JP2004131716A - 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。 (4) The present invention relates to a thermoplastic resin composition having excellent impact resistance, in particular, excellent balance between impact resistance at low temperature and fluidity, and also having excellent chemical resistance and coating properties.
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 resin is excellent in chemical resistance, mechanical strength, heat resistance, abrasion resistance, etc., and is widely used as electric and electronic parts, mechanical parts and automobile parts, but has the disadvantage of poor impact resistance. Have. On the other hand, rubber-reinforced styrene resins such as HIPS (high impact styrene copolymer resin), ABS resin (acrylonitrile-butadiene-styrene copolymer resin), and AES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer resin) ), 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, electric parts and the like. However, it has a disadvantage that it is inferior in chemical resistance and abrasion 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, in order to compensate for the mutual disadvantages of these resins, a blend of a polyamide resin and an ABS resin has been proposed (see Patent Document 1). However, since the polyamide resin and the ABS resin have poor compatibility, an unsaturated carboxylic acid-modified copolymer obtained by copolymerizing an unsaturated carboxylic acid with styrene or acrylonitrile is blended as a compatibilizer with the polyamide resin and the ABS resin. (See Patent Literature 2), and some improvement in impact resistance has been obtained with such improvement in compatibility.
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, as home appliances and automotive parts have become larger and thinner, the molding cycle has been improved and the productivity has been improved. / A rubber-reinforced styrenic resin composition, in particular, a polyamide resin / ABS resin composition has been required.
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 the polyamide resin / rubber reinforced styrenic resin composition, and has an excellent balance between impact resistance and fluidity, and further has an excellent chemical resistance and paintability. It is an object of the present invention 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のグラフト重合体２０〜８０重量部と、
（Ｃ）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の不飽和カルボン酸変性共重合体０．５〜６０重量部と、
（Ｄ）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％及び上記単量体と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０〜５０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 to 80 parts by weight of a polyamide resin,
(B) 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 diameter of 100 to 600 nm, 50 to 90% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer A graft polymerization of 20 to 60% by weight of a monomer mixture consisting of 10 to 50% by weight of a monomer and 0 to 30% by weight of another vinyl monomer copolymerizable with the above monomer, 20-80 parts by weight of a graft polymer having a number average molecular weight of 20,000 to 200,000,
(C) A number obtained by copolymerizing 0.05 to 20% by weight of an unsaturated carboxylic acid monomer, 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% by weight of a vinyl cyanide monomer. 0.5 to 60 parts by weight of an unsaturated carboxylic acid-modified copolymer having an average molecular weight of 22,000 to 60000,
(D) 50 to 90% by weight of an aromatic vinyl monomer, 10 to 50% by weight of a vinyl cyanide monomer and 0 to 60% by weight of another vinyl monomer copolymerizable with the above monomer From 0 to 50 parts by weight (provided that the total of the above (A), (B), (C) and (D) is 100 parts by weight). The present invention provides a thermoplastic resin composition.
