JPH0456044B2 - - Google Patents
Info
- Publication number
- JPH0456044B2 JPH0456044B2 JP30605186A JP30605186A JPH0456044B2 JP H0456044 B2 JPH0456044 B2 JP H0456044B2 JP 30605186 A JP30605186 A JP 30605186A JP 30605186 A JP30605186 A JP 30605186A JP H0456044 B2 JPH0456044 B2 JP H0456044B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- monomer mixture
- vinyl
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 31
- -1 vinyl cyanide compound Chemical class 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920001971 elastomer Polymers 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims 2
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 claims 1
- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 claims 1
- 229940125773 compound 10 Drugs 0.000 claims 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000008360 acrylonitriles 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
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 2
- 229940082004 sodium laurate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-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
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- YIEXROAWVNRRMJ-UHFFFAOYSA-N buta-1,3-diene;butyl prop-2-enoate Chemical compound C=CC=C.CCCCOC(=O)C=C YIEXROAWVNRRMJ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
（産業上の利用分野）
本発明は、艶消しされた外観を有し、かつ耐衝
撃性、剛性、耐熱変形性、成形加工性、表面外観
に優れた熱可塑性樹脂の製造方法に関するもので
ある。
（従来の技術と問題点）
ABS系樹脂は、その優れた耐衝撃性、耐熱変
形性、成形加工性及び良好な表面光沢を有するた
め種々の用途に供されている。一方、自動車内装
部品、弱電部品等の分野では落ち着き感、高級
感、光の反射を抑える事による安全性などの確保
のために部品表面の光沢（反射率）を抑えたもの
に対する需要が高まつている。
光沢を抑え艶消しされた部品を得る方法として
は、金型面からの改良、艶消し塗装による方法、
あついは無機質やゴム成分を配合する方法等がと
られてきた。しかし、これらの方法では十分な効
果が得られていないのが現状である。すなわち、
金型面からの改良では金型の補修、管理が難し
く、また成形条件によつても艶の状態が変わり、
一定の艶の成形品を得ることは難しい。無機質の
配合では耐衝撃性の低下が大きく、ゴム質の配合
では耐熱変形性、剛性が低下し、フローマークや
ウエルトラインが生じやすく、外観の優れた成形
品を得ることが難しい。
（問題を解決するための手段及び作用効果）
本発明者らは、かかる欠点を改良すべく鋭意検
討した結果、ゴム状重合体の存在下に特定の成分
を含有した単量体混合物を重合させたのち、ビニ
ル系単量体混合物を重合させたものが艶消しされ
た外観を有し、熱的・機械的物性及び成形加工性
に優れていることを見い出し、本発明に至つた。
すなわち、本発明は、ゴム状重合体５〜35重量
部の存在下にビニル系単量体95〜65重量部を重合
させる際に、α，β−不飽和酸のグリシジルエス
テル化合物0.1〜40重量％、シアン化ビニル化合
