JPH0517938B2 - - Google Patents
Info
- Publication number
- JPH0517938B2 JPH0517938B2 JP17261184A JP17261184A JPH0517938B2 JP H0517938 B2 JPH0517938 B2 JP H0517938B2 JP 17261184 A JP17261184 A JP 17261184A JP 17261184 A JP17261184 A JP 17261184A JP H0517938 B2 JPH0517938 B2 JP H0517938B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylate
- methacrylic resin
- resin composition
- methacrylate
- 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 - Fee Related
Links
- 239000000113 methacrylic resin Substances 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- ARYIITVULFDIQB-UHFFFAOYSA-N (2-methyloxiran-2-yl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1(C)CO1 ARYIITVULFDIQB-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- -1 phosphorus compound Chemical class 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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 2
- DMBUODUULYCPAK-UHFFFAOYSA-N 1,3-bis(docosanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCC DMBUODUULYCPAK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920006163 vinyl copolymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- JZVIGYINCGLMQW-UHFFFAOYSA-N 1-(oxiran-2-yl)ethyl prop-2-enoate Chemical compound C=CC(=O)OC(C)C1CO1 JZVIGYINCGLMQW-UHFFFAOYSA-N 0.000 description 1
- WECGLUPZRHILCT-GSNKCQISSA-N 1-linoleoyl-sn-glycerol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OC[C@@H](O)CO WECGLUPZRHILCT-GSNKCQISSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QHZLMUACJMDIAE-UHFFFAOYSA-N Palmitic acid monoglyceride Natural products CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- DCBSHORRWZKAKO-UHFFFAOYSA-N alpha-glycerol monomyristate Natural products CCCCCCCCCCCCCC(=O)OCC(O)CO DCBSHORRWZKAKO-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001530 fumaric acid 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012766 organic filler Substances 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔〕 産業上の利用分野
本発明は、帯電防止性能に優れたメタクリル樹
脂組成物に関する。更に詳しくは、帯電防止性能
の耐久性、耐水性を著しく向上させたメタクリル
樹脂組成物に関する。
メタクリル樹脂は、その卓越した透明性、良好
な機械的性質、加工性、成形品の外観の美麗さに
よつて照明器具、看板、装飾品等に広く使用され
ている。しかしメタクリル樹脂は表面固有抵抗が
非常に高く、接触、摩擦等で誘起された静電気が
逃散、消失しにくく、使用中の樹脂表面にほこり
等が付着し美しい外観を損い易い欠点を有してい
る。
本発明は、上記欠点を改良したものであり、か
かる分野で広く利用できるメタクリル樹脂組成物
を提供する。
〔〕 従来の技術と問題点
従来、このような静電気障害を除く方法として
高級脂肪酸モノグリセライドとポリアルキレング
リコールを練り込む方法（特開昭50−121350号公
報）、メタクリル酸とメチルメタクリレートの共
重合体にグリセリンモノ脂肪酸エステルを練り込
む方法（特開昭53−113852号公報）、メタクリル
樹脂にグリセリンモノ脂肪酸エステルと燐化合物
を練り込む方法（特開昭59−93745号公報）等が
行われている。その他メタクリル樹脂にグリセリ
ンモノ脂肪酸エステルと燐化合物、ポリアルキレ
ングリコールを添加する方法（特開昭51−49246
号公報）、メタクリル樹脂製造時の重合の前と後
２回に分けてグリセリンモノ脂肪酸エステルを添
加する方法（特開昭58−112949号公報）、メタク
リル樹脂にグリセリンモノ脂肪酸エステルとホウ
酸エステルを添加する方法（特開昭52−102362号
公報）が記載されている。しかし、これらの方法
はいづれも成形直後の初期は帯電防止性能を有す
るが、耐久性、耐水性が極めて悪く、水と接触す
るとすぐに帯電防止性能が無くなり、また成形後
経時的に性能が低下してくるという欠点を有して
いる。
〔〕発明の目的
本発明は、上記従来の問題点を解消するもので
あり、メタクリル樹脂の帯電防止性能の耐久性と
耐水性を飛躍的に向上させた組成物を提供するこ
とを目的とする。
〔〕発明の構成
本発明はメタクリル樹脂70〜99.4重量％、グリ
セリンモノ脂肪酸エステル0.3〜15重量％および
エポキシ基を含有するビニル系重合物より成る樹
脂組成物において、該樹脂組成物中のエポキシ基
含有単量体成分が0.05〜15重量％であることを特
徴とする帯電防止性能に優れたメタクリル樹脂組
成物に関する。
本発明のメタクリル樹脂としてはメタクリル酸
メチル単独重合体、または80重量％以上のメタク
リル酸メチルとアクリル酸エステルもしくはメタ
クリル酸エステル、アクリル酸、メタクリル酸、
スチレン、アクリロニトリル等との共重合物をい
う。アクリル酸エステルとしてはメチルアクリレ
ート、エチルアクリレート、ブチルアクリレート
など、メタクリル酸エステルとしてはメタクリル
酸エチル、メタクリル酸ブチル、メタクリル酸シ
クロヘキシルなどを用いることが可能である。
本発明に用いられるグリセリンモノ脂肪酸エス
テルとしては炭素数８〜22の高級脂肪酸のグリセ
リンモノエステルであつて、例えばラウリン酸モ
ノグリセライド、ミリスチン酸モノグリセライ
ド、パルミチン酸モノグリセライド、オレイン酸
モノグリセライド、ステアリン酸モノグリセライ
