JPS6367807B2 - - Google Patents
Info
- Publication number
- JPS6367807B2 JPS6367807B2 JP59000942A JP94284A JPS6367807B2 JP S6367807 B2 JPS6367807 B2 JP S6367807B2 JP 59000942 A JP59000942 A JP 59000942A JP 94284 A JP94284 A JP 94284A JP S6367807 B2 JPS6367807 B2 JP S6367807B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- monomer
- parts
- graft
- resin
- 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
- 239000000178 monomer Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 15
- 229920000578 graft copolymer Polymers 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000004816 latex Substances 0.000 claims description 11
- 229920000126 latex Polymers 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- -1 vinyl aromatic compounds Chemical class 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 150000008360 acrylonitriles Chemical class 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 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
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、帯電防止性を有し、且つ表面艶消し
効果のある樹脂の製造方法に関するものである。
従来から耐衝撃性熱可塑性樹脂として知られて
いるABS樹脂は、その優れた成形性、耐衝撃性
及び良好な表面光沢を有することから種々の用途
に使用される。しかしながら、逆に成形体の表面
光沢の低いものが望まれる用途があり、例えば自
動車用の内装部品、家庭用電気機器の外部部品の
一部の用途では、成形体表面を艶消し状態として
落着いた感じにし、安全性に寄与させる場合があ
る。成形体表面を艶消しにする方法としては、表
面にシボ加工を施したり、艶消し塗装とする方法
等があるが、シボ加工では十分な艶消し効果が得
られず、艶消し塗装では塗装のコストがかさむ上
に塗装被膜の強度、塗料に含まれるシンナーによ
る成形体塗面の劣化の問題が発生する。従つて、
材質そのものの表面光沢を下げて艶を消すことが
より望ましい。
艶消しにする方法としては、タルク・炭酸カル
シウム・シリカ等の無機充填剤を添加する等して
成形品の表面の光沢を低下させる方法があるが、
これらの方法ではいずれの場合でもその効果は乏
しく、衝撃強度及び成形性の低下が生じる。また
一般に熱可塑性樹脂は電気抵抗が大きく、摩擦ま
たは接触により容易に帯電し、ゴミやほこりを吸
引して外観を損ねる等、成形体・シート・フイル
ム・繊維等の分野で様々なトラブルの原因になつ
ている。この欠点を改良するために、従来いろい
ろな方法が提案されている。例えば帯電防止剤を
練り込みする方法がある。この加熱して混練する
方法は簡単であるが、表面に存在する帯電防止剤
を水洗、摩擦等の手段で除去すると、帯電防止能
が失われる。それでも成形体内部に含まれている
帯電防止剤が一部表面にブリードして、これを補
つているが、特にポリスチレンやABC樹脂では
帯電防止剤が内部から表面にブリードし難いため
帯電防止能が回復し難い等の問題がある。また、
熱可塑性樹脂を化学的に改質する方法がある。帯
電防止能のある単量体を共重合させる方法等であ
るが、一般に成形性が著しく低下するという問題
があつた。
本発明は、上記の様な艶消し性及び帯電防止性
のある樹脂を得る上での諸欠点を一挙に改善し、
艶消し効果があり、且つ帯電防止性のある熱可塑
性樹脂の製造方法を提供するものである。
具体的な応用分野としては、例えばカセツトテ
ープレコーダーケース、計器類カバー等の電気機
器部、包装用品、照明器具、建材その他、帯電防
止性を必要とし、表面反射が嫌われる用途、特に