物10〜35重量％、芳香族ビニル化合物50〜89.9重
量％、他の共重合可能なビニル化合物０〜30重量
％から成る単量体混合物（合わせて100重量％）
(A)２〜40重量部を重合させたのち、シアン化ビニ
ル化合物10〜40重量％、芳香族ビニル化合物60〜
90重量％及び他の共重合可能なビニル化合物０〜
30重量％から成る単量体混合物（合わせて100重
量％）(B)25〜93重量部を重合させて成る艶消し性
熱可塑性樹脂の製造方法を内容とするものであ
る。
本発明においては、ゴム状重合体の存在下に単
量体混合物(A)、単量体混合物(B)の順序に添加す
る。この際、単量体混合物(A)及び(B)の添加方法は
特に限定されるものではないが、単量体混合物(A)
の大部分が重合した後、単量体混合物(B)を添加す
ることが好ましい。単量体混合物(A)及び(B)は、そ
の一部を分割して添加することももちろん可能で
ある。
ここでゴム状重合体部数、単量体混合物(A)及び
(B)の部数、組成は所望される樹脂の物理的性質に
より最適点があるが、ゴム状重合体の量としては
５〜35重量部が好ましく、それ以外では耐衝撃
性、耐熱性、艶消し性、成形加工性等から好まし
くない。本発明に用いるゴム状重合体としては、
ポリブタジエンゴム、スチレン−ブタジエンゴム
（SBR）、アクリロニトリル、ブタジエンゴム
（NBR）、ブチルアクリレート−ブタジエンゴム
等のジエン系ゴム；ポリブチルアクリレート等の
アクリル系ゴム；エチレン−プロピレン−非共役
ジエンゴム（EPDM）等のポリオレフイン系ゴ
ム等が用いられる。
単量体混合物(A)は２〜40重量部、好ましくは２
〜30重量部であり、その組成としては、α，β−
不飽和酸のグリシジルエステル化合物0.1〜40重
量％、好ましくは0.5〜30重量％、シアン化ビニ
ル化合物10〜35重量％、芳香族ビニル化合物50〜
89.9重量％、他の共重合可能なビニル化合物０〜
30重量％である。
α，β−不飽和酸のグリシジルエステル化合物
としては、アクリル酸グリシジル、メタクリル酸
グリシジル、エタクリル酸グリシジル等が例示さ
れる。シアン化ビニル化合物としては、アクリロ
ニトリル、メタクリルニトリル等が例示され、芳
香族ビニル化合物としては、スチレン、メチルス
チレン、クロルスチレン、α−メチルスチレン等
が例示される。さらに他の共重合可能なビニル化
合物としては、メチルメタクリレート、エチルメ
タクリレート、エチルアクリレート、ブチルアク
リレート、アクリル酸、メタクリル酸、フエニル
マレイミド、ヒドロキシアクリレート等が例示さ
れる。単量体混合物(A)の量が２〜40重量部の範囲
外では耐衝撃性、成形加工性、艶消し性等が低下
して好ましくない。単量体混合物(A)において、
α，β−不飽和酸のグリシジルエステル化合物は
0.1〜40重量％が好ましく、0.1重量％未満では艶
消し効果が不十分であり、40重量％以上では成形
加工性、耐衝撃性の低下があり好ましくない。シ
アン化ビニル化合物は10〜35重量％が好ましく、
その範囲外では耐衝撃性が低下したり、成形加工
時に熱着色が生じたりして好ましくない。芳香族
ビニル化合物は50〜89.9重量％が好ましく、その
範囲外では耐衝撃性が低下したりして好ましくな
い。
単量体混合物(B)は25〜93重量部であり、その組
成はシアン化ビニル化合物は10〜40重量％が好ま
しく、その範囲外では耐衝撃性が低下したり、成
形加工時に熱着色が生じたりして好ましくない。
芳香族ビニル化合物は60〜90重量％が好ましく、
その範囲外では耐衝撃性が低下したり、成形加工
性が低下したりして好ましくない。単量体混合物
(B)で使用されるシアン化ビニル化合物、芳香族ビ
ニル化合物、さらに共重合可能なビニル系化合物
は単量体混合物(A)で使用した種類のものが使用可
能である。耐熱性を高めるためには芳香族ビニル
化合物としてα−メチルスチレンを使用すること
が好ましい。
得られるポリマーのメチルエチルケトン可溶成
物の固有粘度（dl／ｇ、30℃，Ｎ，N′−ジメチ
ルホルムアミド溶液）は0.25〜1.5の範囲が好ま
しい。その範囲外では耐衝撃性、剛性が低下した
り、成形加工性が低下したりして好ましくない。
本発明の樹脂の製造方法は、好ましくは乳化重
合によるが、乳化重合に限定されるものではな
い。例えば懸濁重合、溶液重合、塊状重合、乳化
−塊状重合、乳化−懸濁重合等が例示される。
乳化重合は通常の方法により実施できる。例え
ば前記単量体混合物をゴム状重合体存在下に水性
分散媒体中、ラジカル開始剤で重合させればよ
い。ラジカル開始剤としては過硫酸カリ、過硫酸
アンモニウム、キユメンハイドロパーオキサイド
等の過酸化物を例示することができる。その他、
重合促進剤、重合度調節剤、乳化剤等も適宜選択