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のグラフト重合体３０〜３００重量部と、
（Ｃ）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の不飽和カルボン酸変性共重合体１〜２５０重量部と、
（Ｄ）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％及び上記単量体と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０〜１２０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,
(A) 100 parts by weight of a polyamide resin,
(B) 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 diameter of 100 to 600 nm, 40 to 90 parts by weight of an aromatic vinyl monomer and vinyl cyanide monomer Monomer mixture consisting of 10 to 40 parts by weight of a polymer and 0 to 20 parts by weight of another vinyl monomer copolymerizable with the above monomer (provided that the above aromatic vinyl monomer, vinyl cyanide The total amount of the monomer and the other vinyl monomer is 100 parts by weight.) Graft polymerization of 20 to 60% by weight, and a graft polymer having a number average molecular weight of 20,000 to 200,000 of an acetone-soluble component is 30 to 20%. 300 parts by weight,
(C) 0.05 to 20% by weight of an unsaturated carboxylic acid monomer, 45 to 89.95% by weight of an aromatic vinyl monomer and 10 to 35% by weight of a vinyl cyanide monomer are copolymerized. 1 to 250 parts by weight of an unsaturated carboxylic acid-modified copolymer having a number average molecular weight of 22,000 to 60,000,
(D) 45 to 90% by weight of an aromatic vinyl monomer, 10 to 45% by weight of a vinyl cyanide monomer, and 0 to 10% by weight of another vinyl monomer copolymerizable with the above monomer And a thermoplastic resin composition comprising 0 to 120 parts by weight of a copolymer obtained by copolymerizing
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 compatibilizer, and, if necessary, an aromatic vinyl monomer-vinyl cyanide. Acetonitrile-based copolymer, which has a number-average molecular weight in a range where acetone-soluble components are limited as a graft polymer in a rubber-reinforced styrene-based resin, and has an unsaturated carboxylic acid-modified copolymer. Has a number average molecular weight in a limited range, so that it has excellent impact resistance and fluid balun, as well as excellent 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, as the polyamide resin (A), for example, 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) methanedodecamide, Polybis (3-methyl-4-amino (Cyclohexyl) methandodecamide, polymethaxylylene adipamide, nylon 11T, polyundecamethylenehexahydroterephthalamide, polyamide elastomer and the like. In the above, I indicates an isophthalic acid component, and T indicates 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。 According to the present invention, among these, nylon 6, nylon 46, nylon 66, nylon 12, nylon 6T / 6I, nylon 6 / 6T and nylon 66 / 6T are particularly preferably used.
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) refers to an aromatic vinyl-based monomer 50 to 80% by weight in the presence of a rubbery polymer 40 to 80% by weight having a swelling degree of 10 to 80 and a weight average particle diameter of 100 to 600 nm. 90 to 60% by weight of a monomer mixture comprising 90% by weight, 10 to 50% by weight of a vinyl cyanide monomer and 0 to 30% by weight of another vinyl monomer copolymerizable with the above monomer. It is obtained by graft polymerization and has a number average molecular weight in the range of 20,000 to 200,000, 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) is an aromatic vinyl monomer 40-80% by weight in the presence of 40-80% by weight of a rubbery polymer having a swelling degree of 10 to 80 and a weight average particle diameter of 100 to 600 nm. To 90 parts by weight, 10 to 40 parts by weight of a vinyl cyanide-based monomer, and 0 to 20 parts by weight of another vinyl monomer copolymerizable with the above monomer (however, The total of the vinyl group-based monomer, vinyl cyanide-based monomer and other vinyl monomer is 100 parts by weight.) Graft polymerization of 20 to 60% by weight is carried out, and the number average of acetone-soluble components is increased. It refers to those having a molecular weight 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, examples of the rubbery polymer used for the production of the graft polymer include conjugated diene rubbers represented by, for example, 1,3-polybutadiene and polyisoprene, and conjugated dienes and monomers 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 styrene, aromatic vinyl monomers such as α-methylstyrene, acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, and methyl Examples thereof include unsaturated carboxylic acid alkyl ester monomers such as acrylate, ethyl acrylate, and methyl methacrylate. Accordingly, 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, if necessary, copolymerizing them. It can be obtained by graft-polymerizing other vinyl monomers having the same. 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-based monomer include acrylonitrile, methacrylonitrile, and the like. These may be 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 between the aromatic vinyl monomer and the vinyl cyanide monomer include, for example, maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide, O-chloro-N Maleimide monomers such as -phenylmaleimide; and unsaturated carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and 2-ethylhexyl acrylate.