その反射光が安全性に障害となる用途や艶消しに
よる高級感のある用途等に適している。
本発明者は、洗浄等により帯電防止効果が低下
しない永久帯電防止性を有し、且つ艶消しによる
高級感のある樹脂を得るために鋭意検討の結果、
(A) 共役ジエン系単量体を50重量％以上含むジエ
ン系共重合体ラテツクス５〜80重量部（固形分
換算）の存在下に、下記一般式（）
（式中、R1，R2，R3は水素又は炭素数１〜
４のアルキル基、ｎは３〜50の整数）
で示される単量体５〜50重量％、ビニル芳香族
化合物、メタクリル酸エステル、アクリル酸エ
ステルおよびビニルシアン化合物から選ばれた
少なくとも１種の単量体95〜50重量％からなる
単量体組成物95〜20重量部をグラフト重合する
にあたり、一般式（）で示される単量体使用
量の少なくとも80重量％以上を含む単量体混合
物をグラフト重合した後、残りの単量体混合物
をグラフト重合して得られるグラフト共重合体
10〜100重量部と
(B) 上記グラフト共重合体と相溶性のある熱可塑
性樹脂90〜０重量部
とからなり、ジエン系共重合体の割合が５〜30重
量％である樹脂が、艶消し効果があり、且つ帯電
防止性を有することを見い出し、本発明を完成し
た。
ポリアルキレンオキサイド基を含む単量体を共
重合して帯電防止性を有する樹脂組成物を製造す
る方法については、例えば特開昭58―98317に記
載されている。この方法の様に、グラフト鎖単量
体中にポリエチレンオキサイド基を有する単量体
を、単に均一に混在させるだけでは帯電防止性を
有する樹脂を得ることはできても、本発明の様な
艶消し性で且つ帯電防止性を有する樹脂を得るこ
とはできない。
以下更に詳しく本発明を説明する。
まず本発明において使用するジエン系共重合体
は、ブタジエン、イソプレンなどの共役ジエン系
単量体50〜100重量％とこれと共重合しうるスチ
レン、アクリロニトリル、アクリル酸エステルま
たはメタクリル酸エステルなどのビニル系単量体
50〜０重量％とを重合させることによりえられ
る。ジエン系共重合体ラテツクスとしては、好ま
しくは平均粒子径0.15μ以上、ゲル含有率70重量
％以上のものが用いられる。
次に、グラフト共重合で使用されるグラフト鎖
単量体は前記一般式（）で表わされる親水性の
単量体、ビニル芳香族化合物、メタクリル酸エス
テル、アクリル酸エステルおよびビニルシアン化
合物である。一般式（）で表わされる単量体と
しては、ポリエチレングリコールモノメタクリレ
ート、ポリエチレングリコールモノアクリレー
ト、ポリプロピレングリコールモノメタクリレー
ト、メトキシポリエチレングリコールモノメタク
リレート等がある。ポリアルキレンオキサイド基
の数ｎは３〜50であり、特に５〜30が好ましい。
ｎが２以下では十分な帯電防止効果及び艶消し効
果が得られず、51以上では重合性が悪くなる。
ビニル芳香族化合物、メタクリル酸エステル、
アクリル酸エステルおよびビニルシアン化合物と
しては、スチレン、α―メチルスチレン、ビニル
トルエン、ｔ―ブチルスチレン、クロロスチレ
ン、メタクリル酸メチル、メタクリル酸エチル、
メタクリル酸プロピル、メタクリル酸ブチル、メ
タクリル酸２―エチルヘキシル、アクリル酸メチ
ル、アクリル酸エチル、アクリル酸プロピル、ア
クリル酸ブチル、アクリル酸２―エチルヘキシ
ル、アクリロニトリル、メタクリロニトリル等で
ある。
一般式（）で表わされる単量体の使用量は、
グラフト重合に使用する単量体全体の５〜50重量
％、好ましくは10〜40重量％である。５重量％未
満では艶消し及び帯電防止効果が発揮され難い。
特に、艶消し効果が損なわれる。また、50重量％
を越えると親水性が強くなり過ぎるため樹脂の機
械的性質の低下を招く傾向がでてくるので、本発
明においては５〜50重量％と定めた。
グラフト共重合の方法としては、先ず一般式
（）で示される単量体使用量の80〜100重量％を
含む単量体混合物をグラフト重合した後、残りの
単量体混合物をグラフト重合することが必要であ
る。一般式（）で示される単量体を高い割合で
含む単量体混合物を先ず始めにグラフト重合しな
いと表面の艶消し効果があり、且つ帯電防止性を
有する樹脂は得られない。例えば、全グラフト単
量体の均一混合物をグラフト共重合した場合、帯
電防止性のある樹脂は得られるが、艶消し効果は
得られない。また、一般式（）の単量体を高い
割合で含む単量体混合物をグラフト重合の後半に
重合させる方法では、グラフト共重合体ラテツク
ス系が著しく不安定となり、製造が困難である。
ジエン系共重合体とグラフト単量体との割合
は、重量比で５：95〜80：20で、好ましくは10：
90〜70：30である。ジエン系共重合体が５重量％
未満では艶消し効果及び帯電防止が得られない。