して使用できる。重合温度としては30〜90℃が好
ましい。得られたラテツクスから樹脂を得る方法
は公知の方法でよい。例えば塩化カルシウム、塩
化マグネシウム、硫酸アルミニウム等の無機塩や
塩酸、硫酸、酢酸、リン酸等の酸類により凝固し
て得られる。また、必要に応じて、安定剤、滑
剤、可塑剤、顔料、フイラー等を加えてもよい。
また、ポリカーボネート樹脂、ポリ塩化ビニル樹
脂、ABS系樹脂、AS系樹脂、PET樹脂、PBT
樹脂等とブレンドして使用することも可能であ
る。
本発明の熱可塑性樹脂組成物は艶消しされた外
観を有し、かつ耐衝撃性、剛性、耐熱変形性、成
形加工性、表面外観性に優れたものである。
（実施例）
以下に実施例を示し、本発明を具体的に説明す
るが、実施例に限定されるものではない。尚、以
下で「部」は特にことわりのない限り「重量部」
であり、「％」は重量％である。
実施例及び比較例
水 250部
ラウリン酸ソーダ 0.5部
ソジウムホルムアルデヒドスルホキシレート
0.4部
エチレンジアミンテトラ酢酸２ナトリウム
0.01部
硫酸第一鉄 0.0025部
これらの物質を攪拌機つき反応機に仕込み、脱
酸素後、窒素気流中で60℃に加熱攪拌後、表−１
のゴムラテツクス、単量体混合物(A)及び(B)を順次
仕込んだ。単量体混合物(A)及び(B)は、時間当り10
部の割合で連続的に滴下し、滴下終了後、１時間
60℃で攪拌を続け重合を終了させた。尚、ラウリ
ン酸ソーダは単量体混合物(A)の滴下開始後１時間
目、４時間目の各々１部を添加した。また、実施
例７は単量体混合物(B)を（Ｂ−１）と（Ｂ−２）
に分割し、（Ｂ−１）滴下終了後、（Ｂ−２）を滴
下した。さらに実施例８は単量体混合物(B)を（Ｂ
−１）と（Ｂ−２）に分割し、（Ｂ−１）を一括
して仕込み、（Ｂ−２）を６時間かけて連続的に
滴下した。
重合途中及び重合終了時のラテツクスをサンプ
リングして分析に供した。
得られた重合体ラテツクスにフエノール系の酸
化防止剤を加え、塩化カルシウムで塩析し凝固さ
せた後、水洗過、乾燥して、ベント式押出機で
ペレツト化し、物理的性質の測定に供した。
(Field of Industrial Application) The present invention relates to a method for producing a thermoplastic resin that has a matte appearance and is excellent in impact resistance, rigidity, heat deformation resistance, moldability, and surface appearance. . (Prior Art and Problems) ABS resins have excellent impact resistance, heat deformation resistance, moldability, and good surface gloss, and are used for various purposes. On the other hand, in the fields of automobile interior parts, light electrical parts, etc., there is a growing demand for products with reduced gloss (reflectance) on the surface of parts to ensure a sense of calm, luxury, and safety by suppressing light reflection. ing. Methods to suppress gloss and obtain matte parts include improving the mold surface, using matte coating,
For heat treatment, methods such as blending inorganic substances or rubber components have been used. However, the current situation is that these methods do not have sufficient effects. That is,
It is difficult to repair and manage the mold when improving from the mold side, and the gloss condition changes depending on the molding conditions.
