて、これらに共重合性を有するその他のビニル単量体をグラフト重合させることによって得ることができる。上記芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、クロロスチレン、ブロモスチレン等を挙げることができ、これらは単独で、又は２種以上の混合物として用いられる。これらのなかでは、特に、スチレンやα−メチルスチレンが好ましく用いられる。他方、シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル等を挙げることができ、これらも単独で、又は２種以上の混合物として用いられる。特に、アクリロニトリルが好ましく用いられる。 According to the present invention, the graft polymer (B) is prepared by adding an aromatic vinyl monomer and a vinyl cyanide monomer to such a rubber-like polymer, and optionally copolymerizing them. It can be obtained by graft polymerization of other vinyl monomers. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, bromostyrene, and the like, and these are used alone or as a mixture of two or more. Of these, styrene and α-methylstyrene are particularly preferably used. On the other hand, examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and these are also used alone or as a mixture of two or more. In particular, acrylonitrile is preferably used.
上記芳香族ビニル系単量体とシアン化ビニル系単量体に共重合性を有するその他のビニル単量体として、例えば、マレイミド、メチルマレイミド、エチルマレイミド、Ｎ−フェニルマレイミド、Ｏ−クロル−Ｎ−フェニルマレイミド等のマレイミド系単量体、メチルアクリレート、エチルアクリレート、メチルメタアクリレート、エチルメタアクリレート、２−エチルヘキシルアクリレート等の不飽和カルボン酸エステル系単量体等を挙げることができる。 Other vinyl monomers having copolymerizability with the above aromatic vinyl monomer and vinyl cyanide monomer include, for example, maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide, O-chloro-N -Maleimide monomers such as phenylmaleimide, unsaturated carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl acrylate.
本発明におけるグラフト重合体の製造に用いる上記ゴム状重合体は、１０〜８０、好ましくは、１５〜５０、特に好ましくは、２５〜４５の範囲の膨潤度を有する。ここに、本発明における膨潤度とは、次のようにして求められる値である。即ち、ラテックスを凝固、乾燥させて、ポリマーを得、このポリマーを１ｇ精秤し、これを５０ｇのトルエン中に温度２３℃で４８時間浸漬して、ポリマーを膨潤させた後、トルエンをデカンテーションにて除き、ここで、膨潤したポリマーを精秤した後、８０℃で２４時間減圧乾燥して、ポリマーが吸収したトルエンを蒸発、除去し、再び、精秤して、次式により膨潤度を算出する。 The rubbery polymer used in the production of the graft polymer in the present invention has a degree of swelling of 10 to 80, preferably 15 to 50, particularly preferably 25 to 45. Here, the degree of swelling in the present invention is a value obtained as follows. That is, the latex was coagulated and dried to obtain a polymer, 1 g of this polymer was precisely weighed, and this was immersed in 50 g of toluene at a temperature of 23 ° C. for 48 hours to swell the polymer. Excluded by decantation, and after precisely weighing the swollen polymer, it was dried under reduced pressure at 80 ° C. for 24 hours to evaporate and remove the toluene absorbed by the polymer. Calculate the degree.
膨潤度＝（ＷS−Ｗ0)／Ｗ0 Swelling degree = (W S −W 0 ) / W 0
ここに、ＷS は膨潤したポリマーの重量であり、Ｗ0 は乾燥したポリマーの重量である。 Here, W S is the weight of the swollen polymer and W 0 is the weight of the dried polymer.
本発明によれば、グラフト重合体の製造に用いる前記ゴム状重合体の膨潤度が１０よりも小さいとき、又は８０よりも大きいとき、得られる熱可塑性樹脂組成物が耐衝撃性において劣る。 According to the present invention, when the degree of swelling of the rubbery polymer used for the production of the graft polymer is smaller than 10 or larger than 80, the resulting thermoplastic resin composition is inferior in impact resistance.
更に、本発明によれば、グラフト重合体の製造に用いる上記ゴム状重合体は、重量平均粒子径が１００〜６００ｎｍの範囲にあり、特に、１５０〜４５０ｎｍの範囲にあることが好ましい。従って、本発明によれば、例えば、ゴム状重合体の粒子が上記重量平均粒子径を有するときは、そのまま、グラフト重合体の製造に供してもよく、また、必要に応じて、ゴム状重合体の粒子を凝集、肥大化させて、これをグラフト重合体の製造に供してもよい。ゴム状重合体の粒子を凝集、肥大化させるには、既によく知られているように、機械的に凝集させてもよく、また、ラテックスに酸性物質を加えてもよい。 Further, according to the present invention, the rubber-like polymer used in the production of the graft polymer has a weight average particle diameter of Ri range near the 100-600 nm, particularly preferably in the range of 150 to 450 nm. Therefore, according to the present invention, for example, when the rubber-like polymer particles have the above-mentioned weight average particle diameter, they may be used for the production of the graft polymer as they are, and if necessary, the rubber-like polymer particles may be used. The coalesced particles may be aggregated and enlarged to be used for the production of a graft polymer. In order to agglomerate and enlarge the particles of the rubber-like polymer, as well known, it may be agglomerated mechanically, or an acidic substance may be added to the latex.
更に、本発明においては、このようにして得られるグラフト重合体のアセトン可溶分の数平均分子量は、２００００〜２０００００の範囲である。グラフト重合体のアセトン可溶分の数平均分子量が２００００よりも小さいときは、得られる熱可塑性樹脂組成物が耐衝撃強度に劣り、他方、２０００００を越えるときは、得られる熱可塑性樹脂組成物が流動性に劣る。本発明においては、グラフト重合体のアセトン可溶分の数平均分子量は、好ましくは、２００００〜１０００００の範囲にあり、特に好ましくは、２００００〜６００００の範囲にある。本発明において、このようなグラフト重合体を製造する方法は、特に制限されるものではなく、従来より知られている方法によればよく、従って、例えば、乳化重合法、懸濁重合法、塊状重合法、溶液重合法又はこれらの組み合わせを適宜に用いることができる。 Furthermore, in this invention, the number average molecular weight of the acetone soluble part of the graft polymer obtained in this way is the range of 20000-200000. When the number average molecular weight of the acetone-soluble part of the graft polymer is less than 20000, the resulting thermoplastic resin composition is inferior in impact strength. On the other hand, when it exceeds 200,000, the resulting thermoplastic resin composition is Poor fluidity. In the present invention, the number average molecular weight of the acetone soluble part of the graft polymer is preferably in the range of 20000 to 100,000, and particularly preferably in the range of 20000 to 60000. In the present invention, a method for producing such a graft polymer is not particularly limited, and may be a conventionally known method. Therefore, for example, an emulsion polymerization method, a suspension polymerization method, a block shape, and the like. A polymerization method, a solution polymerization method, or a combination thereof can be appropriately used.
