JP4013338B2 - Thermoplastic resin composition excellent in paintability and molded article for automobile - Google Patents
Thermoplastic resin composition excellent in paintability and molded article for automobile Download PDFInfo
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- JP4013338B2 JP4013338B2 JP17598798A JP17598798A JP4013338B2 JP 4013338 B2 JP4013338 B2 JP 4013338B2 JP 17598798 A JP17598798 A JP 17598798A JP 17598798 A JP17598798 A JP 17598798A JP 4013338 B2 JP4013338 B2 JP 4013338B2
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- 239000011342 resin composition Substances 0.000 title claims description 26
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 20
- 229920000642 polymer Polymers 0.000 claims description 77
- 239000000178 monomer Substances 0.000 claims description 52
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 51
- 229920000578 graft copolymer Polymers 0.000 claims description 31
- 229920001971 elastomer Polymers 0.000 claims description 30
- 239000005060 rubber Substances 0.000 claims description 27
- 229920002959 polymer blend Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 description 31
- 238000003786 synthesis reaction Methods 0.000 description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 13
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920003244 diene elastomer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 vinyl cyanide compound Chemical class 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、優れた塗装性を有し、耐衝撃性及び加工性のバランスも良好な、自動車用外装部品の成形材料として好適な熱可塑性樹脂組成物及びこのような熱可塑性樹脂組成物を成形して得られる自動車用成形品に関する。
【０００２】
【従来の技術】
ＡＢＳ樹脂は、優れた加工性、耐衝撃性、機械特性、耐薬品性を有していることから、車両分野、家電分野など、広範な分野において各種構成部材の成形材料として使用されている。例えば、近年、車両分野では、ＡＢＳ樹脂の優れた２次加工性、特に、塗装性に着目して、ドアミラー等の車両外装用途に使用展開が図られている。
【０００３】
しかし、塗装性は、樹脂組成物の特性や成形条件、塗装方法、塗装環境などの因子により影響を受け易く、著しい塗装不良を起こす場合がある。この塗装不良の中でも、塗料に含まれるシンナー等の溶媒が作用して起こるブリスター現象（塗装面に小さな穴が多数個発生する現象。）及び吸い込み現象（塗装面に微細な凹凸が発生し、光沢むらとして観察される現象。）は代表的な塗装不良に挙げられ、最終製品の商品価値を著しく損なわせる。
【０００４】
塗装後のブリスター現象は、経験的に近年のハイサイクル化や成形品の薄肉化に伴い発生し易く、特に冬場などの低温環境時に著しく発生し易いことから、塗装現場においてこの点の改良が強く望まれている。一方で、ブリスター現象は、一般的に吸い込み現象と相反する傾向にあり、これが改良対策を複雑化させている。
【０００５】
このような状況において、ブリスター現象と吸い込み現象を同時に改良するべく、従来、樹脂中のシアン化ビニル化合物の含有量を増やしたり、樹脂の分子量を高めたり、更には、使用するジエン系ゴムのゲル含有量、粒子径、グラフト構造の最適化が試みられてきたが、低温環境下におけるブリスター現象と吸い込み現象とを同時に改良し、しかも樹脂そのものの基本物性として要求される耐衝撃性及び加工性とのバランスを高く維持することは極めて困難であった。
【０００６】
特開平４−２５５５５号公報には、特定のシアン化ビニル化合物単位を含む樹脂と特定のゴム質共重合体を用い、かつ低分子量成分含有率を小さくすることで、ブリスター現象と吸い込み現象とを同時に解消した樹脂組成物が開示されている。
【０００７】
また、特開平９−２１６９２０号公報には、ジエン系ゴム質重合体の平均粒子径とその分布、組成物中の溶剤可溶分の還元粘度、及び該ゴム質重合体への単量体のグラフト率とグラフト層の厚みを規定することで、耐衝撃性、加工性及び塗装性を改善した樹脂組成物が開示されている。
【０００８】
しかしながら、本発明者等が追試した結果、上記いずれの樹脂組成物においても、夏場を想定した環境温度での塗装性には優れるものの、冬場を想定した低温環境下では、ブリスター現象が多数発生し、年間を通じての使用に耐えないことが判明した。
【０００９】
【発明が解決しようとする課題】
本発明は、上記従来の問題を解決し、塗装性に優れ、特に低温環境下におけるブリスター現象及び吸い込み現象が抑制され、かつ耐衝撃性及び加工性のバランスも良好で、自動車用外装部品の成形材料として好適な熱可塑性樹脂組成物を提供することを目的とする。
【００１０】
【課題を解決するための手段】