ジエン系共重合体が80重量％を越えると機械的性
質が低下する。
ジエン系共重合体及びグラフト共重合体の製造
方法は通常の乳化重合法が採用できる。
グラフト共重合体と相溶性のある熱可塑性樹脂
は、所望の特性に樹脂を改質するために用いられ
る。その組成はグラフト共重合体に用いるグラフ
ト鎖単量体及び又は一般式（）の単量体を用い
るのが好ましいが、グラフト共重合体と相溶性の
ある樹脂であればこれ以外の熱可塑性樹脂も使用
できる。
グラフト共重合体(A)と熱可塑性樹脂(B)との混合
割合は、重量比で10：90〜100：０であり、好ま
しくは30：70〜100：０である。(B)が90重量％を
越えると帯電防止性及び艶消し性が損なわれる。
樹脂中のジエン系共重合体の割合は、機械的性
質、流動性等の観点から５〜30重量％である。
(A)と(B)との混合は公知の方法を採用できる。た
とえばラテツクス状態での混合、粉末あるいはペ
レツトをロール、押出機等で混練する方法があ
る。
本発明の艶消し性且つ帯電防止性樹脂は、射出
成形法、押出成形法、圧縮成形法、真空成形法等
の通常の加工方法を適用できる。
以下実施例により本発明を説明する。
実施例１〜３及び比較例１〜５
(1) グラフト共重合体(A)の製造
撹拌機つき反応器に、
ドデシルベンゼンスルホン酸ソーダ
1.0重量部
ナトリウムホルムアルデヒドスルホキシレー
ト 0.2 〃
エチレンジアミンテトラ酢酸ソーダ
0.01 〃
硫酸第１鉄 0.0025 〃
脱塩水 250 〃
を仕込み、脱酸素後、窒素気流中で60℃に加熱撹
拌後、表１の例Ａ―１〜Ａ―８にそれぞれ示す処
方に従つて、ポリブタジエンラテツクス（平均粒
子径0.22μ、ゲル含有率85％）於び単量体混合物
(イ)を仕込み、60℃で２時間重合した後、単量体混
合物(ロ)を仕込み、60℃で２時間重合して重合体ラ
テツクスを得た。
The present invention relates to a method for producing a resin that has antistatic properties and has a matte surface effect. ABS resin, which has been conventionally known as an impact-resistant thermoplastic resin, is used for various purposes because of its excellent moldability, impact resistance, and good surface gloss. However, on the contrary, there are applications in which a molded product with a low surface gloss is desired; for example, in some applications such as interior parts for automobiles and external parts for household electrical appliances, the surface of the molded product may be left in a matte state. It may make people feel better and contribute to safety. There are methods to make the surface of the molded object matte, such as applying texture to the surface or applying a matte coating. In addition to increasing costs, problems arise in the strength of the paint film and deterioration of the coated surface of the molded product due to the thinner contained in the paint. Therefore,
It is more desirable to reduce the surface gloss of the material itself to eliminate its luster. One way to make the molded product matte is to reduce the gloss on the surface of the molded product by adding inorganic fillers such as talc, calcium carbonate, or silica.