ド、モンタン酸モノグリセライド、リノール酸モ
ノグリセライド、ベヘニン酸モノグリセライド、
が好ましい例としてあげられる。これらは単独で
あるいは必要に応じて２種以上を用いることもで
きる。高級脂肪酸モノグリセライドの添加量は
0.3〜15重量％、好ましくは１〜10重量％用いら
れる。添加量が0.3重量％より少い場合にはメタ
クリル樹脂の帯電防止性能はほとんど期待できな
い。また15重量％以上添加した場合はコストも高
く、またメタクリル樹脂が白濁して透明性が低下
してくるため好ましくなく、耐熱性等の物性低下
が顕著であるため好ましくない。
本発明のエポキシ基を含有するビニル系重合体
はグリセリンモノ脂肪酸エステルの帯電防止性能
に耐久性、耐水性を持たせるために特に有効なも
のである。このエポキシ基を含有するビニル系重
合体ないしは共重合体としては例えばグリシジル
アクリレート、グリシジルメタクリレート、β−
メチルグリシジルアクリレート、およびβ−メチ
ルグリシジルメタクリレートのうち少なくとも１
種の単量体成分の単独重合体、あるいはこれらの
単量体を少なくとも５重量％と他の共重合体のビ
ニル系モノマーとの共重合体である。他の共重合
体のビニル系モノマーとしてはメチル（メタ）ア
クリレート（メチルアクリレートとメチルメタク
リレートを表わす。）、エチル（メタ）アクリレー
ト、ブチル（メタ）アクリレート、２−エチルヘ
キシル（メタ）アクリレート、ラウリル（メタ）
アクリレート、シクロヘキシル（メタ）アクリレ
ート、エチルセロソルブ（メタ）アクリレート、
ベンジル（メタ）アクリレート、β−ヒドロキシ
エチル（メタ）アクリレート、β−ヒドロキシプ
ロピル（メタ）アクリレート、（メタ）アクリル
酸、スチレン、ビニルトルエン、アクリロニトリ
ル、アクリルアマイド、さらにはフマル酸、マレ
イン酸、イタコン酸及びこれらのアルキルエステ
ル類などがある。
エポキシ基を含有するビニル系重合体ないし共
重合体の量は樹脂組成物中、エポキシ基含有単量
体成分が0.05〜15重量％（好ましくは0.1〜７重
量％）になる量を要する。エポキシ基含有単量体
成分の量が0.05重量％より少いと帯色防止性能の
耐久性、耐水性はほとんど期待できなく、15重量
％以上加えるとアクリル樹脂の透明性が低下する
ため好ましくない。
本発明の組成物はメタクリル樹脂、グリセリン
モノ脂肪酸エステル、エポキシ基を含有するビニ
ル系重合物を押出機などで溶融混練することによ
つて得られる。また別の方法としてはメタクリル
樹脂を製造するに当り、原料モノマーの重合の際
にグリセンリンモノ脂肪酸エステル、エポキシ基
を含有するビニル系重合体の一部或いは全量を添
加することにより得ることもできる。
その他本発明の組成物には顔料、無機充填剤、
有機充填剤を配合することもできる。
〔〕 実施例
実施例１〜５比較例１〜３
メチルメタクリレート500ｇ、ｎ−ブチルメタ
クリレート600ｇ、グリシジルメタクリレート800
ｇ、アゾビスイソブチロニトリル40ｇおよびジ−
ｔ−ブチルパーオキシド20ｇを予め120℃に加熱
したキシレンの２中に４時間亘つて滴下した。
滴下終了後さらに125℃で５時間反応させ、200
℃、１mmＨｇ減圧下で溶剤を留出させグリシジル
メタクリレート40重量％含有する共重合体を得
た。この共重合体を重合体Ａとする。
メチルメタクリレート97重量％及びメチルアク
リレート３重量％からなるメタアクリル樹脂とス
テアリン酸モノグリセライド（理研ビタミン(株)
製、リケマール
S100A）を第１表に示す割合に
混合した後、40mmφ押出機を用いて250℃でペレ
ツト化したのち10オンス射出成形機によつて250
℃で射出成形し50×50×３mmの平板を得た。この
板を23℃、50％湿度の恒温室で48時間状態調整し
たのち表面固有抵抗及び、半減期を測定し、その
結果を第１表に示した。また測定後板を30℃の水
中で洗浄した後23℃、50％湿度の恒温室で48時間
状態調整したのちの表面固有抵抗及び半減期も併
せて第１表に示した。
なお表面固有抵抗値は極超絶縁計SM−10型
（東亜電波工業(株)製）を用いて測定し半減期はス
タテイツクオネストメーター（(株)宍戸商会製）を
用いて測定した。
[] Industrial Application Field The present invention relates to a methacrylic resin composition with excellent antistatic performance. More specifically, the present invention relates to a methacrylic resin composition that has significantly improved antistatic properties, durability, and water resistance. Methacrylic resin is widely used in lighting equipment, signboards, decorative items, etc. due to its excellent transparency, good mechanical properties, processability, and beautiful appearance of molded products. However, methacrylic resin has a very high surface resistivity, which makes it difficult for static electricity induced by contact or friction to dissipate or disappear, and it has the disadvantage that dust and other substances tend to adhere to the resin surface during use, damaging its beautiful appearance. There is. The present invention improves the above drawbacks and provides a methacrylic resin composition that can be widely used in such fields. [] Conventional techniques and problems Conventionally, as a method to eliminate such static electricity damage, a method of kneading higher fatty acid monoglyceride and polyalkylene glycol (Japanese Patent Application Laid-open No. 121350/1982), a copolymer of methacrylic acid and methyl methacrylate have been used. Methods such as kneading glycerin monofatty acid ester into methacrylic resin (Japanese Unexamined Patent Publication No. 53-113852), and kneading glycerin monofatty acid ester and phosphorus compound into methacrylic resin (Japanese Unexamined Patent Publication No. 59-93745) have been carried out. . Other methods of adding glycerin monofatty acid ester, phosphorus compound, and polyalkylene glycol to methacrylic resin (JP-A-51-49246