本発明の熱可塑性樹脂組成物は、ジエン系ゴム質重合体の存在下に芳香族ビニル及びシアン化ビニルを含む単量体混合物を共重合させてなるゴム含有グラフト共重合体であって、該ゴム含有グラフト共重合体中のジエン系ゴム質重合体の含有量は４０〜７０重量％であり、該芳香族ビニル及びシアン化ビニルを含む単量体混合物がグラフトした硬質重合体成分の重量平均分子量が２５００００〜４５００００であるゴム含有グラフト共重合体（Ａ）：１５〜５０重量部と、芳香族ビニル単量体及びシアン化ビニル単量体を含む硬質重合体であって、重量平均分子量が１０００００〜２０００００で、シアン化ビニル単量体を２０〜３０重量％含む硬質重合体（Ｂ−I）と、重量平均分子量が１０００００未満で、シアン化ビニル単量体を３５〜５０重量％含む硬質重合体（Ｂ−II）とを含む混合物であり、かつ該混合物中の硬質重合体（Ｂ−II）含有量が２０〜５０重量％である硬質重合体混合物（Ｂ）：８５〜５０重量部とを含むことを特徴とする。
【００１１】
ただし、本発明の熱可塑性樹脂組成物において、ゴム含有グラフト共重合体（Ａ）と硬質重合体混合物（Ｂ）とは、合計で１００重量部とする。
【００１２】
一般に、ブリスター現象は、射出成形時に成形品が冷却される過程で発生する残留応力の大きい部位にシンナー等の溶媒がアタックし、成形品表面にクラックを生じると共に溶媒がそのクラックに残留し、乾燥工程で膨張して塗装膜を突き破る現象であると考えられる。一方、吸い込み現象は、射出成形の過程で成形品に発生する樹脂の表層配向によりゴムが変形し、シンナー等の溶剤により応力緩和されるに伴い、塗装面に微細なクレーズが発生し光沢の低下をもたらす現象と考えられる。
【００１３】
特に、冬場の低温環境時にブリスター現象が起こりやすい原因の明確な因果関係は詳かではないが、成形品が急激に冷却され特定部位に残留応力が発生しやすいこと、塗料の溶剤が揮発しにくく樹脂をアタックしやすいことなどが挙げられる。
【００１４】
本発明者らは、上記知見に基き、塗装性、特に低温環境下におけるブリスター現象及び吸い込み現象を抑制し、かつ耐衝撃性及び加工性のバランスも良好な熱可塑性樹脂組成物を開発するべく鋭意研究を重ねた結果、特定のグラフト構造を持つジエン系ゴム質共重合体と、分子量、組成の規制された２種類の硬質共重合体を特定量ブレンドすることで、低温環境下でもブリスター現象及び吸い込み現象の発生しない塗装性に優れた樹脂組成物を得ることができ、同時に実用的な耐衝撃性及び加工性を達成することができることを見出し、本発明を完成させた。
【００１５】
本発明においては、特に、硬質重合体混合物（Ｂ）が硬質重合体（Ｂ−I）と硬質重合体（Ｂ−II）とからなり、硬質重合体（Ｂ−I）／硬質重合体（Ｂ−II）の重量比が１〜４であることが好ましく、とりわけ、硬質重合体混合物（Ｂ）が芳香族ビニル単量体とシアン化ビニル単量体とからなることが好ましい。
【００１６】
本発明の自動車用成形品は、このような本発明の熱可塑性樹脂組成物を成形してなるものである。
【００１７】
【発明の実施の形態】
以下に本発明の実施の形態を詳細に説明する。
【００１８】
本発明に係るゴム含有グラフト共重合体（Ａ）は、ジエン系ゴム質重合体の存在下に芳香族ビニル、シアン化ビニルを含む単量体混合物を共重合させてなるジエン系ゴム含有グラフト重合体である。
【００１９】
ゴム含有グラフト共重合体（Ａ）中のジエン系ゴム質重合体としては、ポリブタジエン、スチレン−ブタジエン、アクリロニトリル−ブタジエンなどのブタジエンとこれと共重合可能なビニル単量体との共重合体、ポリイソプレンなどが挙げられ、これらのうちの１種又は２種以上を用いることができる。
【００２０】
ゴム含有グラフト共重合体（Ａ）中のジエン系ゴム質重合体の含有量は、４０〜７０重量％であり、この含有量が４０重量％未満では耐衝撃性に劣り、７０重量％を超えてもグラフト率が低下することから耐衝撃性に劣るものとなる。
【００２１】
ゴム含有グラフト共重合体（Ａ）中の芳香族ビニル単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン、ブロムスチレン等が挙げられ、特にスチレン、α−メチルスチレンが好ましく、また、シアン化ビニル単量体としては、アクリロニトリル、メタクリロニトリル等が挙げられ、特にアクリロニトリルが好ましい。これらの単量体についても、１種又は２種以上を用いることができる。
【００２２】
ゴム含有グラフト共重合体（Ａ）中の芳香族ビニル単量体、シアン化ビニル単量体と共に用いることができる他の共重合可能な単量体としては、メタクリル酸メチル、アクリル酸メチル等のメタクリル酸又はアクリル酸エステル、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等のマレイミド化合物、アクリル酸、メタクリル酸、イタコン酸、フマル酸等の不飽和カルボン酸化合物が挙げられ、それぞれ１種又は２種以上用いることができる。
【００２３】
本発明に係るゴム含有グラフト共重合体（Ａ）において、芳香族ビニル単量体、シアン化ビニル単量体を含む混合物がグラフトした硬質重合体成分の重量平均分子量は、２５００００〜４５００００である。この重量平均分子量が２５００００未満では、吸い込み現象が発生し、４５００００を超えるとブリスター現象及び吸い込み現象が発生し易くなる。なお、本発明において、該硬質重合体成分の重量平均分子量は、ゴム含有グラフト共重合体（Ａ）をアセトンに溶解し、その不溶分を取り出してオゾン分解処理行い、硬質重合体成分を抽出し、これをＧ．Ｐ．Ｃ（ゲル・パーミエーション・クロマトグラフィー）を用いて標準ポリスチレン換算法にて算出した値である。
【００２４】
本発明の硬質重合体混合物（Ｂ）は、芳香族ビニル単量体とシアン化ビニル単量体と、更に必要に応じて用いられる共重合可能な他の単量体を共重合してなる硬質重合体からなり、ここで芳香族ビニル単量体とシアン化ビニル単量体と、更に必要に応じて用いられる共重合可能な他の単量体は、上述のゴム含有グラフト共重合体（Ａ）にグラフトさせる単量体と同様な単量体を使用することができる。
【００２５】
本発明の硬質重合体混合物（Ｂ）は、上記単量体を用いて、特定構造を有する２つの硬質重合体を含む。
【００２６】
即ち、重量平均分子量が１０００００〜２０００００で、シアン化ビニル単量体を２０〜３０重量％含む硬質重合体（Ｂ−I）と、重量平均分子量が１０００００未満で、シアン化ビニル単量体を３５〜５０重量％含む硬質重合体（Ｂ−II）とを有する混合物であり、かつ該硬質重合体混合物（Ｂ）中の硬質重合体（Ｂ−II）含有量が２０〜５０重量％のものである。
【００２７】