本発明において、不飽和カルボン酸変性共重合体（Ｃ）とは、不飽和カルボン酸単量体０．０５〜２０重量％、芳香族ビニル系単量体５０〜９０重量％及びシアン化ビニル系単量体１０〜５０重量％を共重合してなる数平均分子量２２０００〜６００００の共重合体である。 In the present invention, the unsaturated carboxylic acid-modified copolymer (C) is an unsaturated carboxylic acid monomer 0.05 to 20% by weight, an aromatic vinyl monomer 50 to 90% by weight, and a vinyl cyanide monomer. It is a copolymer having a number average molecular weight of 22,000 to 60,000 obtained by copolymerizing 10 to 50% by weight of monomers.
本発明の好ましい態様によれば、不飽和カルボン酸変性共重合体（Ｃ）は、不飽和カルボン酸単量体０．０５〜２０重量％、芳香族ビニル系単量体４５〜８９．９５重量％及びシアン化ビニル系単量体１０〜３５重量％を共重合してなる数平均分子量２２０００〜６００００の共重合体である。より好ましい態様によれば、不飽和カルボン酸変性共重合体（Ｃ）は、不飽和カルボン酸単量体０．５〜１０重量％、芳香族ビニル系単量体５５〜８７．５重量％及びシアン化ビニル系単量体１２〜３５重量％を共重合してなる共重合体であり、最も好ましい態様によれば、不飽和カルボン酸変性共重合体（Ｃ）は、不飽和カルボン酸単量体０．８〜７重量％、芳香族ビニル系単量体６０〜８５．２重量％及びシアン化ビニル系単量体１４〜３３重量％を共重合してなる共重合体である。 According to a preferred embodiment of the present invention, the unsaturated carboxylic acid-modified copolymer (C) comprises an unsaturated carboxylic acid monomer of 0.05 to 20% by weight and an aromatic vinyl monomer of 45 to 89.95%. % And a vinyl cyanide monomer of 10 to 35% by weight are copolymerized with a number average molecular weight of 22,000 to 60,000. According to a more preferred embodiment, the unsaturated carboxylic acid-modified copolymer (C) comprises 0.5 to 10% by weight of unsaturated carboxylic acid monomer, 55 to 87.5% by weight of aromatic vinyl monomer, and It is a copolymer obtained by copolymerizing 12 to 35% by weight of a vinyl cyanide monomer, and according to the most preferred embodiment, the unsaturated carboxylic acid-modified copolymer (C) is an unsaturated carboxylic acid monomer. It is a copolymer obtained by copolymerizing 0.8 to 7% by weight of a polymer, 60 to 85.2% by weight of an aromatic vinyl monomer, and 14 to 33% by weight of a vinyl cyanide monomer.
上記不飽和カルボン酸変性共重合体（Ｃ）を形成する不飽和カルボン酸単量体としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸等が挙げられ、これらは単独で、又は２種以上の混合物として用いられる。これらのなかでは、特に、メタクリル酸が好ましく用いられる。芳香族ビニル系単量体とシアン化ビニル系単量体としては、前記グラフト重合体（Ｂ）の製造に用いたものと同じものを用いることができる。 Examples of the unsaturated carboxylic acid monomer that forms the unsaturated carboxylic acid-modified copolymer (C) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and the like. Used as a mixture of two or more. Among these, methacrylic acid is particularly preferably used. As the aromatic vinyl monomer and the vinyl cyanide monomer, the same ones used for the production of the graft polymer (B) can be used.
本発明によれば、不飽和カルボン酸変性共重合体（Ｃ）を構成する芳香族ビニル系単量体の一部をこれに共重合可能な他のビニル系単量体、例えば、メチルアクリレート、エチルアクリレート、ブチルアクリレート、メチルメタアクリレート、エチルメタアクリレート、２−エチルヘキシルアクリレート等の不飽和カルボン酸エステル系単量体等に置き換えることができる。 According to the present invention, another vinyl monomer capable of copolymerizing a part of the aromatic vinyl monomer constituting the unsaturated carboxylic acid-modified copolymer (C), for example, methyl acrylate, It can be replaced with unsaturated carboxylic acid ester monomers such as ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and 2-ethylhexyl acrylate.
本発明によれば、得られる樹脂組成物が耐衝撃性と流動性のバランスにすぐれるように、不飽和カルボン酸変性共重合体は、数平均分子量が２２０００〜６００００の範囲にあることが必要である。不飽和カルボン酸変性共重合体（Ｃ）の数平均分子量が２２０００よりも小さいときは、得られる樹脂組成物が耐薬品性や塗装性に劣り、他方、６００００を越えるときは、得られる樹脂組成物が流動性に劣ることとなる。ここに、不飽和カルボン酸変性共重合体（Ｃ）の数平均分子量は、この共重合体をテトラヒドロフランに溶解させ、ＧＰＣ法（ゲル浸透クロマトグラフ法）によって測定した分子量である。 According to the present invention, the unsaturated carboxylic acid-modified copolymer needs to have a number average molecular weight in the range of 22000 to 60000 so that the resulting resin composition has a good balance between impact resistance and fluidity. It is. When the number average molecular weight of the unsaturated carboxylic acid-modified copolymer (C) is less than 22000, the resulting resin composition is inferior in chemical resistance and paintability. On the other hand, when it exceeds 60000, the resulting resin composition Things are inferior in fluidity. Here, the number average molecular weight of the unsaturated carboxylic acid-modified copolymer (C) is a molecular weight measured by GPC method (gel permeation chromatography) after dissolving the copolymer in tetrahydrofuran.
また、不飽和カルボン酸変性共重合体（Ｃ）において、不飽和カルボン酸単量体の量が０．０５重量％未満であるときは、この共重合体が樹脂組成物への相溶性に劣るので、得られる樹脂組成物が耐衝撃性と塗装性において劣り、他方、２０重量％を越えるときは、得られる樹脂組成物の流動性の低下が著しい。 Further, in the unsaturated carboxylic acid-modified copolymer (C), when the amount of the unsaturated carboxylic acid monomer is less than 0.05% by weight, the copolymer is inferior in compatibility with the resin composition. Therefore, the resulting resin composition is inferior in impact resistance and paintability. On the other hand, when it exceeds 20% by weight, the fluidity of the resulting resin composition is remarkably lowered.