In either case, these methods have poor effects, resulting in a decrease in impact strength and formability. In addition, thermoplastic resins generally have a high electrical resistance and are easily charged by friction or contact, attracting dirt and dust and causing various problems in the fields of molded products, sheets, films, fibers, etc. It's summery. Various methods have been proposed to overcome this drawback. For example, there is a method of incorporating an antistatic agent. This method of heating and kneading is simple, but if the antistatic agent present on the surface is removed by washing with water, friction, or other means, the antistatic ability is lost. Even so, some of the antistatic agent contained inside the molded product bleeds to the surface to compensate for this, but especially with polystyrene and ABC resins, it is difficult for the antistatic agent to bleed from the inside to the surface, so the antistatic ability is reduced. There are problems such as difficulty in recovery. Also,
There is a method of chemically modifying thermoplastic resins. These methods involve copolymerizing monomers with antistatic properties, but generally there is a problem in that moldability is significantly reduced. The present invention improves at once the various drawbacks in obtaining a resin with matte and antistatic properties as described above,
The present invention provides a method for producing a thermoplastic resin that has a matte effect and antistatic properties. Specific application fields include, for example, electrical equipment parts such as cassette tape recorder cases and instrument covers, packaging supplies, lighting equipment, building materials, and other applications that require antistatic properties and where surface reflection is disliked, especially the reflected light. It is suitable for applications where the color is a hindrance to safety, and applications where the matte finish gives a luxurious feel. As a result of intensive studies, the present inventor has developed a method using (A) a conjugated diene monomer in order to obtain a resin that has permanent antistatic properties that do not deteriorate due to washing, etc., and has a matte, luxurious appearance. In the presence of 5 to 80 parts by weight (in terms of solid content) of a diene copolymer latex containing 50% by weight or more, the following general formula () (In the formula, R 1 , R 2 , R 3 are hydrogen or have 1 to 1 carbon atoms.
4 alkyl group, n is an integer of 3 to 50), at least one monomer selected from vinyl aromatic compounds, methacrylic esters, acrylic esters, and vinyl cyan compounds. When graft polymerizing 95 to 20 parts by weight of a monomer composition consisting of 95 to 50% by weight, a monomer mixture containing at least 80% by weight of the monomer represented by the general formula () is used. Graft copolymer obtained by graft polymerizing the remaining monomer mixture after graft polymerization
A resin consisting of 10 to 100 parts by weight and (B) 90 to 0 parts by weight of a thermoplastic resin compatible with the above-mentioned graft copolymer, in which the proportion of the diene copolymer is 5 to 30% by weight, It was discovered that it has an erasing effect and antistatic properties, and the present invention was completed. A method for producing a resin composition having antistatic properties by copolymerizing a monomer containing a polyalkylene oxide group is described, for example, in JP-A-58-98317. Although it is possible to obtain a resin with antistatic properties by simply uniformly mixing monomers having polyethylene oxide groups in the graft chain monomers as in this method, it is possible to obtain a resin with antistatic properties, but it is possible to obtain a resin with antistatic properties. It is not possible to obtain a resin that is erasable and has antistatic properties. The present invention will be explained in more detail below. First, the diene copolymer used in the present invention consists of 50 to 100% by weight of a conjugated diene monomer such as butadiene or isoprene, and vinyl such as styrene, acrylonitrile, acrylic ester, or methacrylic ester that can be copolymerized with this. system monomer
It can be obtained by polymerizing 50 to 0% by weight. The diene copolymer latex preferably has an average particle diameter of 0.15 μm or more and a gel content of 70% by weight or more. Next, the graft chain monomers used in the graft copolymerization are hydrophilic monomers represented by the above general formula (), vinyl aromatic compounds, methacrylic esters, acrylic esters, and vinyl cyanide compounds. Examples of the monomer represented by the general formula () include polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, and methoxypolyethylene glycol monomethacrylate. The number n of polyalkylene oxide groups is 3 to 50, particularly preferably 5 to 30.