硬質重合体（Ｂ−I）の重量平均分子量が１０００００未満では吸い込み現象が発生しやすく、２０００００を超えるとブリスター現象が発生しやすく、吸い込み現象も発生する。更に、流動性も悪化する。また、硬質重合体（Ｂ−II）の重量平均分子量が１０００００以上ではブリスター現象が発生しやすい。硬質重合体（Ｂ−II）の好ましい重量平均分子量は５００００〜８００００である。更に、硬質重合体（Ｂ−I）中のシアン化ビニル単量体含有量が２０重量％未満では吸い込み現象が発生しやすく、３０重量％を超えるとブリスター現象が発生する。また、硬質重合体（Ｂ−II）中のシアン化ビニル単量体含有量が３５重量％未満では吸い込み現象が激しく、なおかつブリスター現象も発生し、５０重量％を超えるとブリスター現象が激しく発生する。また、硬質重合体混合物（Ｂ）中の硬質重合体（Ｂ−II）の含有量が２０重量％未満では吸い込み現象及びブリスター現象が発生し、５０重量％を超えると吸い込み現象が著しく発生する。
【００２８】
なお、各硬質重合体中のシアン化ビニルの含有量は、Ｃ．Ｈ．Ｎ．コーダを用いて、各元素分析値より算出した。
【００２９】
本発明においては、特に、硬質重合体混合物（Ｂ）が硬質重合体（Ｂ−I）と硬質重合体（Ｂ−II）とからなり、硬質重合体（Ｂ−I）／硬質重合体（Ｂ−II）の重量比が１〜４であることが好ましく、とりわけ硬質重合体混合物（Ｂ）は芳香族ビニル単量体とシアン化ビニル単量体とからなることが好ましい。
【００３０】
なお、硬質重合体（Ｂ−I）と硬質重合体（Ｂ−II）とに使用される単量体及びその製造方法は、同一でも、異なっていても良い。製造方法としては、乳化、懸濁、塊状又はこれらを複合化した公知の重合方法をいずれも適用できる。
【００３１】
本発明の熱可塑性樹脂組成物を調製する方法として、特に制限はないが、溶融混練りが好ましく、例えば、押出機、バンバリーミキサー等を用いて実施することができる。
【００３２】
本発明の熱可塑性樹脂組成物には、必要に応じて更に、顔料、染料、滑剤、酸化防止剤、紫外線吸収剤、帯電防止剤、補強剤、充填剤など各種添加剤を、その物性等を損なわない範囲内において配合することができる。
【００３３】
なお、上記ゴム含有グラフト共重合体（Ａ）と硬質重合体混合物（Ｂ）とを混合してなる本発明の熱可塑性樹脂組成物において、ゴム含有グラフト共重合体（Ａ）の含有量が１５重量部未満で硬質重合体混合物（Ｂ）の含有量が８５重量部を超えると塗装性、耐衝撃性が劣るものとなり、ゴム含有グラフト共重合体（Ａ）の含有量が５０重量部を超え、硬質重合体混合物（Ｂ）の含有量が５０重量部未満であると塗装性が低下する。
【００３４】
本発明の自動車用成形品は、このような本発明の熱可塑性樹脂組成物を常法に従って成形して得られるものである。
【００３５】
【実施例】
以下に、合成例、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り以下の実施例により何ら限定されるものではない。
【００３６】
なお、以下において、「部」は「重量部」を意味するものとする。また、ゴム含有グラフト共重合体（Ａ成分）中のゴム質重合体に共重合した硬質重合体成分と、各硬質重合体（Ｂ成分）の重量平均分子量は、東ソー（株）製：Ｇ．Ｐ．Ｃ（ゲル・パーミエーション・クロマトグラフィー）を用いた標準ポリスチレン換算法にて算出した。また、各硬質重合体中のシアン化ビニル単量体含有量は、Ｃ．Ｈ．Ｎ．コーダ（Ｙａｎａｃｏ社製：ＣＨＮ CORDER ＭＴ−３）を用いて、各元素の分析値より算出した。
【００３７】
合成例１：ゴム含有グラフト共重合体（Ａ−１）の製造
以下の配合にて、乳化重合法によりＡＢＳ共重合体を合成した。
【００３８】
［配合］
スチレン（ＳＴ） ：３５部
アクリロニトリル（ＡＮ） ：１５部
ポリブタジエン・ラテックス ：５０部
不均化ロジン酸カリウム ：１部
水酸化カリウム ：０．０３部
クメンハイドロパーオキサイド ：０．３部
ターシャリ−ドデシルメルカプタン（ｔ−ＤＭ） ：０．０５部
硫酸第一鉄 ：０．００７部
ピロリン酸ナトリウム ：０．１部
結晶ブドウ糖 ：０．３部
蒸留水 ：１９０部
オートクレーブに蒸留水、不均化ロジン酸カリウム、水酸化カリウム及びポリブタジエン・ラテックスを仕込み、６０℃に加熱後、硫酸第一鉄、ピロリン酸ナトリウム、結晶ブドウ糖を添加し、６０℃に保持したままＳＴ、ＡＮ、ｔ−ＤＭ及びクメンハイドロパーオキサイドを２時間かけて連続添加した。その後、７０℃に昇温して１時間保って反応を完結した。かかる反応によって得たラテックスに酸化防止剤を添加し、その後硫酸により凝固し、十分水洗後、乾燥してグラフト共重合体（Ａ−１）を得た。得られたグラフト共重合体中のグラフトされた硬質重合体成分の重量平均分子量を測定したところ、３５００００であった。
【００３９】
合成例２：ゴム含有グラフト重合体（Ａ−２）の製造
以下の原料配合で、合成例１と同様にしてグラフト共重合体（Ａ−２）を得た。
【００４０】
［配合］
スチレン（ＳＴ） ：２５部
アクリロニトリル（ＡＮ） ：１０部
ポリブタジエン・ラテックス ：６５部
不均化ロジン酸カリウム ：１部
水酸化カリウム ：０．０３部
クメンハイドロパーオキサイド ：０．３部
ターシャリ−ドデシルメルカプタン（ｔ−ＤＭ） ：０．１部
硫酸第一鉄 ：０．００７部
ピロリン酸ナトリウム ：０．１部
結晶ブドウ糖 ：０．３部
蒸留水 ：１９０部
得られたグラフト共重合体中のグラフトされた硬質重合体成分の重量平均分子量を測定したところ、１１００００であった。
【００４１】
合成例３：ゴム含有グラフト共重合体（Ａ−３）の製造
ｔ−ＤＭを加えなかったこと以外は合成例２と同様にしてグラフト共重合体（Ａ−３）を得た。得られたグラフト共重合体中のグラフトされた硬質重合体成分の重量平均分子量を測定したところ、４９００００であった。
【００４２】
合成例４：硬質重合体（Ｂ−I−１）の合成
窒素置換した反応器に水１２０部、アルキルベンゼンスルホン酸ソーダ０．００２部、ポリビニルアルコール０．５部、アゾイソブチロニトリル０．３部、ターシャリ−ドデシルメルカプタン（ｔ−ＤＭ）０．５部と、アクリロニトリル２７部、スチレン７３部からなる単量体混合物を加え、開始温度６０℃として５時間加熱後、１２０℃に昇温し、４時間反応後、重合物を取り出した。転化率は９６％で、得られた硬質重合体（Ｂ−I−１）の重量平均分子量は１３００００、アクリロニトリル含有量は２６．３％であった。
【００４３】
合成例５：硬質重合体（Ｂ−I−２）の合成
ｔ−ＤＭを１．０部としたこと以外は合成例４と同様にして重合を行った。転化率は９８％で、得られた硬質重合体（Ｂ−I−２）の重量平均分子量は６００００、アクリロニトリル含有量は２５．７％であった。
【００４４】
合成例６：硬質重合体（Ｂ−I−３）の合成
ｔ−ＤＭを０．０１部としたこと以外は合成例４と同様にして重合を行った。転化率は９７％で、得られた硬質重合体（Ｂ−I−３）の重量平均分子量は２４００００、アクリロニトリル含有量は２６．２％であった。
【００４５】
合成例７：硬質重合体（Ｂ−I−４）の合成