It is difficult to obtain a molded product with a constant gloss. Inorganic formulations significantly reduce impact resistance, while rubber formulations reduce heat deformation resistance and rigidity, tend to cause flow marks and welt lines, and make it difficult to obtain molded products with excellent appearance. (Means and Effects for Solving the Problems) As a result of intensive studies to improve these drawbacks, the inventors of the present invention polymerized a monomer mixture containing specific components in the presence of a rubbery polymer. Later, it was discovered that a polymerized vinyl monomer mixture has a matte appearance and excellent thermal and mechanical properties and moldability, leading to the present invention. That is, in the present invention, when 95 to 65 parts by weight of a vinyl monomer is polymerized in the presence of 5 to 35 parts by weight of a rubbery polymer, 0.1 to 40 parts by weight of a glycidyl ester compound of an α,β-unsaturated acid is added. %, a monomer mixture consisting of 10-35% by weight of a vinyl cyanide compound, 50-89.9% by weight of an aromatic vinyl compound, and 0-30% by weight of other copolymerizable vinyl compounds (total 100% by weight)
After polymerizing 2-40 parts by weight of (A), 10-40% by weight of vinyl cyanide compound and 60-40% by weight of vinyl aromatic compound.
90% by weight and 0 to other copolymerizable vinyl compounds
The subject matter is a method for producing a matte thermoplastic resin by polymerizing 25 to 93 parts by weight of a monomer mixture (total 100% by weight) (B) consisting of 30% by weight. In the present invention, the monomer mixture (A) and the monomer mixture (B) are added in this order in the presence of the rubbery polymer. At this time, the method of adding monomer mixtures (A) and (B) is not particularly limited;
It is preferable to add the monomer mixture (B) after most of the monomer mixture (B) has been polymerized. Of course, monomer mixtures (A) and (B) can also be added in portions. Here, the number of rubbery polymer parts, monomer mixture (A) and
The number and composition of (B) have an optimal point depending on the desired physical properties of the resin, but the amount of rubbery polymer is preferably 5 to 35 parts by weight. Unfavorable in terms of erasability, moldability, etc. The rubbery polymer used in the present invention includes:
Diene rubbers such as polybutadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile, butadiene rubber (NBR), butyl acrylate-butadiene rubber; acrylic rubbers such as polybutyl acrylate; ethylene-propylene-nonconjugated diene rubber (EPDM), etc. Polyolefin rubber and the like are used. The monomer mixture (A) contains 2 to 40 parts by weight, preferably 2 parts by weight.
~30 parts by weight, and its composition is α, β-
Glycidyl ester compounds of unsaturated acids 0.1-40% by weight, preferably 0.5-30% by weight, vinyl cyanide compounds 10-35% by weight, aromatic vinyl compounds 50-40% by weight
89.9% by weight, 0 to other copolymerizable vinyl compounds
It is 30% by weight. Examples of glycidyl ester compounds of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Examples of vinyl cyanide compounds include acrylonitrile and methacrylnitrile, and examples of aromatic vinyl compounds include styrene, methylstyrene, chlorostyrene, and α-methylstyrene. Examples of other copolymerizable vinyl compounds include methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, phenylmaleimide, and hydroxyacrylate. If the amount of the monomer mixture (A) is outside the range of 2 to 40 parts by weight, impact resistance, moldability, matting properties, etc. will deteriorate, which is not preferable. In the monomer mixture (A),
Glycidyl ester compounds of α,β-unsaturated acids are
The content is preferably 0.1 to 40% by weight; if it is less than 0.1% by weight, the matting effect will be insufficient, and if it is more than 40% by weight, moldability and impact resistance will deteriorate, which is not preferable. The vinyl cyanide compound is preferably 10 to 35% by weight,
Outside this range, impact resistance may deteriorate or thermal coloring may occur during molding, which is not preferable. The amount of the aromatic vinyl compound is preferably 50 to 89.9% by weight, and if it is outside this range, the impact resistance may deteriorate, which is not preferable. The monomer mixture (B) is 25 to 93 parts by weight, and the vinyl cyanide compound is preferably 10 to 40 parts by weight. Outside this range, impact resistance may decrease or thermal discoloration may occur during molding. This is not desirable.