本発明において、熱可塑性樹脂組成物における不飽和カルボン酸変性共重合体（Ｃ）の量が余りに少ないときは、樹脂組成物に均一に分散されず、得られる樹脂組成物が耐衝撃性と塗装性に劣り、他方、余りに多いときは、樹脂組成物が流動性に劣る。 In the present invention, when the amount of the unsaturated carboxylic acid-modified copolymer (C) in the thermoplastic resin composition is too small, it is not uniformly dispersed in the resin composition, and the resulting resin composition has impact resistance and coating. On the other hand, when the amount is too large, the resin composition is inferior in fluidity.
本発明によれば、このように、数平均分子量が２２０００〜６００００の範囲にあると共に、不飽和カルボン酸単量体が０．０５〜２０重量％、好ましくは、０．５〜１０重量％、最も好ましくは、０．７〜８重量％の範囲にある不飽和カルボン酸変性共重合体（Ｃ）を樹脂組成物に適正な範囲で配合することによって、ポリアミド樹脂とスチレン系樹脂との相溶性をすぐれたものとし、更に、耐衝撃性と流動性のバランスにすぐれ、特に、低温での耐衝撃強度にすぐれた熱可塑性樹脂組成物を得ることができる。 According to the present invention, the number average molecular weight is in the range of 22000 to 60000, and the unsaturated carboxylic acid monomer is 0.05 to 20% by weight, preferably 0.5 to 10% by weight. Most preferably, the compatibility between the polyamide resin and the styrenic resin is obtained by adding the unsaturated carboxylic acid-modified copolymer (C) in the range of 0.7 to 8% by weight to the resin composition in an appropriate range. Furthermore, it is possible to obtain a thermoplastic resin composition having an excellent balance between impact resistance and fluidity, and particularly excellent impact strength at low temperatures.
不飽和カルボン酸変性共重合体（Ｃ）も、その製造方法において、何ら制限されるものではなく、従来より知られている適宜の方法、例えば、乳化重合法、塊状重合法、懸濁重合法、溶液重合法等によって得ることができる。よく知られているように、このような不飽和カルボン酸変性共重合体（Ｃ）の数平均分子量は、重合温度や用いる単量体の添加方法、用いる開始剤や、例えば、ｔ−ドデシルメルカプタン等のような重合連鎖移動剤の種類や量によって任意に調整することができる。 The unsaturated carboxylic acid-modified copolymer (C) is not limited in its production method, and any conventionally known method such as an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method is known. It can be obtained by a solution polymerization method or the like. As is well known, the number average molecular weight of such an unsaturated carboxylic acid-modified copolymer (C) depends on the polymerization temperature, the method of adding the monomer used, the initiator used, for example, t-dodecyl mercaptan. It can be arbitrarily adjusted depending on the type and amount of the polymerization chain transfer agent such as.
本発明において、共重合体（Ｄ）とは、芳香族ビニル系単量体５０〜９０重量％、シアン化ビニル系単量体１０〜５０重量％及びこれらに共重合性を有するその他のビニル単量体０〜６０重量％を共重合してなる共重合体である。好ましい態様によれば、共重合体（Ｄ）は、芳香族ビニル系単量体４５〜９０重量％、シアン化ビニル系単量体１０〜４５重量％及びこれらに共重合性を有するその他のビニル単量体０〜１０重量％を共重合してなる共重合体である。 In the present invention, the copolymer (D) means an aromatic vinyl monomer of 50 to 90% by weight, a vinyl cyanide monomer of 10 to 50% by weight, and other vinyl monomers having copolymerizability therewith. It is a copolymer obtained by copolymerizing 0 to 60% by weight of a monomer. According to a preferred embodiment, the copolymer (D) is composed of 45 to 90% by weight of an aromatic vinyl monomer, 10 to 45% by weight of a vinyl cyanide monomer, and other vinyls copolymerizable therewith. It is a copolymer obtained by copolymerizing 0 to 10% by weight of monomers.
上記芳香族ビニル系単量体及びシアン化ビニル系単量体としては、前記グラフト重合体（Ｂ）の製造に用いたものと同様のものが用いられる。また、上記共重合性を有するその他のビニル単量体として、例えば、マレイミド、メチルマレイミド、エチルマレイミド、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｏ−クロル−Ｎ−フェニルマレイミド等のマレイミド系単量体、メチルアクリレート、エチルアクリレート、メチルメタアクリレート、エチルメタアクリレート、２−エチルヘキシルアクリレート等の不飽和カルボン酸エステル系単量体等が用いられる。 As the aromatic vinyl monomer and the vinyl cyanide monomer, those similar to those used in the production of the graft polymer (B) are used. Further, as other vinyl monomers having the above-mentioned copolymerizability, maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, O-chloro-N-phenylmaleimide, etc. Body, unsaturated carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, etc. are used.
本発明において、この共重合体（Ｄ）は、その重量平均分子量において、何ら限定されるものではないが、通常、５００００〜２５００００の範囲であり、好ましくは、５５０００〜２０００００の範囲である。このような共重合体（Ｄ）は、従来より知られている乳化重合法、塊状重合法、懸濁重合法、溶液重合法等、適宜の方法によって得ることができる。 In the present invention, the copolymer (D) is not limited in terms of its weight average molecular weight, but is usually in the range of 50,000 to 250,000, preferably in the range of 55,000 to 200,000. Such a copolymer (D) can be obtained by an appropriate method such as a conventionally known emulsion polymerization method, bulk polymerization method, suspension polymerization method, solution polymerization method and the like.
本発明による熱可塑性樹脂組成物は、上述したように、ポリアミド樹脂（Ａ）２０〜８０重量部、グラフト重合体（Ｂ）２０〜８０重量部、不飽和カルボン酸変性共重合体（Ｃ）０．５〜６０重量部及び共重合体（Ｄ）０〜５０重量部（但し、（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）の合計を１００重量部とする。）からなり、いずれかの成分がこの範囲を外れるときは、所期の特性を有する熱可塑性樹脂を得ることができない。特に、不飽和カルボン酸変性共重合体（Ｃ）については、１〜３５重量部の範囲が好ましい。 As described above, the thermoplastic resin composition according to the present invention comprises 20 to 80 parts by weight of the polyamide resin (A), 20 to 80 parts by weight of the graft polymer (B), and the unsaturated carboxylic acid-modified copolymer (C) 0. 5 to 60 parts by weight and copolymer (D) 0 to 50 parts by weight (provided that the total of (A), (B), (C) and (D) is 100 parts by weight). If any of these components is out of this range, a thermoplastic resin having the desired characteristics cannot be obtained. In particular, the unsaturated carboxylic acid-modified copolymer (C) is preferably in the range of 1 to 35 parts by weight.