アクリロニトリル１５部、スチレン８５部からなる単量体を使用したこと以外は、合成例４と同様にして重合を行った。転化率は９６％で、得られた硬質重合体（Ｂ−I−４）の重量平均分子量は１４００００、アクリロニトリル含有量は１５．５％であった。
【００４６】
合成例８：硬質重合体（Ｂ−I−５）の合成
アクリロニトリル３５部、スチレン６５部からなる単量体を使用し、スチレンの一部を逐次添加したこと以外は、合成例４と同様にして重合を行った。転化率は９６％で、得られた硬質重合体（Ｂ−I−５）の重量平均分子量は１６００００、アクリロニトリル含有量は３５．８％であった。
【００４７】
合成例９：硬質重合体（Ｂ−II−１）の合成
窒素置換した反応器に水１２０部、アルキルベンゼンスルホン酸ソーダ０．００２部、ポリビニルアルコール０．５部、アゾイソブチロニトリル０．３部、ターシャリ−ドデシルメルカプタン（ｔ−ＤＭ）０．７５部と、アクリロニトリル４１部、スチレン５９部からなる単量体を加え、スチレンの一部は逐次添加した。重合は、開始温度６０℃として５時間加熱後、１２０℃に昇温し、４時間反応後、重合物を取り出した。転化率は９６％で、得られた硬質重合体（Ｂ−II−１）の重量平均分子量は５４０００、アクリロニトリル含有量は４１．３％であった。
【００４８】
合成例１０：硬質重合体（Ｂ−II−２）の合成
ｔ−ＤＭを０．０１部としたこと以外は合成例９と同様にして重合を行った。転化率は９７％で、得られた硬質重合体（Ｂ−II−２）の重量平均分子量は１５００００、アクリロニトリル含有量は４０．５％であった。
【００４９】
合成例１１：硬質重合体（Ｂ−II−３）の合成
アクリロニトリル３０部、スチレン７０部からなる単量体を使用したこと以外は、合成例９と同様にして重合を行った。転化率は９６％で、得られた硬質重合体（Ｂ−II−３）の重量平均分子量は６００００、アクリロニトリル含有量は３１．４％であった。
【００５０】
合成例１２：硬質重合体（Ｂ−II−４）の合成
アクリロニトリル５５部、スチレン４５部からなる単量体を使用したこと以外は、合成例９と同様にして重合を行った。転化率は９５％で、得られた硬質重合体（Ｂ−II−４）の重量平均分子量は６５００００、アクリロニトリル含有量は５４．６％であった。
【００５１】
実施例１〜３、比較例１〜１１
上記方法にて得られた重合体を表１に示す割合にて、０．５重量部の滑剤（「ＰＲＮ−２０８」日本油脂（株）製）と共にヘンシリングさせた後、２２０℃で２軸押出機（東芝（株）製：ＴＥＸ−４４）にて溶融混合し、ペレット化した。このペレットを４オンス射出成形機（日本製鋼（株）製）で２４０℃にて成形し、必要なテストピースを作成し、それぞれ次のような評価を行い、結果を表１に示した。
【００５２】
［塗装性］
図１に示す平板テストピース（１６０ｍｍ×６０ｍｍ、肉厚２．５ｍｍ）１に対し、５℃の環境温度下、ウレタン系塗料をスプレー塗装した。得られた塗装成形品のサイド２点のゲート２付近と端の部分に発生するブリスター現象及びゲート付近に主に現れる吸い込み現象を肉眼で観察し、ブリスター現象、吸い込み現象ともに以下の判断基準で評価した。
○ ：全く発生せず
△ ：一部発生
× ：著しい発生
［耐衝撃性］
アイゾット衝撃強度（Ｋｇ−ｃｍ／ｃｍ）：ＡＳＴＭ−Ｄ２５６ 厚み：１／４’’（常温）
［成形加工性］
メルトフローインデックス（ｇ／１０ｍｉｎ）：ＡＳＴＭ−Ｄ１２３８（２２０℃／１０Ｋｇ）
【００５３】
【表１】
表１に示す結果より、次のことが明らかである。
【００５５】
即ち、実施例１〜３の結果から、本発明の範囲内であれば、ブリスター現象と吸い込み現象が抑制され、しかも、良好な耐衝撃性と成形加工性が得られることが分かる。
【００５６】
比較例１，２の結果から、グラフト重合体中のゴム質重合体に供重合した硬質重合体成分の分子量が本発明の範囲外では、耐衝撃性、成形加工性は良好であるものの、ブリスター現象及び／又は吸い込み現象が発生し、塗装性に劣るものとなることが分かる。
【００５７】
比較例３〜６の結果から、硬質重合体混合物（Ｂ）中の硬質重合体（Ｂ−I）の分子量又はシアン化ビニル単量体であるアクリロニトリルの含有量が本発明の範囲外であると、ブリスター現象及び／又は吸い込み現象が発生し、塗装性に劣るものとなり、特に比較例４においては、成形加工性が悪化することが分かる。
【００５８】
比較例７〜９の結果から、硬質重合体混合物（Ｂ）中の硬質重合体（Ｂ−II）の分子量又はシアン化ビニル単量体であるアクリルニトリルの含有量が本発明の範囲外であると、ブリスター現象及び／又は吸い込み現象が発生し、塗装性に劣るものとなり、特に比較例７においては成形加工性が著しく悪化することが分かる。
【００５９】
比較例１０，１１の結果から、ゴム含有グラフト共重合体の含有量が本発明の範囲外であるとブリスター現象及び／又は吸い込み現象が発生し、塗装性が劣るものとなり、特に比較例１０においては、耐衝撃性が悪化することが分かる。
【００６０】
以上の結果から、本発明に従って、特定のゴム含有グラフト共重合体と、２種の特定硬質重合体とを含む、特定樹脂組成比率の混合物とにすることによって初めて、優れた塗装性と、耐衝撃性及び、成形加工性とを兼ね揃える熱可塑性樹脂組成物が実現できることがわかる。
【００６１】
【発明の効果】
以上詳述した通り、本発明の熱可塑性樹脂組成物は、優れた塗装性を有し、しかも、耐衝撃性、成形加工性についても高度の状態でバランスが取れていることから、本発明によれば、従来のＡＢＳ樹脂に代表されるゴム含有スチレン系樹脂の欠点を改良した画期的な高特性成形材料が提供される。従って、本発明の熱可塑性樹脂組成物は、自動車用部品等の成形材料として、その工業的な実用価値は極めて大きい。
【００６２】
本発明の自動車用成形品は、このような本発明の熱可塑性樹脂組成物を成形してなるものであり、塗装性、耐衝撃性、成形加工性に優れ、ドアミラー等の自動車用外装部品等に極めて有用である。
【図面の簡単な説明】
【図１】塗装性の評価に用いた平板テストピースの正面図である。
【符号の説明】
１ 平板テストピース
２ ゲート[0001]
BACKGROUND OF THE INVENTION
The present invention is a thermoplastic resin composition suitable as a molding material for automobile exterior parts having excellent paintability and a good balance between impact resistance and workability, and molding such a thermoplastic resin composition. It is related with the molded article for motor vehicles obtained by doing.