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、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、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、このポリマーを約１ｇ精秤し、これを約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。 According to the present invention, the rubbery polymer used for producing the graft polymer has a swelling degree in the range of 10 to 80, preferably 15 to 50, particularly preferably 25 to 45. Here, the degree of swelling is a value obtained as follows. That is, the latex is coagulated and dried to obtain a polymer. About 1 g of the polymer is precisely weighed and immersed in about 50 g of toluene at a temperature of 23 ° C. for 48 hours to swell the polymer. After removing by decantation, the swollen polymer was precisely weighed, and then 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 The degree of swelling = (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。 Where 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 obtained 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の範囲にあることが好ましく、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。 Furthermore, according to the present invention, the rubbery polymer used for producing the graft polymer preferably has a weight average particle diameter in the range of 100 to 600 nm, and 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 size, they may be directly used for the production of the graft polymer, and if necessary, the rubber-like polymer may be used. The coalesced particles may be agglomerated and enlarged, and used for the production of the graft polymer. In order to coagulate and enlarge the rubber-like polymer particles, as is well known, mechanical coagulation may be performed, 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。 (4) In the present invention, the number average molecular weight of the acetone-soluble component of the thus obtained graft polymer is in the range of 20,000 to 200,000. When the number average molecular weight of the acetone-soluble component of the graft polymer is smaller than 20,000, the obtained thermoplastic resin composition is inferior in impact resistance. On the other hand, when it exceeds 200,000, the obtained thermoplastic resin composition is Poor fluidity. In the present invention, the number average molecular weight of the acetone-soluble component of the graft polymer is preferably in the range of 20,000 to 100,000, and particularly preferably in the range of 20,000 to 60,000. 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 polymerization method, a solution polymerization method, or a combination thereof can be used as appropriate.
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) refers to 0.05 to 20% by weight of an unsaturated carboxylic acid monomer, 50 to 90% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer. It is a copolymer having a number average molecular weight of 22,000 to 60000 obtained by copolymerizing 10 to 50% by weight of a monomer.
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 0.05 to 20% by weight of an unsaturated carboxylic acid monomer and 45 to 89.95% by weight of an aromatic vinyl monomer. % And a vinyl cyanide monomer in an amount of from 10 to 35% by weight. According to a more preferred embodiment, the unsaturated carboxylic acid-modified copolymer (C) contains 0.5 to 10% by weight of an unsaturated carboxylic acid monomer, 55 to 87.5% by weight of an aromatic vinyl monomer and It is a copolymer obtained by copolymerizing 12 to 35% by weight of a vinyl cyanide-based monomer. According to the most preferred embodiment, the unsaturated carboxylic acid-modified copolymer (C) is an unsaturated carboxylic acid monomer. 0.8 to 7% by weight of a copolymer, 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 forming the unsaturated carboxylic acid-modified copolymer (C) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and these may be used alone or Used as a mixture of two or more. Of these, methacrylic acid is particularly preferably used. As the aromatic vinyl monomer and the vinyl cyanide monomer, the same ones used in 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 an unsaturated carboxylic acid ester monomer 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 obtained resin composition has an excellent 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 22,000, the obtained resin composition is inferior in chemical resistance and paintability, while when it exceeds 60000, the obtained resin composition The material is inferior in fluidity. Here, the number average molecular weight of the unsaturated carboxylic acid-modified copolymer (C) is a molecular weight measured by dissolving the copolymer in tetrahydrofuran and measuring by GPC (gel permeation chromatography).
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％以下であるときは、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。 When the amount of the unsaturated carboxylic acid monomer in the unsaturated carboxylic acid-modified copolymer (C) is 0.05% by weight or less, the copolymer has poor compatibility with the resin composition. Therefore, the obtained resin composition is inferior in impact resistance and coatability, and when it exceeds 20% by weight, the fluidity of the obtained resin composition is remarkably reduced.
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 an impact resistance and coating property. When the resin composition is inferior, on the other hand, too much, the resin composition has poor 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, as described above, 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 unsaturated carboxylic acid-modified copolymer (C) in the range of 0.7 to 8% by weight is blended with the resin composition in an appropriate range, so that the compatibility between the polyamide resin and the styrene-based resin is improved. And a thermoplastic resin composition having an excellent balance between impact resistance and fluidity, and particularly excellent in impact resistance 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 method for producing the unsaturated carboxylic acid-modified copolymer (C) is also not limited at all, and may be any conventionally known suitable method, for example, an emulsion polymerization method, a bulk polymerization method, or a suspension polymerization method. And a solution polymerization method. 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, and, for example, t-dodecyl mercaptan. It can be arbitrarily adjusted depending on the type and amount of the polymerization chain transfer agent such as above.
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) refers to 50 to 90% by weight of an aromatic vinyl monomer, 10 to 50% by weight of a vinyl cyanide monomer, and another vinyl monomer having copolymerizability with these. It is a copolymer obtained by copolymerizing 0 to 60% by weight of a monomer. According to a preferred embodiment, the copolymer (D) comprises 45 to 90% by weight of an aromatic vinyl-based monomer, 10 to 45% by weight of a vinyl cyanide-based monomer and other vinyl copolymerizable therewith. It is a copolymer obtained by copolymerizing 0 to 10% by weight of a monomer.