The aromatic vinyl compound is preferably 60 to 90% by weight,
Outside this range, impact resistance and moldability may deteriorate, which is undesirable. monomer mixture
The vinyl cyanide compound, aromatic vinyl compound, and copolymerizable vinyl compound used in (B) can be the same as those used in monomer mixture (A). In order to improve heat resistance, it is preferable to use α-methylstyrene as the aromatic vinyl compound. The intrinsic viscosity (dl/g, 30 DEG C., N,N'-dimethylformamide solution) of the resulting polymer soluble in methyl ethyl ketone is preferably in the range of 0.25 to 1.5. Outside this range, impact resistance and rigidity may be reduced, and moldability may be reduced, which is not preferable. The method for producing the resin of the present invention preferably involves emulsion polymerization, but is not limited to emulsion polymerization. Examples include suspension polymerization, solution polymerization, bulk polymerization, emulsion-bulk polymerization, and emulsion-suspension polymerization. Emulsion polymerization can be carried out by conventional methods. For example, the monomer mixture may be polymerized using a radical initiator in an aqueous dispersion medium in the presence of a rubbery polymer. Examples of the radical initiator include peroxides such as potassium persulfate, ammonium persulfate, and kyumene hydroperoxide. others,
Polymerization accelerators, polymerization degree regulators, emulsifiers, etc. can also be selected and used as appropriate. The polymerization temperature is preferably 30 to 90°C. A known method may be used to obtain the resin from the obtained latex. For example, it is obtained by coagulating with inorganic salts such as calcium chloride, magnesium chloride, and aluminum sulfate, and acids such as hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid. Further, stabilizers, lubricants, plasticizers, pigments, fillers, etc. may be added as necessary.
In addition, polycarbonate resin, polyvinyl chloride resin, ABS resin, AS resin, PET resin, PBT
It is also possible to use it by blending it with a resin or the like. The thermoplastic resin composition of the present invention has a matte appearance and is excellent in impact resistance, rigidity, heat deformation resistance, moldability, and surface appearance. (Example) The present invention will be specifically described below with reference to Examples, but the present invention is not limited to the Examples. In addition, "parts" below refer to "parts by weight" unless otherwise specified.
and "%" is % by weight. Examples and Comparative Examples Water 250 parts Sodium laurate 0.5 parts Sodium formaldehyde sulfoxylate
0.4 parts Disodium ethylenediaminetetraacetate
0.01 part Ferrous sulfate 0.0025 part These substances were charged into a reactor equipped with a stirrer, deoxidized, heated to 60°C in a nitrogen stream and stirred, Table 1
Rubber latex and monomer mixtures (A) and (B) were sequentially charged. Monomer mixtures (A) and (B) at 10 per hour
1 hour after the dripping is finished.
Stirring was continued at 60°C to complete polymerization. Incidentally, 1 part of sodium laurate was added each 1 hour and 4 hours after the start of dropping the monomer mixture (A). In addition, in Example 7, the monomer mixture (B) was divided into (B-1) and (B-2).
After the completion of dropping (B-1), (B-2) was added dropwise. Furthermore, in Example 8, the monomer mixture (B) was
-1) and (B-2), (B-1) was charged all at once, and (B-2) was continuously added dropwise over 6 hours. The latex was sampled during the polymerization and at the end of the polymerization and was subjected to analysis. A phenolic antioxidant was added to the obtained polymer latex, which was salted out with calcium chloride and coagulated, washed with water, dried, pelletized using a vented extruder, and subjected to measurement of physical properties. .
【表】【table】
【表】【table】
【表】【table】
【表】
また参考例１として、実施例２と同じ組成のも
のを通常の乳化重合で、ゴム状重合体に単量体混
合物(A)を重合させたものを作成してパウダー化し
たもの及び単量体混合物(B)のみを重合させたもの
を作成してパウダー化したもの、双方をブレンド
して得た。参考例２として、実施例２と同じ組成
のものを通常の乳化重合で、ゴム状重合体に単量
体混合物(B)を重合させたものを作成しパウダー化
したもの及び単量体混合物(A)のみを重合させたも
のを作成してパウダー化したもの、双方をブレン
ドして得た。[Table] In addition, as Reference Example 1, a product with the same composition as Example 2 was prepared by polymerizing the monomer mixture (A) into a rubbery polymer by ordinary emulsion polymerization, and then powdered. One was prepared by polymerizing only the monomer mixture (B), the other was made into powder, and the other was obtained by blending both. As Reference Example 2, a product with the same composition as Example 2 was prepared by polymerizing monomer mixture (B) into a rubber-like polymer by ordinary emulsion polymerization, and was made into powder, and a monomer mixture ( One was obtained by polymerizing only A), the other was made into a powder, and the other was obtained by blending both.