[0002]
[Prior art]
ABS resin has excellent processability, impact resistance, mechanical properties, and chemical resistance, and is therefore used as a molding material for various components in a wide range of fields such as the vehicle field and the home appliance field. For example, in recent years, in the vehicle field, attention has been paid to the excellent secondary processability of ABS resin, in particular, paintability, and the use and development of vehicle exterior applications such as door mirrors have been attempted.
[0003]
However, the paintability is easily affected by factors such as the characteristics of the resin composition, molding conditions, the coating method, and the coating environment, and may cause significant coating failure. Among these poor coatings, the blister phenomenon (a phenomenon in which many small holes occur on the painted surface) caused by the action of solvents such as thinner contained in the paint, and the suction phenomenon (fine irregularities occur on the painted surface, resulting in gloss Phenomenon observed as unevenness) is listed as a typical poor coating, which significantly impairs the commercial value of the final product.
[0004]
The blister phenomenon after painting is empirically easy to occur with the recent high cycle and thinned molded parts, and is particularly likely to occur in low temperature environments such as in winter. It is desired. On the other hand, the blister phenomenon generally tends to conflict with the suction phenomenon, which complicates the improvement measures.
[0005]
In such a situation, in order to improve the blister phenomenon and the suction phenomenon at the same time, conventionally, the content of vinyl cyanide compound in the resin is increased, the molecular weight of the resin is increased, and further, the diene rubber gel used. Attempts have been made to optimize the content, particle size, and graft structure, but simultaneously improving the blistering phenomenon and the suction phenomenon in a low-temperature environment, and also the impact resistance and workability required as the basic physical properties of the resin itself. It was extremely difficult to maintain a high balance.
[0006]
JP-A-4-25555 discloses a blister phenomenon and a suction phenomenon by using a resin containing a specific vinyl cyanide compound unit and a specific rubbery copolymer and reducing the content of low molecular weight components. A resin composition that has been eliminated at the same time is disclosed.
[0007]
Japanese Patent Application Laid-Open No. 9-216920 discloses an average particle size and distribution of a diene rubber polymer, a reduced viscosity of a solvent-soluble component in the composition, and a monomer content in the rubber polymer. A resin composition having improved impact resistance, workability and paintability by specifying the graft ratio and the thickness of the graft layer is disclosed.
[0008]
However, as a result of further trials by the present inventors, although any of the above resin compositions is excellent in paintability at an environmental temperature assuming a summer season, many blister phenomena occur in a low temperature environment assuming a winter season. It turned out to be unbearable throughout the year.
[0009]
[Problems to be solved by the invention]
The present invention solves the above-mentioned conventional problems, is excellent in paintability, particularly suppresses blistering and suction phenomena in a low-temperature environment, and has a good balance between impact resistance and workability, and molding automotive exterior parts An object is to provide a thermoplastic resin composition suitable as a material.
[0010]
[Means for Solving the Problems]
The thermoplastic resin composition of the present invention is a rubber-containing graft copolymer by copolymerizing a monomer mixture containing an aromatic vinyl and vinyl cyanide in the presence of a diene rubber polymer, the The content of the diene rubbery polymer in the rubber-containing graft copolymer is 40 to 70% by weight, and the weight average of the hard polymer component grafted by the monomer mixture containing the aromatic vinyl and vinyl cyanide A rubber-containing graft copolymer (A) having a molecular weight of 250,000-450,000, a hard polymer containing 15-50 parts by weight, an aromatic vinyl monomer and a vinyl cyanide monomer, and having a weight average molecular weight 100 to 200,000, a hard polymer (B-I) containing 20 to 30% by weight of a vinyl cyanide monomer, a weight average molecular weight of less than 100,000, and a vinyl cyanide monomer of 35 to 35% A hard polymer mixture (B) containing 50% by weight of a hard polymer (B-II) and having a hard polymer (B-II) content of 20 to 50% by weight in the mixture: And 85 to 50 parts by weight.
[0011]
However, in the thermoplastic resin composition of the present invention, the rubber-containing graft copolymer (A) and the hard polymer mixture (B) are 100 parts by weight in total.
[0012]
In general, the blister phenomenon is caused by a solvent such as thinner attacking a site with a large residual stress generated during the process of cooling the molded product during injection molding, causing cracks on the surface of the molded product and the solvent remaining in the crack. It is thought that this is a phenomenon that expands in the process and breaks through the coating film. On the other hand, the suction phenomenon is caused by the deformation of the rubber due to the surface orientation of the resin that occurs in the molded product during the injection molding process, and as the stress is relaxed by a solvent such as thinner, a fine craze is generated on the painted surface and the gloss decreases. It is thought that this phenomenon brings about
[0013]
In particular, the clear cause and effect of blistering in the low-temperature environment in winter is not detailed, but the molded product is cooled rapidly and residual stress is likely to occur in specific parts, and the solvent of the paint is difficult to volatilize. It is easy to attack the resin.