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。 芳香 As the aromatic vinyl monomer and the vinyl cyanide monomer, the same ones as those used in the production of the graft polymer (B) are used. Further, as the other vinyl monomer having copolymerizability, for example, maleimide-based monomer such as maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, O-chloro-N-phenylmaleimide And unsaturated carboxylic acid ester-based monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and 2-ethylhexyl acrylate.
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 weight average molecular weight of the copolymer (D) is not particularly limited, 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 an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a solution polymerization method which are conventionally known.
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 0 to 80 parts by weight of 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). When such a component is out of this range, a thermoplastic resin having desired characteristics cannot be obtained. In particular, for the unsaturated carboxylic acid-modified copolymer (C), the range of 1 to 35 parts by weight is preferable.
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) 1 to 3 parts of an unsaturated carboxylic acid-modified copolymer. (A) 100 parts by weight of a polyamide resin, (B) 30 to 150 parts by weight of a graft polymer, and (C) an unsaturated carboxylic acid. It is composed of 1 to 120 parts by weight of an acid-modified copolymer and 0 to 120 parts by weight of a copolymer (D), most preferably (A) 100 parts by weight of a polyamide resin, and (B) 35 to 130 parts by weight of a 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 a 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, the content of the rubbery polymer in the entire resin composition is preferably in the range of 8 to 40% by weight from the viewpoint of the balance of physical properties of the obtained thermoplastic resin composition. In particular, the content is preferably in the range of 10 to 25% by weight.
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-mentioned polyamide resin (A), graft polymer (B), unsaturated carboxylic acid-modified copolymer (C) and copolymer (D). , But the order of mixing is not limited at all. Therefore, for example, all the components may be mixed together at the same time, or, for example, after any one of the two components is first preliminarily mixed, the remaining two components are added thereto and mixed. Is also good. When the mixture of such components is melt-mixed, an extruder, a Banbury mixer, a roll mill, or the like can be used.
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、カーボン繊維、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。 Further, if necessary, the above-mentioned components include α-olefins such as polyethylene and polypropylene, α-olefin copolymers thereof, styrene-based resins such as polystyrene and high-impact styrene, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, and polymethyl methacrylate. Other thermoplastic resins such as acrylate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyethersulfone, polyimide, polyetherimide, and polyetheretherketone, as well as antioxidants, ultraviolet absorbers, light stabilizers, and antistatic agents Add various additives such as lubricants, dyes, pigments, plasticizers, flame retardants, release agents, glass fibers, carbon fibers, metal fibers, carbon fibers, metal flakes, talc, graphite, reinforcing materials, fillers, etc. can do.
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。 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
(Production of rubbery polymer)
A pressure vessel is charged with 100 parts of 1,3-butadiene, 0.3 parts of t-dodecyl mercaptan, 0.25 parts 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 terminating the polymerization in 20 hours had a solid content of 37%, a weight average particle diameter of 65 nm, and a degree of swelling 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 diameter of 50 nm, and a degree of swelling 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 swelling degree 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. %, A degree of swelling of 41, and a weight-average particle diameter of 300 nm to obtain an enlarged diene rubber latex (b-2).
（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)
A stainless steel container was charged with 50 parts (solid content) of the enlarged diene rubber latex (b-1), 1.5 parts of sodium dodecylbenzenesulfonate and 0.3 parts of potassium persulfate. 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-based antioxidant per 100 parts by weight (solid content) of the graft polymer latex, the mixture is coagulated, dehydrated and dried using magnesium sulfate to obtain a graft weight. Combined B-1 was obtained. The degree of swelling of the rubbery polymer in the graft polymer B-1 was 36, the weight average particle diameter was 320 nm, the content of the rubbery 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。 Further, in the production of the above graft polymer, a polymerization temperature is set to 50 ° C. by a redox catalyst system using cumene hydroperoxide as an initiator and ferrous sulfate as a reducing agent, and a monomer mixture comprising styrene and acrylonitrile is used. Was added in the initial stage to obtain a graft polymer B-2 in the same manner as described above. The degree of swelling of the rubbery polymer in the graft polymer B-2 was 41, the weight average particle diameter was 290 nm, the content of the rubbery 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. After continuously adding 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 over 5 hours, the temperature of the reaction system was raised to 70 ° C, Aging was performed at this temperature for 1 hour to complete the polymerization. Thereafter, 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, the 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 composed of 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, except that a monomer mixture consisting of 73 parts of styrene, 24 parts of acrylonitrile, 3 parts of methacrylic acid and 1 part of t-dodecylmercaptan 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 26,000.