好ましい態様によれば、本発明による熱可塑性樹脂組成物は、（Ａ）ポリアミド樹脂１００重量部、（Ｂ）グラフト重合体３０〜３００重量部、（Ｃ）不飽和カルボン酸変性共重合体１〜２５０重量部及び（Ｄ）共重合体０〜１２０重量部とからなり、より好ましくは、（Ａ）ポリアミド樹脂１００重量部、（Ｂ）グラフト重合体３０〜１５０重量部、（Ｃ）不飽和カルボン酸変性共重合体１〜１２０重量部及び（Ｄ）共重合体０〜１２０重量部とからなり、最も好ましくは、（Ａ）ポリアミド樹脂１００重量部、（Ｂ）グラフト重合体３５〜１３０重量部、（Ｃ）不飽和カルボン酸変性共重合体２〜１１０重量部及び（Ｄ）共重合体０〜１００重量部とからなる。 According to a preferred embodiment, the thermoplastic resin composition according to the present invention comprises (A) 100 parts by weight of a polyamide resin, (B) 30 to 300 parts by weight of a graft polymer, and (C) an unsaturated carboxylic acid-modified copolymer 1 to 1 part. 250 parts by weight and (D) copolymer 0 to 120 parts by weight, more preferably (A) 100 parts by weight of polyamide resin, (B) 30 to 150 parts by weight of graft polymer, (C) unsaturated carbon It comprises 1 to 120 parts by weight of an acid-modified copolymer and 0 to 120 parts by weight of (D) copolymer, and most preferably (A) 100 parts by weight of polyamide resin and (B) 35 to 130 parts by weight of graft polymer. (C) 2 to 110 parts by weight of an unsaturated carboxylic acid-modified copolymer and (D) 0 to 100 parts by weight of the copolymer.
更に、本発明によれば、得られる熱可塑性樹脂組成物の物性のバランスの観点から、樹脂組成物全体に占めるゴム状重合体の含有量は、８〜４０重量％の範囲であることが好ましく、特に、１０〜２５重量％の範囲であることが好ましい。 Furthermore, according to the present invention, from the viewpoint of balance of physical properties of the obtained thermoplastic resin composition, the content of the rubber-like polymer in the entire resin composition is preferably in the range of 8 to 40% by weight. In particular, the range of 10 to 25% by weight is preferable.
本発明による熱可塑性樹脂組成物は、上述したポリアミド樹脂（Ａ）、グラフト重合体（Ｂ）、不飽和カルボン酸変性共重合体（Ｃ）及び共重合体（Ｄ）を均一に溶融混合することによって得ることができるが、その混合の順序は何ら限定されるものではない。従って、例えば、すべての成分を一括して同時に混合してもよく、また、例えば、いずれかの２成分を先ず、予備的に混合した後、これに残余の２成分を加えて、混合してもよい。このような各成分の混合物の溶融混合に際しては、押出機、バンバリーミキサー、ロールミル等を用いることができる。 The thermoplastic resin composition according to the present invention is obtained by uniformly melting and mixing the above-described polyamide resin (A), graft polymer (B), unsaturated carboxylic acid-modified copolymer (C), and copolymer (D). However, the mixing order is not limited at all. Thus, for example, all the components may be mixed together at the same time, or, for example, any two components may be preliminarily mixed and then the remaining two components may be added and mixed. Also good. An extruder, a Banbury mixer, a roll mill, or the like can be used for melting and mixing such a mixture of components.
また、必要に応じて、上記成分にポリエチレン、ポリプロピレン等のα−オレフィンやそのα−オレフィン共重合体、ポリスチレン、ハイインパクトスチレン等のスチレン系樹脂、ポリカーボネート、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリメチルメタアクリレート、ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリスルホン、ポリエーテルスルホン、ポリイミド、ポリエーテルイミド、ポリエーテルエーテルケトン等の他の熱可塑性樹脂、更には、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、滑剤、染料、顔料、可塑剤、難燃剤、離型剤、ガラス繊維、金属繊維、炭素繊維、金属フレーク、タルク、グラファイト等の種々の添加剤、補強材、充填材等を添加することができる。 In addition, if necessary, α-olefin such as polyethylene and polypropylene, α-olefin copolymer thereof, styrene resin such as polystyrene and high-impact styrene, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polymethyl methacrylate Other thermoplastic resins such as acrylate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyethersulfone, polyimide, polyetherimide, polyetheretherketone, antioxidants, UV absorbers, light stabilizers, antistatic agents Add various additives such as lubricants, dyes, pigments, plasticizers, flame retardants, mold release agents, glass fibers , metal fibers, carbon fibers, metal flakes, talc, graphite, reinforcing materials, fillers, etc. it can.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。部及び％は重量基準である。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Parts and percentages are by weight.
参考例１
（ゴム状重合体の製造）
耐圧容器に１，３−ブタジエン１００部、ｔ−ドデシルメルカプタン０．３部、過硫酸カリウム０．２５部、オレイン酸カリウム２．５部、水酸化カリウム０．１部及び純水１７０部を仕込み、６５℃に昇温した後、重合を開始した。重合を２０時間で終了させて得られたジエン系ゴムラテックス（ｂ−（１））は、固形分３７％、重量平均粒子径６５ｎｍ、膨潤度２０であった。重合を１２時間で終了させたジエン系ゴムラテックス（ｂ−（２））は、固形分２５％、重量平均粒子径５０ｎｍ、膨潤度４０であった。ゴム状重合体の膨潤度は、前述したようにして求めた。
Reference example 1
(Manufacture of rubbery polymer)
A pressure vessel is charged with 100 parts of 1,3-butadiene, 0.3 part of t-dodecyl mercaptan, 0.25 part of potassium persulfate, 2.5 parts of potassium oleate, 0.1 part of potassium hydroxide and 170 parts of pure water. After the temperature was raised to 65 ° C., polymerization was started. The diene rubber latex (b- (1)) obtained by completing the polymerization in 20 hours had a solid content of 37%, a weight average particle diameter of 65 nm, and a swelling degree of 20. The diene rubber latex (b- (2)) whose polymerization was completed in 12 hours had a solid content of 25%, a weight average particle size of 50 nm, and a swelling degree of 40. The degree of swelling of the rubbery polymer was determined as described above.