[0014]
Based on the above findings, the present inventors have earnestly developed a thermoplastic resin composition that suppresses the paintability, particularly the blister phenomenon and the suction phenomenon in a low-temperature environment, and has a good balance between impact resistance and workability. As a result of repeated research, by blending a specific amount of a diene rubbery copolymer with a specific graft structure and two types of hard copolymers with regulated molecular weight and composition, the blister phenomenon and The present inventors have found that a resin composition excellent in paintability that does not cause a suction phenomenon can be obtained, and at the same time, practical impact resistance and workability can be achieved, and the present invention has been completed.
[0015]
In the present invention, in particular, the hard polymer mixture (B) comprises a hard polymer (BI) and a hard polymer (B-II), and the hard polymer (BI) / hard polymer (B The weight ratio of -II) is preferably 1 to 4, and it is particularly preferable that the hard polymer mixture (B) is composed of an aromatic vinyl monomer and a vinyl cyanide monomer.
[0016]
The molded article for automobiles of the present invention is formed by molding such a thermoplastic resin composition of the present invention.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0018]
The rubber-containing graft copolymer (A) according to the present invention is a diene rubber-containing graft polymer obtained by copolymerizing a monomer mixture containing aromatic vinyl and vinyl cyanide in the presence of a diene rubbery polymer. It is a coalescence.
[0019]
Examples of the diene rubbery polymer in the rubber-containing graft copolymer (A) include copolymers of butadiene such as polybutadiene, styrene-butadiene, acrylonitrile-butadiene, and vinyl monomers copolymerizable therewith, poly Isoprene and the like can be mentioned, and one or more of these can be used.
[0020]
The content of diene rubber polymer in the rubber-containing graft copolymer (A), 40 to 70 wt% der is, the content is inferior in the impact resistance is less than 40 wt%, 70 wt% Even if it exceeds, the graft ratio is lowered, so that the impact resistance is poor.
[0021]
Examples of the aromatic vinyl monomer in the rubber-containing graft copolymer (A) include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, etc., and styrene and α-methylstyrene are particularly preferable. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. Also about these monomers, 1 type (s) or 2 or more types can be used.
[0022]
Other copolymerizable monomers that can be used with the aromatic vinyl monomer and vinyl cyanide monomer in the rubber-containing graft copolymer (A) include methyl methacrylate and methyl acrylate. Examples include maleimide compounds such as methacrylic acid or acrylic acid esters, N-phenylmaleimide, N-cyclohexylmaleimide, and unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and one or more of each. Can be used.
[0023]
In the rubber-containing graft copolymer (A) according to the present invention, the weight average molecular weight of the hard polymer component grafted with a mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer is 250,000 to 450,000. If the weight average molecular weight is less than 250,000, a suction phenomenon occurs, and if it exceeds 450,000, a blister phenomenon and a suction phenomenon tend to occur. In the present invention, the weight average molecular weight of the hard polymer component is determined by dissolving the rubber-containing graft copolymer (A) in acetone, taking out the insoluble matter, performing an ozonolysis treatment, and extracting the hard polymer component. , G. P. It is the value calculated by the standard polystyrene conversion method using C (gel permeation chromatography).
[0024]
The hard polymer mixture (B) of the present invention is a hard polymer obtained by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, and another copolymerizable monomer used as necessary. The polymer is composed of an aromatic vinyl monomer, a vinyl cyanide monomer, and other copolymerizable monomers used as necessary. The rubber-containing graft copolymer (A A monomer similar to the monomer to be grafted to (3) can be used.
[0025]
The hard polymer mixture (B) of the present invention contains two hard polymers having a specific structure using the monomer.
[0026]
That is, a hard polymer (BI) having a weight average molecular weight of 100,000 to 200,000 and 20 to 30% by weight of a vinyl cyanide monomer, and a weight average molecular weight of less than 100,000 and a vinyl cyanide monomer of 35 A hard polymer (B-II) containing about 50% by weight and a hard polymer (B-II) content in the hard polymer mixture (B) of 20-50% by weight. is there.
[0027]
If the weight average molecular weight of the hard polymer (BI) is less than 100,000, a suction phenomenon tends to occur, and if it exceeds 200,000, a blister phenomenon tends to occur, and a suction phenomenon also occurs. Furthermore, the fluidity is also deteriorated. In addition, when the weight average molecular weight of the hard polymer (B-II) is 100,000 or more, a blister phenomenon is likely to occur. The preferred weight average molecular weight of the hard polymer (B-II) is 50,000 to 80,000. Furthermore, if the vinyl cyanide monomer content in the hard polymer (BI) is less than 20% by weight, a suction phenomenon tends to occur, and if it exceeds 30% by weight, a blister phenomenon occurs. In addition, when the content of vinyl cyanide monomer in the hard polymer (B-II) is less than 35% by weight, the suction phenomenon is severe, and the blister phenomenon also occurs. When the content exceeds 50% by weight, the blister phenomenon occurs severely. . Further, when the content of the hard polymer (B-II) in the hard polymer mixture (B) is less than 20% by weight, the suction phenomenon and the blister phenomenon occur, and when it exceeds 50% by weight, the suction phenomenon remarkably occurs.
[0028]
The content of vinyl cyanide in each hard polymer is C.I. H. N. It calculated from each elemental analysis value using the coder.
[0029]
In the present invention, in particular, the hard polymer mixture (B) comprises a hard polymer (BI) and a hard polymer (B-II), and the hard polymer (BI) / hard polymer (B The weight ratio of -II) is preferably 1 to 4, and the hard polymer mixture (B) is preferably composed of an aromatic vinyl monomer and a vinyl cyanide monomer.
[0030]
In addition, the monomer used for a hard polymer (BI) and a hard polymer (B-II) and its manufacturing method may be the same, or may differ. As the production method, any known polymerization method in which emulsification, suspension, block, or a combination thereof is combined can be applied.
[0031]
Although there is no restriction | limiting in particular as a method of preparing the thermoplastic resin composition of this invention, Melt kneading is preferable and it can implement using an extruder, a Banbury mixer etc., for example.