When n is less than 2, sufficient antistatic effect and matte effect cannot be obtained, and when n is more than 51, polymerizability deteriorates. Vinyl aromatic compounds, methacrylic acid esters,
Examples of acrylic esters and vinyl cyanide compounds include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, methyl methacrylate, ethyl methacrylate,
These include propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, methacrylonitrile, and the like. The usage amount of the monomer represented by the general formula () is:
The amount is 5 to 50% by weight, preferably 10 to 40% by weight of the total monomers used in graft polymerization. If the amount is less than 5% by weight, matting and antistatic effects are difficult to exhibit.
In particular, the matte effect is impaired. Also, 50% by weight
If the content exceeds 5% by weight, the hydrophilicity becomes too strong and the mechanical properties of the resin tend to deteriorate. The method of graft copolymerization is to first graft-polymerize a monomer mixture containing 80 to 100% by weight of the monomer usage amount represented by general formula (), and then graft-polymerize the remaining monomer mixture. is necessary. Unless a monomer mixture containing a high proportion of the monomer represented by the general formula () is first graft-polymerized, a resin with a matte surface effect and antistatic properties cannot be obtained. For example, when a homogeneous mixture of all graft monomers is graft copolymerized, a resin with antistatic properties is obtained, but a matting effect is not obtained. Furthermore, in a method in which a monomer mixture containing a high proportion of the monomer of the general formula () is polymerized in the latter half of the graft polymerization, the graft copolymer latex system becomes extremely unstable and production is difficult. The weight ratio of the diene copolymer to the graft monomer is 5:95 to 80:20, preferably 10:
90-70:30. 5% by weight of diene copolymer
If it is less than that, the matting effect and antistatic effect cannot be obtained.
If the diene copolymer content exceeds 80% by weight, mechanical properties will deteriorate. The diene copolymer and graft copolymer can be produced by a conventional emulsion polymerization method. Thermoplastic resins that are compatible with the graft copolymer are used to modify the resin to desired properties. As for its composition, it is preferable to use the graft chain monomer used in the graft copolymer and/or the monomer of the general formula (), but other thermoplastic resins may be used as long as they are compatible with the graft copolymer. can also be used. The mixing ratio of the graft copolymer (A) and the thermoplastic resin (B) is 10:90 to 100:0 by weight, preferably 30:70 to 100:0. If (B) exceeds 90% by weight, antistatic properties and matte properties will be impaired.
The proportion of the diene copolymer in the resin is 5 to 30% by weight from the viewpoint of mechanical properties, fluidity, etc. A known method can be used to mix (A) and (B). For example, there is a method of mixing in a latex state, and a method of kneading powder or pellets using a roll, extruder, etc. The matte and antistatic resin of the present invention can be processed by conventional processing methods such as injection molding, extrusion molding, compression molding, and vacuum forming. The present invention will be explained below with reference to Examples. Examples 1 to 3 and Comparative Examples 1 to 5 (1) Production of graft copolymer (A) In a reactor equipped with a stirrer, sodium dodecylbenzenesulfonate
1.0 parts by weight Sodium formaldehyde sulfoxylate 0.2 Sodium ethylenediaminetetraacetate
0.01 〃 Ferrous sulfate 0.0025 〃 Demineralized water 250 〃 were charged, deoxidized, heated to 60°C in a nitrogen stream, and stirred. Polybutadiene was prepared according to the recipes shown in Examples A-1 to A-8 of Table 1, respectively. Latex (average particle size 0.22μ, gel content 85%) and monomer mixture
After charging (a) and polymerizing at 60°C for 2 hours, monomer mixture (b) was charged and polymerizing at 60°C for 2 hours to obtain a polymer latex.