(Japanese Patent Application Laid-open No. 112949/1983), a method of adding glycerin monofatty acid ester and boric acid ester to methacrylic resin twice, before and after polymerization (Japanese Patent Application Laid-Open No. 112949/1982). A method of addition (Japanese Unexamined Patent Publication No. 102362/1983) is described. However, all of these methods have antistatic properties in the initial stage immediately after molding, but their durability and water resistance are extremely poor, and when they come into contact with water, the antistatic properties disappear immediately, and the performance deteriorates over time after molding. It has the disadvantage of being []Object of the invention The present invention solves the above-mentioned conventional problems, and aims to provide a composition that dramatically improves the durability and water resistance of the antistatic performance of methacrylic resin. . []Structure of the Invention The present invention provides a resin composition comprising 70 to 99.4% by weight of a methacrylic resin, 0.3 to 15% by weight of a glycerin monofatty acid ester, and a vinyl polymer containing an epoxy group. The present invention relates to a methacrylic resin composition with excellent antistatic performance, characterized in that the monomer component contained is 0.05 to 15% by weight. As the methacrylic resin of the present invention, methyl methacrylate homopolymer, 80% by weight or more of methyl methacrylate and acrylic ester or methacrylic ester, acrylic acid, methacrylic acid,
A copolymer with styrene, acrylonitrile, etc. As the acrylic ester, methyl acrylate, ethyl acrylate, butyl acrylate, etc. can be used, and as the methacrylic ester, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, etc. can be used. The glycerin monofatty acid esters used in the present invention include glycerin monoesters of higher fatty acids having 8 to 22 carbon atoms, such as lauric acid monoglyceride, myristic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, stearic acid monoglyceride, and montanic acid. Monoglyceride, linoleic acid monoglyceride, behenic acid monoglyceride,
is given as a preferable example. These can be used alone or in combination of two or more, if necessary. The amount of higher fatty acid monoglyceride added is
It is used in an amount of 0.3 to 15% by weight, preferably 1 to 10% by weight. If the amount added is less than 0.3% by weight, almost no antistatic performance can be expected from the methacrylic resin. Further, if it is added in an amount of 15% by weight or more, the cost is high, the methacrylic resin becomes cloudy and the transparency decreases, which is undesirable, and the physical properties such as heat resistance are significantly deteriorated, which is undesirable. The epoxy group-containing vinyl polymer of the present invention is particularly effective for imparting antistatic properties to glycerin monofatty acid esters with durability and water resistance. Examples of vinyl polymers or copolymers containing epoxy groups include glycidyl acrylate, glycidyl methacrylate, β-
At least one of methylglycidyl acrylate and β-methylglycidyl methacrylate