[0032]
If necessary, the thermoplastic resin composition of the present invention may further contain various additives such as pigments, dyes, lubricants, antioxidants, ultraviolet absorbers, antistatic agents, reinforcing agents, fillers, and other properties. It can mix | blend within the range which does not impair.
[0033]
In the thermoplastic resin composition of the present invention obtained by mixing the rubber-containing graft copolymer (A) and the hard polymer mixture (B), the content of the rubber-containing graft copolymer (A) is 15 When the content of the hard polymer mixture (B) is less than 85 parts by weight and exceeds 85 parts by weight, the paintability and impact resistance become poor, and the content of the rubber-containing graft copolymer (A) exceeds 50 parts by weight. When the content of the hard polymer mixture (B) is less than 50 parts by weight, the paintability is lowered.
[0034]
The molded article for automobiles of the present invention is obtained by molding the thermoplastic resin composition of the present invention according to a conventional method.
[0035]
【Example】
Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
[0036]
In the following, “part” means “part by weight”. The weight average molecular weight of the hard polymer component copolymerized with the rubber-like polymer in the rubber-containing graft copolymer (component A) and each hard polymer (component B) was manufactured by Tosoh Corporation: P. It was calculated by a standard polystyrene conversion method using C (gel permeation chromatography). The vinyl cyanide monomer content in each hard polymer is C.I. H. N. It calculated from the analytical value of each element using the coder (Yanaco company_made: CHN CORDER MT-3).
[0037]
Synthesis Example 1: Production of rubber-containing graft copolymer (A-1) An ABS copolymer was synthesized by an emulsion polymerization method with the following composition.
[0038]
[Combination]
Styrene (ST): 35 parts Acrylonitrile (AN): 15 parts Polybutadiene latex: 50 parts Disproportionated potassium rosinate: 1 part Potassium hydroxide: 0.03 parts Cumene hydroperoxide: 0.3 parts Tertiary dodecyl mercaptan (T-DM): 0.05 part ferrous sulfate: 0.007 part sodium pyrophosphate: 0.1 part crystalline glucose: 0.3 part distilled water: 190 parts distilled water in an autoclave, disproportionated potassium rosinate , Potassium hydroxide and polybutadiene latex were added, heated to 60 ° C, ferrous sulfate, sodium pyrophosphate and crystalline glucose were added, and ST, AN, t-DM and cumene hydroperoxide were kept at 60 ° C. Was continuously added over 2 hours. Thereafter, the temperature was raised to 70 ° C. and maintained for 1 hour to complete the reaction. An antioxidant was added to the latex obtained by such a reaction, then coagulated with sulfuric acid, sufficiently washed with water, and dried to obtain a graft copolymer (A-1). It was 350,000 when the weight average molecular weight of the grafted hard polymer component in the obtained graft copolymer was measured.
[0039]
Synthesis Example 2: Production of rubber-containing graft polymer (A-2) A graft copolymer (A-2) was obtained in the same manner as in Synthesis Example 1 with the following raw material composition.
[0040]
[Combination]
Styrene (ST): 25 parts Acrylonitrile (AN): 10 parts Polybutadiene latex: 65 parts Disproportionated potassium rosinate: 1 part Potassium hydroxide: 0.03 parts Cumene hydroperoxide: 0.3 parts Tertiary-dodecyl mercaptan (T-DM): 0.1 part ferrous sulfate: 0.007 part sodium pyrophosphate: 0.1 part crystalline glucose: 0.3 part distilled water: 190 parts Grafted in the obtained graft copolymer The measured weight average molecular weight of the hard polymer component was 110,000.
[0041]
Synthesis Example 3: Production of rubber-containing graft copolymer (A-3) A graft copolymer (A-3) was obtained in the same manner as in Synthesis Example 2 except that t-DM was not added. The weight average molecular weight of the grafted hard polymer component in the obtained graft copolymer was 490000.
[0042]
Synthesis Example 4 Synthesis of Rigid Polymer (BI-1) 120 parts of water, 0.002 part of sodium alkylbenzene sulfonate, 0.5 part of polyvinyl alcohol, 0.3 part of azoisobutyronitrile in a nitrogen-substituted reactor Part, tertiary-dodecyl mercaptan (t-DM) 0.5 part, 27 parts of acrylonitrile, and a monomer mixture consisting of 73 parts of styrene, heated at 120 ° C. for 5 hours with a starting temperature of 60 ° C., After reacting for 4 hours, the polymer was taken out. The conversion was 96%, and the obtained hard polymer (B-I-1) had a weight average molecular weight of 130,000 and an acrylonitrile content of 26.3%.
[0043]
Synthesis Example 5: Synthesis of Rigid Polymer (B-I-2) Polymerization was carried out in the same manner as in Synthesis Example 4 except that 1.0 part of t-DM was used. The conversion was 98%, and the obtained hard polymer (B-I-2) had a weight average molecular weight of 60000 and an acrylonitrile content of 25.7%.
[0044]
Synthesis Example 6: Synthesis of Rigid Polymer (BI-3) Polymerization was performed in the same manner as in Synthesis Example 4 except that 0.01 part of t-DM was used. The conversion was 97%, and the obtained hard polymer (B-I-3) had a weight average molecular weight of 240000 and an acrylonitrile content of 26.2%.
[0045]
Synthesis Example 7: Synthesis of hard polymer (BI-4) Polymerization was carried out in the same manner as in Synthesis Example 4 except that a monomer composed of 15 parts of acrylonitrile and 85 parts of styrene was used. The conversion was 96%, and the obtained hard polymer (BI-4) had a weight average molecular weight of 140,000 and an acrylonitrile content of 15.5%.
[0046]
Synthesis Example 8: Synthesis of Rigid Polymer (BI-5) As in Synthesis Example 4, except that a monomer composed of 35 parts of acrylonitrile and 65 parts of styrene was used and a part of styrene was sequentially added. Polymerization was performed. The conversion was 96%, and the obtained hard polymer (BI-5) had a weight average molecular weight of 160000 and an acrylonitrile content of 35.8%.