【表】
(2) 熱可塑性樹脂(B)の製造
撹拌機つき反応器に、
ドデシルベンゼンスルホン酸ソーダ
1.5重量部
ナトリウムホルムアルデヒドスルホキシレー
ト 0.4 〃
エチレンジアミンテトラ酢酸ソーダ
0.01 〃
硫酸第１鉄 0.0025 〃
脱塩水 250 〃
を仕込み、脱酸素後、窒素気流中で60℃に加熱撹
拌後、
α―メチルスチレン 50重量部
アクリロニトリル 25 〃
スチレン 25 〃
クメンハイドロパーオキサイド 0.3 〃
ドデシルメルカプタン 0.4 〃
を仕込んで重合し、重合体ラテツクスを得た。
特性の測定方法
グラフト共重合体(A)のラテツクス及び熱可塑性
樹脂(B)のラテツクスを、表２に示す組成となる様
にラテツクス状態で混合し、酸化防止剤を加え、
塩析した後、水洗、過、乾燥してペレツト化
し、射出成形機にて平板とテストピースの成形を
行なつた。得られたサンプルを用いて、
(i) ASTM（D256―54T）に従い、23℃における
ノツチ付アイゾツト衝撃強度を測定した。
(ii) 表面光沢の測定は、デジタル変角光沢計
VGV―4D（スガ試験機(株)製）を用い、入射角
60゜、反射角60゜での表面光沢を測定した。
(iii) 表面固有抵抗は、23℃，50％相対湿度の雰囲
気に１週間放置した後、超絶縁抵抗計（タケダ
理研(株)製）を使用して測定した。
(iv) 帯電圧半減期は、23℃，50％相対湿度の雰囲
気に１週間放置した後、スタチツクオネストメ
ータ（関戸商会製）を使用して測定した。
これらの結果を表２に併記した。
本発明による実施例１，２及び３の場合は比較
例１〜５に比べて耐衝撃強度も高く、帯電防止性
があり、且つ表面光沢も低いことがわかる。[Table] (2) Production of thermoplastic resin (B) In a reactor equipped with a stirrer, add sodium dodecylbenzenesulfonate.
1.5 parts by weight Sodium formaldehyde sulfoxylate 0.4 Sodium ethylenediaminetetraacetate
0.01 〃 Ferrous sulfate 0.0025 〃 Demineralized water 250 〃 Prepared, deoxidized, heated to 60℃ in a nitrogen stream, stirred, α-methylstyrene 50 parts by weight Acrylonitrile 25 〃 Styrene 25 〃 Cumene hydroperoxide 0.3 〃 Dodecyl 0.4 〃 of mercaptan was charged and polymerized to obtain a polymer latex. Method for measuring properties The latex of the graft copolymer (A) and the latex of the thermoplastic resin (B) were mixed in a latex state so as to have the composition shown in Table 2, an antioxidant was added,
After salting out, the pellets were washed with water, filtered, and dried to form pellets, which were then molded into flat plates and test pieces using an injection molding machine. Using the obtained sample, (i) Notched Izot impact strength at 23°C was measured in accordance with ASTM (D256-54T). (ii) Surface gloss is measured using a digital variable angle gloss meter.
Using VGV-4D (manufactured by Suga Test Instruments Co., Ltd.),
The surface gloss was measured at an angle of 60° and a reflection angle of 60°. (iii) The surface resistivity was measured using a super insulation resistance meter (manufactured by Takeda Riken Co., Ltd.) after being left in an atmosphere of 23° C. and 50% relative humidity for one week. (iv) The half-life of the charged voltage was measured using a static honest meter (manufactured by Sekido Shokai) after leaving it in an atmosphere of 23° C. and 50% relative humidity for one week. These results are also listed in Table 2. It can be seen that Examples 1, 2, and 3 according to the present invention have higher impact strength, antistatic properties, and lower surface gloss than Comparative Examples 1 to 5.