（ゴム状重合体の凝集、肥大化）
上記ジエン系ゴムラテックス（ｂ−（１））を機械凝集して、膨潤度３６、重量平均粒子径３００ｎｍのゴム状重合体を含む肥大化ジエン系ゴムラテックス（ｂ−１）を得た。また、別に、上記ジエン系ゴムラテックス（ｂ−（２））１００重量部に酢酸０．１部を加え、１０分間攪拌混合した後、１０％水酸化カリウム水溶液１０部を加えて、固形分３４％、膨潤度４１、重量平均粒子径３００ｎｍの肥大化ジエン系ゴムラテックス（ｂ−２）を得た。
(Agglomeration and enlargement of rubbery polymer)
The diene rubber latex (b- (1)) was mechanically aggregated to obtain an enlarged diene rubber latex (b-1) containing a rubbery polymer having a degree of swelling of 36 and a weight average particle diameter of 300 nm. Separately, 0.1 part of acetic acid was added to 100 parts by weight of the diene rubber latex (b- (2)), and the mixture was stirred and mixed for 10 minutes. %, Swelling degree 41, weight-average particle diameter of 300 nm enlarged diene rubber latex (b-2) was obtained.
（グラフト重合体Ｂの製造）
ステンレス容器に上記肥大化ジエン系ゴムラテックス（ｂ−１）５０部（固形分）、ドデシルベンゼンスルホン酸ナトリウム１．５部及び過硫酸カリウム０．３部を仕込み、６５℃に昇温した後、スチレン３５部及びアクリロニトリル１５部からなる単量体混合物を５時間にわたって連続的に加えて、グラフト重合体ラテックスを得た。このグラフト重合体ラテックス１００重量部（固形分）当たりにフェノール系酸化防止剤１部とホスファイト系酸化防止剤２部を加えた後、硫酸マグネシウムを用いて凝固、脱水、乾燥して、グラフト重合体Ｂ−１を得た。このグラフト重合体Ｂ−１におけるゴム状重合体の膨潤度は３６、重量平均粒子径は３２０ｎｍ、ゴム状重合体の含量は６５％、アセトン可溶分の数平均分子量は２２０００であった。
(Production of graft polymer B)
After charging 50 parts (solid content) of the above-mentioned enlarged diene rubber latex (b-1), 1.5 parts of sodium dodecylbenzenesulfonate and 0.3 part of potassium persulfate into a stainless steel container, A monomer mixture consisting of 35 parts of styrene and 15 parts of acrylonitrile was continuously added over 5 hours to obtain a graft polymer latex. After adding 1 part of a phenolic antioxidant and 2 parts of a phosphite antioxidant per 100 parts by weight (solid content) of the graft polymer latex, the mixture is solidified, dehydrated and dried using magnesium sulfate. Combined B-1 was obtained. In this graft polymer B-1, the swelling degree of the rubber-like polymer was 36, the weight average particle size was 320 nm, the content of the rubber-like polymer was 65%, and the number-average molecular weight of the acetone-soluble component was 22,000.
また、上記グラフト重合体の製造において、開始剤としてクメンハイドロパーオキサイドを用いると共に還元剤として硫酸第一鉄を用いるレドックス触媒系によって、重合温度を５０℃とし、スチレンとアクリロニトリルからなる単量体混合物を全量初期に加えた以外は、上記と同様にして、グラフト重合体Ｂ−２を得た。このグラフト重合体Ｂ−２におけるゴム状重合体の膨潤度は４１、重量平均粒子径は２９０ｎｍ、ゴム状重合体の含量は５０％、アセトン可溶分の数平均分子量は４９０００であった。 In the production of the graft polymer, a monomer mixture comprising styrene and acrylonitrile at a polymerization temperature of 50 ° C. by a redox catalyst system using cumene hydroperoxide as an initiator and ferrous sulfate as a reducing agent. A graft polymer B-2 was obtained in the same manner as above except that was added in the initial amount. In this graft polymer B-2, the swelling degree of the rubber-like polymer was 41, the weight average particle diameter was 290 nm, the content of the rubber-like polymer was 50%, and the number-average molecular weight of the acetone-soluble component was 49000.
（不飽和カルボン酸変性共重合体Ｃの製造）
ステンレス容器に純水２００部、過硫酸カリウム０．３部及びドデシルベンゼンスルホン酸ナトリウム２部を仕込み、攪拌下に６５℃に昇温した。スチレン７４部、アクリロニトリル２５部、メタクリル酸１部及びｔ−ドデシルメルカプタン０．５部からなる単量体混合物を５時間にわたって連続的に加えた後、反応系の温度を７０℃に昇温し、この温度で１時間熟成して重合を完結した。その後、塩化カルシウムを用いて塩析、脱水、乾燥して、不飽和カルボン酸変性共重合体Ｃ−１を得た。得られた不飽和カルボン酸、即ち、メタクリル酸変性共重合体Ｃ−１の数平均分子量は５００００あった。
(Production of unsaturated carboxylic acid-modified copolymer C)
A stainless steel container was charged with 200 parts of pure water, 0.3 part of potassium persulfate and 2 parts of sodium dodecylbenzenesulfonate, and the temperature was raised to 65 ° C. with stirring. A monomer mixture consisting of 74 parts of styrene, 25 parts of acrylonitrile, 1 part of methacrylic acid and 0.5 part of t-dodecyl mercaptan was continuously added over 5 hours, and then the temperature of the reaction system was raised to 70 ° C. The polymerization was completed by aging at this temperature for 1 hour. Then, salting out using calcium chloride, dehydration, and drying were performed to obtain an unsaturated carboxylic acid-modified copolymer C-1. The number average molecular weight of the obtained unsaturated carboxylic acid, that is, methacrylic acid-modified copolymer C-1, was 50,000.
上記メタクリル酸変性共重合体Ｃ−１の製造において、単量体混合物として、スチレン７３部、アクリロニトリル２４部、メタクリル酸３部及びｔ−ドデシルメルカプタン０．５部からなる単量体混合物を用いた以外は、上記と同様にして、メタクリル酸変性共重合体Ｃ−２を得た。得られたメタクリル酸変性共重合体Ｃ−２の数平均分子量は４４０００であった。 In the production of the methacrylic acid-modified copolymer C-1, a monomer mixture comprising 73 parts of styrene, 24 parts of acrylonitrile, 3 parts of methacrylic acid and 0.5 part of t-dodecyl mercaptan was used as the monomer mixture. Except for the above, a methacrylic acid-modified copolymer C-2 was obtained in the same manner as described above. The number average molecular weight of the obtained methacrylic acid-modified copolymer C-2 was 44,000.