[0047]
Synthesis Example 9 Synthesis of Rigid Polymer (B-II-1) 120 parts of water, 0.002 part of sodium alkylbenzene sulfonate, 0.5 part of polyvinyl alcohol, 0.3 part of azoisobutyronitrile in a nitrogen-substituted reactor Part, tertiary-decyl mercaptan (t-DM) 0.75 part, a monomer composed of 41 parts acrylonitrile and 59 parts styrene, and a part of styrene was added sequentially. The polymerization was started at 60 ° C. for 5 hours, heated to 120 ° C., reacted for 4 hours, and the polymer was taken out. The conversion was 96%, and the obtained hard polymer (B-II-1) had a weight average molecular weight of 54,000 and an acrylonitrile content of 41.3%.
[0048]
Synthesis Example 10: Synthesis of Rigid Polymer (B-II-2) Polymerization was performed in the same manner as in Synthesis Example 9 except that 0.01 part of t-DM was used. The conversion was 97%, and the obtained hard polymer (B-II-2) had a weight average molecular weight of 150,000 and an acrylonitrile content of 40.5%.
[0049]
Synthesis Example 11: Synthesis of Rigid Polymer (B-II-3) Polymerization was performed in the same manner as in Synthesis Example 9 except that a monomer composed of 30 parts of acrylonitrile and 70 parts of styrene was used. The conversion was 96%, and the obtained hard polymer (B-II-3) had a weight average molecular weight of 60000 and an acrylonitrile content of 31.4%.
[0050]
Synthesis Example 12: Synthesis of Rigid Polymer (B-II-4) Polymerization was performed in the same manner as in Synthesis Example 9 except that a monomer composed of 55 parts of acrylonitrile and 45 parts of styrene was used. The conversion was 95%, and the obtained hard polymer (B-II-4) had a weight average molecular weight of 650000 and an acrylonitrile content of 54.6%.
[0051]
Examples 1-3, Comparative Examples 1-11
The polymer obtained by the above method was hessilled together with 0.5 parts by weight of a lubricant (“PRN-208” manufactured by NOF Corporation) at the ratio shown in Table 1, and then biaxial extrusion at 220 ° C. The mixture was melt-mixed with a machine (Toshiba Corp .: TEX-44) and pelletized. The pellets were molded at 240 ° C. with a 4 ounce injection molding machine (manufactured by Nippon Steel Co., Ltd.), necessary test pieces were prepared, and the following evaluations were performed. The results are shown in Table 1.
[0052]
[Paintability]
A urethane-based paint was spray-coated at an environmental temperature of 5 ° C. on a flat test piece (160 mm × 60 mm, thickness 2.5 mm) 1 shown in FIG. Observe the blistering phenomenon occurring near the
○: Not generated at all △: Partially generated ×: Significantly generated [impact resistance]
Izod impact strength (Kg-cm / cm): ASTM-D256 Thickness: 1/4 "(room temperature)
[Molding processability]
Melt flow index (g / 10min): ASTM-D1238 (220 ° C / 10Kg)
[0053]
[Table 1]
From the results shown in Table 1, the following is clear.
[0055]
That is, it can be seen from the results of Examples 1 to 3 that the blister phenomenon and the suction phenomenon are suppressed and good impact resistance and molding processability can be obtained within the scope of the present invention.
[0056]
From the results of Comparative Examples 1 and 2, when the molecular weight of the hard polymer component polymerized to the rubbery polymer in the graft polymer is outside the range of the present invention, the impact resistance and molding processability are good, but the blister It can be seen that the phenomenon and / or the suction phenomenon occurs, resulting in poor paintability.
[0057]
From the results of Comparative Examples 3 to 6, when the molecular weight of the hard polymer (BI) in the hard polymer mixture (B) or the content of acrylonitrile which is a vinyl cyanide monomer is outside the scope of the present invention. The blister phenomenon and / or the suction phenomenon occur, and the paintability is inferior. In particular, it can be seen that the molding processability deteriorates in Comparative Example 4.
[0058]
From the results of Comparative Examples 7 to 9, the molecular weight of the hard polymer (B-II) in the hard polymer mixture (B) or the content of acrylonitrile which is a vinyl cyanide monomer is outside the scope of the present invention. As a result, a blister phenomenon and / or a suction phenomenon occur, and the paintability is inferior. Particularly, in Comparative Example 7, it can be seen that the molding processability is remarkably deteriorated.
[0059]
From the results of Comparative Examples 10 and 11, when the content of the rubber-containing graft copolymer is outside the scope of the present invention, blistering and / or suction phenomenon occurs, and the paintability is inferior. It can be seen that the impact resistance deteriorates.
[0060]
From the above results, according to the present invention, excellent paintability and resistance are not achieved until a mixture having a specific resin composition ratio including a specific rubber-containing graft copolymer and two specific hard polymers is obtained. It can be seen that a thermoplastic resin composition having both impact properties and moldability can be realized.
[0061]
【The invention's effect】
As described in detail above, the thermoplastic resin composition of the present invention has excellent paintability, and also has a high balance of impact resistance and molding processability. According to this, an epoch-making high-performance molding material in which the defects of the rubber-containing styrenic resin represented by the conventional ABS resin are improved is provided. Accordingly, the industrial value of the thermoplastic resin composition of the present invention is extremely great as a molding material for automobile parts and the like.
[0062]
The molded article for automobiles of the present invention is formed by molding the thermoplastic resin composition of the present invention, and has excellent paintability, impact resistance, molding processability, and exterior parts for automobiles such as door mirrors. Very useful.
[Brief description of the drawings]
FIG. 1 is a front view of a flat plate test piece used for evaluation of paintability.
[Explanation of symbols]
1
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP17598798A JP4013338B2 (en) | 1998-06-23 | 1998-06-23 | Thermoplastic resin composition excellent in paintability and molded article for automobile |
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| Application Number | Priority Date | Filing Date | Title |
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| JP17598798A JP4013338B2 (en) | 1998-06-23 | 1998-06-23 | Thermoplastic resin composition excellent in paintability and molded article for automobile |
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| JP4013338B2 true JP4013338B2 (en) | 2007-11-28 |
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| JP5998299B1 (en) * | 2016-03-10 | 2016-09-28 | ユーエムジー・エービーエス株式会社 | Thermoplastic resin composition and resin molded product |
| JP6407459B1 (en) * | 2018-02-14 | 2018-10-17 | ユーエムジー・エービーエス株式会社 | Coated molding |
| JP6850932B1 (en) * | 2020-11-10 | 2021-03-31 | 日本エイアンドエル株式会社 | Resin composition for painting |
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