Claims (1)
ジエン系共重合体ラテツクス５〜80重量部（固
形分換算）の存在下に、下記一般式（） （式中、R1，R2，R3は水素又は炭素数１〜
４のアルキル基、ｎは３〜50の整数を表わす） で示される単量体５〜50重量％、ビニル芳香族
化合物、メタクリル酸エステル、アクリル酸エ
ステルおよびビニルシアン化合物からなる群か
ら選ばれた少なくとも１種の単量体95〜50重量
％からなる単量体組成物95〜20重量部をグラフ
ト重合するにあたり、一般式（）で示される
単量体使用量の少なくとも80重量％以上を含む
単量体混合物をグラフト重合した後、残りの単
量体混合物をグラフト重合して得られるグラフ
ト共重合体10〜100重量部と (B) 上記グラフト共重合体と相溶性のある熱可塑
性樹脂90〜０重量部 とからなり、ジエン系共重合体の割合が５〜30重
量％であることを特徴とする表面艶消し性帯電防
止性樹脂の製造方法。[Scope of Claims] 1 (A) In the presence of 5 to 80 parts by weight (in terms of solid content) of a diene copolymer latex containing 50% by weight or more of a conjugated diene monomer, the following general formula () (In the formula, R 1 , R 2 , R 3 are hydrogen or have 1 to 1 carbon atoms.
4 alkyl group, n represents an integer of 3 to 50) 5 to 50% by weight of a monomer selected from the group consisting of vinyl aromatic compounds, methacrylic esters, acrylic esters, and vinyl cyanide compounds In graft polymerizing 95 to 20 parts by weight of a monomer composition consisting of 95 to 50 parts by weight of at least one monomer, the monomer composition contains at least 80 parts by weight of the monomer represented by the general formula (). After graft polymerizing the monomer mixture, 10 to 100 parts by weight of a graft copolymer obtained by graft polymerizing the remaining monomer mixture and (B) 90 parts by weight of a thermoplastic resin compatible with the above graft copolymer. 0 parts by weight, and the proportion of the diene copolymer is 5 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP94284A JPS60144314A (en) | 1984-01-06 | 1984-01-06 | Production of matting/antistatic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP94284A JPS60144314A (en) | 1984-01-06 | 1984-01-06 | Production of matting/antistatic resin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8581486A Division JPS6248756A (en) | 1986-04-14 | 1986-04-14 | Matting, antistatic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60144314A JPS60144314A (en) | 1985-07-30 |
| JPS6367807B2 true JPS6367807B2 (en) | 1988-12-27 |
Family
ID=11487723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP94284A Granted JPS60144314A (en) | 1984-01-06 | 1984-01-06 | Production of matting/antistatic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60144314A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60195151A (en) * | 1984-03-16 | 1985-10-03 | Toray Ind Inc | Antistatic resin composition |
| JPH0641548B2 (en) * | 1984-04-11 | 1994-06-01 | 東レ株式会社 | Antistatic resin composition |
| JPS6248756A (en) * | 1986-04-14 | 1987-03-03 | Kanegafuchi Chem Ind Co Ltd | Matting, antistatic resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5536237A (en) * | 1978-09-06 | 1980-03-13 | Kureha Chem Ind Co Ltd | Antistatic resin composition |
| JPS56118446A (en) * | 1980-02-22 | 1981-09-17 | Kureha Chem Ind Co Ltd | Antistatic resin composition |
| JPS56120751A (en) * | 1980-12-15 | 1981-09-22 | Kureha Chem Ind Co Ltd | Antistatic resin composition |
| JPS56125418A (en) * | 1980-03-06 | 1981-10-01 | Kureha Chem Ind Co Ltd | Antistatic agent for thermosetting resin |
-
1984
- 1984-01-06 JP JP94284A patent/JPS60144314A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5536237A (en) * | 1978-09-06 | 1980-03-13 | Kureha Chem Ind Co Ltd | Antistatic resin composition |
| JPS56118446A (en) * | 1980-02-22 | 1981-09-17 | Kureha Chem Ind Co Ltd | Antistatic resin composition |
| JPS56125418A (en) * | 1980-03-06 | 1981-10-01 | Kureha Chem Ind Co Ltd | Antistatic agent for thermosetting resin |
| JPS56120751A (en) * | 1980-12-15 | 1981-09-22 | Kureha Chem Ind Co Ltd | Antistatic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60144314A (en) | 1985-07-30 |
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