上記メタクリル酸変性共重合体Ｃ−２の製造において、単量体混合物として、スチレン７３部、アクリロニトリル２４部、メタクリル酸３部及びｔ−ドデシルメルカプタン１部からなる単量体混合物を用いた以外は、上記と同様にしてメタクリル酸変性共重合体Ｃ−３を得た。得られたメタクリル酸変性共重合体Ｃ−３の数平均分子量は２６０００であった。 In the production of the methacrylic acid-modified copolymer C-2, a monomer mixture consisting of 73 parts of styrene, 24 parts of acrylonitrile, 3 parts of methacrylic acid and 1 part of t-dodecyl mercaptan was used as the monomer mixture. In the same manner as above, a methacrylic acid-modified copolymer C-3 was obtained. The number average molecular weight of the obtained methacrylic acid-modified copolymer C-3 was 26000.
前記メタクリル酸変性共重合体Ｃ−１の製造において、スチレン７２部、アクリロニトリル２３部、メタクリル酸５部及びｔ−ドデシルメルカプタン０．５部からなる単量体混合物を用いた以外は、上記と同様にして、メタクリル酸変性共重合体Ｃ−４を得た。得られたメタクリル酸変性共重合体Ｃ−４の数平均分子量は４６０００であった。 In the production of the methacrylic acid-modified copolymer C-1, the same as above except that a monomer mixture composed of 72 parts of styrene, 23 parts of acrylonitrile, 5 parts of methacrylic acid and 0.5 part of t-dodecyl mercaptan was used. Thus, a methacrylic acid-modified copolymer C-4 was obtained. The number average molecular weight of the obtained methacrylic acid-modified copolymer C-4 was 46000.
更に、上記メタクリル酸変性共重合体Ｃ−２の製造において、スチレン７３部、アクリロニトリル２４部、メタクリル酸３部及びｔ−ドデシルメルカプタン１．６部からなる単量体混合物を用いた以外は、上記と同様にして、メタクリル酸変性共重合体Ｃ−５を得た。得られたメタクリル酸変性共重合体Ｃ−５の数平均分子量は２００００であった。 Further, in the production of the methacrylic acid-modified copolymer C-2, except that a monomer mixture composed of 73 parts of styrene, 24 parts of acrylonitrile, 3 parts of methacrylic acid and 1.6 parts of t-dodecyl mercaptan was used. In the same manner as above, a methacrylic acid-modified copolymer C-5 was obtained. The number average molecular weight of the obtained methacrylic acid-modified copolymer C-5 was 20000.
（共重合体Ｄの製造）
耐圧容器に純水２００部及び過硫酸カリウム０．３部を仕込み、攪拌下に６５℃に昇温した。スチレン７０部、アクリロニトリル３０部及びｔ−ドデシルメルカプタン０．３部からなる単量体混合物とドデシルベンゼンスルホン酸ナトリウム２部を含む乳化剤水溶液３０部をそれぞれ５時間にわたって連続的に加えた後、反応系を７０℃に昇温し、この温度で３時間熟成して重合を完結した。この後、塩化カルシウムを用いて、塩析、脱水、乾燥して、共重合体Ｄ−１を得た。得られた共重合体Ｄ−１の数平均分子量は８９０００であった。
(Production of copolymer D)
A pressure vessel was charged with 200 parts of pure water and 0.3 part of potassium persulfate and heated to 65 ° C. with stirring. A monomer mixture consisting of 70 parts of styrene, 30 parts of acrylonitrile and 0.3 part of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of sodium dodecylbenzenesulfonate were continuously added over 5 hours, respectively. Was heated to 70 ° C. and aged at this temperature for 3 hours to complete the polymerization. Thereafter, salting out, dehydration and drying were performed using calcium chloride to obtain a copolymer D-1. The number average molecular weight of the obtained copolymer D-1 was 89000.
上記共重合体Ｄ−１の製造において、ｔ−ドデシルメルカプタン１．２部を用いた以外は、上記と同様にして、共重合体Ｄ−２を得た。得られた共重合体Ｄ−２の数平均分子量は６００００であった。 In the production of the copolymer D-1, a copolymer D-2 was obtained in the same manner as described above except that 1.2 parts of t-dodecyl mercaptan was used. The number average molecular weight of the obtained copolymer D-2 was 60000.
実施例１〜６、比較例１〜７
ポリアミド樹脂Ａ（宇部興産（株）製ナイロン６（１０２２Ｂ））、グラフト共重合体Ｂ、不飽和カルボン酸変性共重合体Ｃ及び共重合体Ｄを表１に示す割合で混合し、３０ｍｍ二軸押出機を用いて２５０℃で溶融混合し、ペレットとした後、射出成形し、試験片としての熱可塑性樹脂組成物を調製して、それらの物性を評価した。結果を表１及び表２に示す。但し、表中、樹脂組成物の各成分の括弧内の数値は、ポリアミド樹脂を１００重量部としたときの各成分の重量部数である。
Examples 1-6 , Comparative Examples 1-7
Polyamide resin A (Nylon 6 (1022B) manufactured by Ube Industries, Ltd.), graft copolymer B, unsaturated carboxylic acid-modified copolymer C and copolymer D were mixed at the ratio shown in Table 1, and 30 mm biaxial. Using an extruder, the mixture was melt-mixed at 250 ° C. to form pellets, injection molded, and a thermoplastic resin composition as a test piece was prepared, and their physical properties were evaluated. The results are shown in Tables 1 and 2. However, the numerical value in the parenthesis of each component of the resin composition in the table is the number of parts by weight of each component when the polyamide resin is 100 parts by weight.
（耐衝撃性）
ＡＳＴＭ Ｄ−２５６に準拠。１／８インチ、２３℃及び−３０℃。
（流動性）
キャピログラフ（（株）東洋精機製作所製キャピログラフＩＣ）を用いて、温度２６０℃にて剪断速度１０００ｓｅｃ-1のときの溶融粘度（Ｐａ・ｓ）を流動性の指標として測定した。
（耐熱性）
ＡＳＴＭ Ｄ−６４８に準拠。１／４インチ、１．８２ＭＰａ荷重。
（曲げ弾性率）
ＡＳＴＭ Ｄ−７９０に準拠。
（耐薬品性）
射出成形にて作製した短冊状試験片（１５０×１０×２ｍｍ）をベンディングフォ−ム法試験治具に沿わせて固定した後、試験片に薬液（フタル酸２−エチルヘキシル）を塗布し、２３℃の環境下で４８時間放置した後、その外観の変化を目視にて観察した。外観に変化がないときを○、変化が少しあるときを△とした。
（塗装性）
ＪＩＳＫ−５４００に準拠した。即ち、平板状の試験片（１６０ｍｍ×６０ｍｍ、肉厚２．５ｍｍ）の表面に常温、相対湿度８０％の環境下に２液型ウレタン系塗料（関西ペイント（株）製ウレタンＰＧ６０）をスプレー塗装し、１２０時間経過後の塗膜の密着試験を行った。１ｍｍ角の桝目（１００個、ｎ＝２）に剥がれのないときを○とし、剥がれがあったときを×とした。
（ゴム状重合体の粒子径）
スペクトロニック２１Ｄ（Ｍｉｌｔｏｎ Ｒｏｙ製）にて５４６ｎｍの波長で重量平均粒子径を測定。
(Impact resistance)
Conforms to ASTM D-256. 1/8 inch, 23 ° C and -30 ° C.