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 consisting 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 46,000.
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, except that a monomer mixture consisting 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 production of the methacrylic acid-modified copolymer C-2. In the same manner as in the above, methacrylic acid-modified copolymer C-5 was obtained. The number average molecular weight of the obtained methacrylic acid-modified copolymer C-5 was 20,000.
（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)
200 parts of pure water and 0.3 part of potassium persulfate were charged into a pressure vessel, and the temperature was raised to 65 ° C. with stirring. After continuously adding a monomer mixture consisting of 70 parts of styrene, 30 parts of acrylonitrile and 0.3 part of t-dodecylmercaptan and 30 parts of an aqueous emulsifier solution containing 2 parts of sodium dodecylbenzenesulfonate over 5 hours, the reaction system was added. 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。 (4) Copolymer D-2 was obtained in the same manner as described above except that 1.2 parts of t-dodecyl mercaptan was used in the production of copolymer D-1. The number average molecular weight of the obtained copolymer D-2 was 60000.
実施例１〜１１、比較例１及び２
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 to 11, Comparative Examples 1 and 2
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 the mixture was 30 mm biaxial. The mixture was melt-mixed at 250 ° C. using an extruder, pelletized, injection-molded, 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, in the table, the numerical value in parentheses of each component of the resin composition 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℃。
（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。
(Shock resistance)
Conforms to ASTM D-256. 1/8 inch, 23 ° C.
(Liquidity)
Using a Capillograph (Capillograph IC manufactured by Toyo Seiki Seisaku-Sho, Ltd.), the melt viscosity (Pa · s) at a temperature of 260 ° C. and a shear rate of 1000 sec −1 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) prepared by injection molding along a bending jig method test jig, a chemical solution (2-ethylhexyl phthalate) was applied to the test piece. After being left for 48 hours in an environment of ° C., the appearance change was visually observed. When there was no change in the appearance, it was evaluated as ○, and when there was a slight change, as Δ.
(Paintability)
It conformed to JISK-5400. That is, a two-component urethane-based paint (urethane PG60 manufactured by Kansai Paint Co., Ltd.) is spray-coated on the surface of a flat test piece (160 mm × 60 mm, wall thickness 2.5 mm) under an environment of normal temperature and relative humidity of 80%. After 120 hours, the coating film was subjected to an adhesion test. When there was no peeling in the 1 mm square cells (100, n = 2), it was evaluated as ○, and when there was peeling, it was evaluated as ×.
(Particle size of rubbery polymer)
The weight average particle diameter was measured at a wavelength of 546 nm using Spectronic 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.), and B-1 contains 65% of a rubbery polymer having a swelling degree of 36 and a weight average particle diameter of 320 nm, A graft polymer having a styrene / acrylonitrile weight ratio of 30/70 and an acetone-soluble component having a number average molecular weight of 22,000, B-2 contains 50% of a rubbery polymer having a swelling degree of 41 and a weight average particle diameter of 290 nm, A graft polymer having an acrylonitrile weight ratio of 23/77 and an acetone-soluble component having a number average molecular weight of 49000, C-1 is a methacrylic acid-modified copolymer having a methacrylic acid content of 1.0% and a number average molecular weight of 50,000, and 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. A methacrylic acid-modified copolymer of 6000, C-4 is a methacrylic acid content of 5.0%, a methacrylic acid-modified copolymer of a number average molecular weight of 46,000, and C-5 is a methacrylic acid content of 3.0%, A methacrylic acid-modified copolymer having an average molecular weight of 20,000, D-1 is an acrylonitrile / styrene weight ratio of 32/68, a copolymer having a weight average molecular weight of 89000, D-2 is an acrylonitrile / styrene weight ratio of 24/76, 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１〜１１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 did not contain an unsaturated carboxylic acid-modified copolymer, and was inferior in impact resistance, fluidity, coatability, and the like. On the other hand, all of the thermoplastic resin compositions according to Examples 1 to 11 are excellent not only in impact resistance but also in balance between impact resistance and fluidity. In addition, the thermoplastic resin composition according to Comparative Example 2 had a number average molecular weight of 20,000 of the unsaturated carboxylic acid-modified copolymer used, and thus was clearly compared with the thermoplastic resin compositions according to Examples 1 and 2. Thus, it is inferior in chemical resistance and paintability.