【表】【table】
【表】
表−１，２及び３より、本発明の範囲内のもの
が艶消しされた外観を有し、かつ耐衝撃性、剛
性、耐熱変形性、成形加工性、表面外観に優れた
ものであることがわかる。[Table] From Tables 1, 2, and 3, those within the scope of the present invention have a matte appearance and are excellent in impact resistance, rigidity, heat deformation resistance, moldability, and surface appearance. It can be seen that it is.
Claims (1)
系単量体95〜65重量部を重合させる際に、α，β
−不飽和脂肪酸のグリシジルエステル化合物0.1
〜40重量％、シアン化ビニル化合物10〜35重量
％、芳香族ビニル化合物50〜89.9重量％及び他の
共重合可能なビニル系化合物０〜30重量％からな
る単量体混合物 (A) ２〜40重量部を重合させた後、シアン化ビニ
ル化合物10〜40重量％、芳香族ビニル化合物60
〜90重量％及び他の共重合可能なビニル系化合
物０〜30重量％から成る単量体混合物 (B) 25〜93重量部を重合させることを特徴とする
艶消し性熱可塑性樹脂の製造方法。[Scope of Claims] 1. When 95 to 65 parts by weight of a vinyl monomer is polymerized in the presence of 5 to 35 parts by weight of a rubbery polymer, α, β
- Glycidyl ester compounds of unsaturated fatty acids 0.1
Monomer mixture (A) 2 to 40% by weight, vinyl cyanide compound 10 to 35%, aromatic vinyl compound 50 to 89.9% by weight, and other copolymerizable vinyl compounds 0 to 30% by weight After polymerizing 40 parts by weight, vinyl cyanide compound 10-40% by weight, aromatic vinyl compound 60%
A method for producing a matte thermoplastic resin, comprising polymerizing 25 to 93 parts by weight of a monomer mixture (B) comprising ~90% by weight and 0 to 30% by weight of other copolymerizable vinyl compounds. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30605186A JPS63156847A (en) | 1986-12-22 | 1986-12-22 | Delustered thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30605186A JPS63156847A (en) | 1986-12-22 | 1986-12-22 | Delustered thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63156847A JPS63156847A (en) | 1988-06-29 |
| JPH0456044B2 true JPH0456044B2 (en) | 1992-09-07 |
Family
ID=17952462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30605186A Granted JPS63156847A (en) | 1986-12-22 | 1986-12-22 | Delustered thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63156847A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0721096B2 (en) * | 1987-12-18 | 1995-03-08 | 日本合成ゴム株式会社 | Thermoplastic resin composition |
| JPH075814B2 (en) * | 1988-07-05 | 1995-01-25 | 東レ株式会社 | Fiber-reinforced thermoplastic resin composition |
| JPH02214712A (en) * | 1989-02-15 | 1990-08-27 | Hitachi Chem Co Ltd | Matting agent and matted thermoplastic resin composition |
| US5026777A (en) * | 1989-11-17 | 1991-06-25 | General Electric Company | Low gloss thermoplastic molding compositions |
| EP0700971A3 (en) | 1994-09-12 | 1996-07-17 | Gen Electric | Polycarbonate composition for moulding low glass articles |
| KR101225559B1 (en) | 2007-08-21 | 2013-01-24 | 유엠지 에이비에스 가부시키가이샤 | Method for producing enlarged rubber, graft copolymer, thermoplastic resin composition and molded article |
| JP5139195B2 (en) * | 2008-08-08 | 2013-02-06 | 日本エイアンドエル株式会社 | Method for producing rubber-reinforced styrene resin |
-
1986
- 1986-12-22 JP JP30605186A patent/JPS63156847A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63156847A (en) | 1988-06-29 |
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