(Liquidity)
Using a capillograph (Capillograph IC manufactured by Toyo Seiki Seisakusho Co., Ltd.), the melt viscosity (Pa · s) at a shear rate of 1000 sec −1 at a temperature of 260 ° C. was measured as an index of fluidity.
(Heat-resistant)
Conforms to ASTM D-648. 1/4 inch, 1.82 MPa load.
(Flexural modulus)
Conforms to ASTM D-790.
(chemical resistance)
After fixing a strip-shaped test piece (150 × 10 × 2 mm) produced by injection molding along a bending form method test jig, a chemical solution (2-ethylhexyl phthalate) was applied to the test piece, and 23 After leaving for 48 hours in an environment of 0 ° C., the change in the appearance was visually observed. The case where there was no change in the appearance was marked as ◯, and the case where there was a slight change was marked as Δ.
(Paintability)
Conforms to JISK-5400. That is, a two-component urethane paint (Urethane PG60 manufactured by Kansai Paint Co., Ltd.) is spray-coated on the surface of a flat test piece (160 mm x 60 mm, wall thickness 2.5 mm) in an environment of room temperature and relative humidity of 80%. And the adhesion test of the coating film after 120 hours passed was conducted. When the squares of 1 mm square (100 pieces, n = 2) were not peeled, “◯” was given, and when they were peeled, “x” was given.
(Rubber polymer particle size)
The weight average particle diameter was measured at a wavelength of 546 nm using Spectrotronic 21D (manufactured by Milton Roy).
表１及び表２において、Ａはポリアミド樹脂（宇部興産（株）製ナイロン６（１０２２Ｂ））、Ｂ−１は、膨潤度３６、重量平均粒子径３２０ｎｍのゴム状重合体を６５％含有し、スチレン／アクリロニトリル重量比３０／７０、アセトン可溶分の数平均分子量２２０００のグラフト重合体、Ｂ−２は、膨潤度４１、重量平均粒子径２９０ｎｍのゴム状重合体を５０％含有し、スチレン／アクリロニトリル重量比２３／７７、アセトン可溶分の数平均分子量４９０００のグラフト重合体、Ｃ−１は、メタクリル酸含有量１．０％、数平均分子量５００００のメタクリル酸変性共重合体、Ｃ−２は、メタクリル酸含有量３．０％、数平均分子量４４０００のメタクリル酸変性共重合体、Ｃ−３は、メタクリル酸含有量３．０％、数平均分子量２６０００のメタクリル酸変性共重合体、Ｃ−４は、メタクリル酸含有量５．０％、数平均分子量４６０００のメタクリル酸変性共重合体、Ｃ−５は、メタクリル酸含有量３．０％、数平均分子量２００００のメタクリル酸変性共重合体、Ｄ−１は、アクリロニトリル／スチレン重量比３２／６８、重量平均分子量８９０００の共重合体、Ｄ−２は、アクリロニトリル／スチレン重量比２４／７６、重量平均分子量６００００の共重合体である。 In Tables 1 and 2, A is a polyamide resin (Nylon 6 (1022B) manufactured by Ube Industries, Ltd.), B-1 contains 65% of a rubbery polymer having a degree of swelling of 36 and a weight average particle size of 320 nm, Graft polymer having a styrene / acrylonitrile weight ratio of 30/70 and an acetone-soluble number average molecular weight of 22000, B-2 contains 50% of a rubbery polymer having a degree of swelling of 41 and a weight average particle diameter of 290 nm. Graft polymer having acrylonitrile weight ratio of 23/77, acetone-soluble number average molecular weight 49000, C-1 is methacrylic acid-modified copolymer having 1.0% methacrylic acid content and 50000 number average molecular weight, C-2 Is a methacrylic acid-modified copolymer having a methacrylic acid content of 3.0% and a number average molecular weight of 44000, and C-3 is a methacrylic acid content of 3.0% and a number average molecular weight of 2 000 methacrylic acid-modified copolymer, C-4 has a methacrylic acid content of 5.0% and a number-average molecular weight of 46,000 methacrylic acid-modified copolymer, and C-5 has a methacrylic acid content of 3.0%. Methacrylic acid-modified copolymer having an average molecular weight of 20000, D-1 is a copolymer having an acrylonitrile / styrene weight ratio of 32/68 and a weight average molecular weight of 89000, D-2 is an acrylonitrile / styrene weight ratio of 24/76, and a weight average It is a copolymer having a molecular weight of 60000.
比較例１による熱可塑性樹脂組成物は、不飽和カルボン酸変性共重合体を含有しておらず、耐衝撃性、流動性、塗装性等に劣っている。これに対して、実施例１〜６による熱可塑性樹脂組成物はいずれも、耐衝撃性にすぐれているのみならず、耐衝撃性と流動性のバランスにすぐれている。また、比較例２による熱可塑性樹脂組成物は、用いた不飽和カルボン酸変性共重合体の数平均分子量が２００００であるので、実施例１及び２による熱可塑性樹脂組成物と比較して明らかなように、耐薬品性や塗装性に劣っている。
The thermoplastic resin composition according to Comparative Example 1 does not contain an unsaturated carboxylic acid-modified copolymer, and is inferior in impact resistance, fluidity, paintability, and the like. On the other hand, the thermoplastic resin compositions according to Examples 1 to 6 are not only excellent in impact resistance, but also in excellent balance between impact resistance and fluidity. Further, the number average molecular weight of the unsaturated carboxylic acid-modified copolymer used in the thermoplastic resin composition according to Comparative Example 2 is 20000, so that it is clear compared with the thermoplastic resin compositions according to Examples 1 and 2. As such, it is inferior in chemical resistance and paintability.