Claims (10)
（Ｂ）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のグラフト重合体２０〜８０重量部と、
（Ｃ）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の不飽和カルボン酸変性共重合体０．５〜６０重量部と、
（Ｄ）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％及び上記単量体と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０〜５０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 to 80 parts by weight of a polyamide resin,
(B) 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 diameter of 100 to 600 nm, 50 to 90% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer A graft polymerization of 20 to 60% by weight of a monomer mixture consisting of 10 to 50% by weight of a monomer and 0 to 30% by weight of another vinyl monomer copolymerizable with the above monomer, 20-80 parts by weight of a graft polymer having a number average molecular weight of 20,000 to 200,000,
(C) A number obtained by copolymerizing 0.05 to 20% by weight of an unsaturated carboxylic acid monomer, 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% by weight of a vinyl cyanide monomer. 0.5 to 60 parts by weight of an unsaturated carboxylic acid-modified copolymer having an average molecular weight of 22,000 to 60000,
(D) 50 to 90% by weight of an aromatic vinyl monomer, 10 to 50% by weight of a vinyl cyanide monomer and 0 to 60% by weight of another vinyl monomer copolymerizable with the above monomer From 0 to 50 parts by weight (provided that the total of the above (A), (B), (C) and (D) is 100 parts by weight). Thermoplastic resin composition.
（Ｂ）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のグラフト重合体３０〜３００重量部と、
（Ｃ）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の不飽和カルボン酸変性共重合体１〜２５０重量部と、
（Ｄ）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％及び上記単量体と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０〜１２０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) 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 diameter of 100 to 600 nm, 40 to 90 parts by weight of an aromatic vinyl monomer and vinyl cyanide monomer Monomer mixture consisting of 10 to 40 parts by weight of a polymer and 0 to 20 parts by weight of another vinyl monomer copolymerizable with the above monomer (provided that the above aromatic vinyl monomer, vinyl cyanide The total amount of the monomer and the other vinyl monomer is 100 parts by weight.) Graft polymerization of 20 to 60% by weight, and a graft polymer having a number average molecular weight of 20,000 to 200,000 of an acetone-soluble component is 30 to 20%. 300 parts by weight,
(C) 0.05 to 20% by weight of an unsaturated carboxylic acid monomer, 45 to 89.95% by weight of an aromatic vinyl monomer and 10 to 35% by weight of a vinyl cyanide monomer are copolymerized. 1 to 250 parts by weight of an unsaturated carboxylic acid-modified copolymer having a number average molecular weight of 22,000 to 60,000,
(D) 45 to 90% by weight of an aromatic vinyl monomer, 10 to 45% by weight of a vinyl cyanide monomer, and 0 to 10% by weight of another vinyl monomer copolymerizable with the above monomer A thermoplastic resin composition comprising 0 to 120 parts by weight of a copolymer obtained by copolymerizing
The thermoplastic resin composition according to claim 1, comprising a rubber-like polymer in a range of 10 to 25% by weight.
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| JP2009091421A (en) * | 2007-10-05 | 2009-04-30 | Umg Abs Ltd | Thermoplastic resin composition and molded article |
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| JP2016188292A (en) * | 2015-03-30 | 2016-11-04 | 東レ株式会社 | Thermoplastic resin composition and molded product thereof |
| WO2017130931A1 (en) * | 2016-01-28 | 2017-08-03 | 東洋紡株式会社 | Heat-aging-resistant polyamide resin composition |
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