Claims (6)
（Ｂ）膨潤度１５〜４５（但し、膨潤度は、ゴム状重合体を１ｇ精秤し、これを５０ｇのトルエン中に温度２３℃で４８時間浸漬して、ポリマーを膨潤させた後、トルエンをデカンテーションにて除き、ここで、膨潤したポリマーを精秤した後、８０℃で２４時間減圧乾燥して、ポリマーが吸収したトルエンを蒸発、除去し、再び、精秤して、ＷS を膨潤したポリマーの重量とし、Ｗ0 を乾燥したポリマーの重量とするとき、式（ＷS−Ｗ0)／Ｗ0 により算出される値である。）、重量平均粒子径１００〜６００ｎｍのゴム状重合体４０〜８０重量％の存在下に、芳香族ビニル系単量体５０〜９０重量％、シアン化ビニル系単量体１０〜５０重量％及び上記単量体に共重合性を有するその他のビニル単量体０〜３０重量％からなる単量体混合物２０〜６０重量％をグラフト重合してなり、アセトン可溶分の数平均分子量が２００００〜１０００００のグラフト重合体２０〜８０重量部と、
（Ｃ）メタクリル酸０．８〜７重量％、スチレン６０〜８５．２重量％及びアクリロニトリル１４〜３３重量％を共重合してなる数平均分子量２６０００〜４６０００の不飽和カルボン酸変性共重合体１０〜２４重量部と、
（Ｄ）スチレン５０〜９０重量％及びアクリロニトリル１０〜５０重量％を共重合してなる共重合体５〜２９重量部（但し、上記（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）の合計を１００重量部とする。）とからなることを特徴とする熱可塑性樹脂組成物。 (A) 20-80 parts by weight of polyamide resin;
(B) Swelling degree 15 to 45 (however, the swelling degree is determined by weighing 1 g of a rubbery polymer and immersing it in 50 g of toluene at a temperature of 23 ° C. for 48 hours to swell the polymer. except by decantation, wherein, after precisely weighed swollen polymer, and dried under reduced pressure for 24 hours at 80 ° C., the polymer has absorbed toluene evaporated to remove again, and precisely weighed, and W S When the weight of the swollen polymer is used and W 0 is the weight of the dried polymer, this is a value calculated by the formula (W S −W 0 ) / W 0. ), Rubber-like having a weight average particle diameter of 100 to 600 nm In the presence of 40 to 80% by weight of polymer, 50 to 90% by weight of aromatic vinyl monomer, 10 to 50% by weight of vinyl cyanide monomer, and other monomers having copolymerizability with the above monomer Monomer mixture consisting of 0-30% by weight vinyl monomers 20 to 60% by weight of graft polymer, 20 to 80 parts by weight of a graft polymer having an acetone-soluble number average molecular weight of 20,000 to 100,000,
(C) Unsaturated carboxylic acid-modified copolymer 10 having a number average molecular weight of 2600 to 46000, obtained by copolymerizing methacrylic acid 0.8 to 7 % by weight, styrene 60 to 85.2 % by weight, and acrylonitrile 14 to 33 % by weight. ~ 24 parts by weight;
(D) 5 to 29 parts by weight of a copolymer obtained by copolymerizing 50 to 90% by weight of styrene and 10 to 50% by weight of acrylonitrile (however, the above (A), (B), (C) and (D) A total of 100 parts by weight.) A thermoplastic resin composition characterized by comprising:
（Ｂ）膨潤度１５〜４５（但し、膨潤度は、ゴム状重合体を１ｇ精秤し、これを５０ｇのトルエン中に温度２３℃で４８時間浸漬して、ポリマーを膨潤させた後、トルエンをデカンテーションにて除き、ここで、膨潤したポリマーを精秤した後、８０℃で２４時間減圧乾燥して、ポリマーが吸収したトルエンを蒸発、除去し、再び、精秤して、ＷS を膨潤したポリマーの重量とし、Ｗ0 を乾燥したポリマーの重量とするとき、式（ＷS−Ｗ0)／Ｗ0 により算出される値である。）、重量平均粒子径１００〜６００ｎｍのゴム状重合体４０〜８０重量％の存在下に、芳香族ビニル系単量体４０〜９０重量部、シアン化ビニル系単量体１０〜４０重量部及び上記単量体に共重合性を有するその他のビニル単量体０〜２０重量部からなる単量体混合物（但し、上記芳香族ビニル系単量体、シアン化ビニル系単量体及びその他のビニル単量体の合計は１００重量部である。）２０〜６０重量％をグラフト重合してなり、アセトン可溶分の数平均分子量が２００００〜１０００００のグラフト重合体３０〜３００重量部と、
（Ｃ）メタクリル酸０．８〜７重量％、スチレン６０〜８５．２重量％及びアクリロニトリル１４〜３３重量％を共重合してなる数平均分子量２６０００〜４６０００の不飽和カルボン酸変性共重合体１７〜８０重量部と、
（Ｄ）スチレン５０〜９０重量％及びアクリロニトリル１０〜５０重量％を共重合してなる共重合体８〜９７重量部とからなることを特徴とする熱可塑性樹脂組成物。 (A) 100 parts by weight of a polyamide resin;
(B) Swelling degree 15 to 45 (however, the swelling degree is determined by weighing 1 g of a rubbery polymer and immersing it in 50 g of toluene at a temperature of 23 ° C. for 48 hours to swell the polymer. except by decantation, wherein, after precisely weighed swollen polymer, and dried under reduced pressure for 24 hours at 80 ° C., the polymer has absorbed toluene evaporated to remove again, and precisely weighed, and W S The weight of the swollen polymer, where W 0 is the weight of the dried polymer, and is a value calculated by the formula (W S −W 0 ) / W 0. ), Rubber-like having a weight average particle diameter of 100 to 600 nm In the presence of 40 to 80% by weight of polymer, 40 to 90 parts by weight of aromatic vinyl monomer, 10 to 40 parts by weight of vinyl cyanide monomer, and other monomers having copolymerizability with the above monomer Monomer mixture comprising 0 to 20 parts by weight of vinyl monomer (However, the total of the above aromatic vinyl monomer, vinyl cyanide monomer and other vinyl monomers is 100 parts by weight.) 20-60% by weight is graft-polymerized and acetone is acceptable. 30 to 300 parts by weight of a graft polymer having a number average molecular weight of a solute of 20,000 to 100,000,
(C) Unsaturated carboxylic acid-modified copolymer 17 having a number average molecular weight of 2600 to 46000, which is obtained by copolymerizing 0.8 to 7% by weight of methacrylic acid, 60 to 85.2% by weight of styrene and 14 to 33% by weight of acrylonitrile. ~ 80 parts by weight,
(D) A thermoplastic resin composition comprising 8 to 97 parts by weight of a copolymer obtained by copolymerizing 50 to 90% by weight of styrene and 10 to 50 % by weight of acrylonitrile.
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