It is a homopolymer of various monomer components, or a copolymer of at least 5% by weight of these monomers and a vinyl monomer of another copolymer. Other copolymer vinyl monomers include methyl (meth)acrylate (representing methyl acrylate and methyl methacrylate), ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. )
Acrylate, cyclohexyl (meth)acrylate, ethyl cellosolve (meth)acrylate,
Benzyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, (meth)acrylic acid, styrene, vinyltoluene, acrylonitrile, acrylamide, as well as fumaric acid, maleic acid, and itaconic acid. and their alkyl esters. The amount of the epoxy group-containing vinyl polymer or copolymer is such that the epoxy group-containing monomer component is 0.05 to 15% by weight (preferably 0.1 to 7% by weight) in the resin composition. If the amount of the epoxy group-containing monomer component is less than 0.05% by weight, the durability and water resistance of the anti-coloring property can hardly be expected, and if it is added in excess of 15% by weight, the transparency of the acrylic resin will decrease, which is not preferable. The composition of the present invention can be obtained by melt-kneading a methacrylic resin, a glycerin monofatty acid ester, and a vinyl polymer containing an epoxy group using an extruder or the like. Alternatively, when producing methacrylic resin, it can be obtained by adding part or all of glycenphosphorus monofatty acid ester and a vinyl polymer containing an epoxy group during polymerization of raw material monomers. . Other compositions of the present invention include pigments, inorganic fillers,
Organic fillers can also be blended. [] Examples Examples 1-5 Comparative Examples 1-3 Methyl methacrylate 500g, n-butyl methacrylate 600g, glycidyl methacrylate 800g
g, azobisisobutyronitrile 40g and di-
20 g of t-butyl peroxide was added dropwise over 4 hours to a solution of xylene preheated to 120°C.
After the completion of the dropwise addition, the reaction was further carried out at 125℃ for 5 hours, and 200℃
The solvent was distilled off at a temperature of 1 mmHg under reduced pressure to obtain a copolymer containing 40% by weight of glycidyl methacrylate. This copolymer is referred to as Polymer A. Methacrylic resin consisting of 97% by weight of methyl methacrylate and 3% by weight of methyl acrylate and stearic acid monoglyceride (Riken Vitamin Co., Ltd.)
Rikemar S100A) were mixed in the proportions shown in Table 1, pelletized at 250°C using a 40mmφ extruder, and then pelletized at 250°C using a 10oz injection molding machine.
A flat plate of 50 x 50 x 3 mm was obtained by injection molding at ℃. After conditioning this plate in a constant temperature room at 23° C. and 50% humidity for 48 hours, the surface resistivity and half-life were measured, and the results are shown in Table 1. Table 1 also shows the surface resistivity and half-life after washing the plate in water at 30°C after measurement and conditioning it in a constant temperature room at 23°C and 50% humidity for 48 hours. The surface resistivity value was measured using a ultra-super insulation meter SM-10 model (manufactured by Toa Denpa Kogyo Co., Ltd.), and the half-life was measured using a static honest meter (manufactured by Shishido Shokai Co., Ltd.).
【表】
比較例１、２においては水洗前は帯電防止性能
はあるが水洗することで完全になくなつた。比較
例３は成形体の白濁が見られた。
実施例５〜７、比較例４
β−メチルグリシジルアクリレート200ｇ、メ
チルメタクリレート400ｇ、ラウリルメルカプタ
ン24ｇ、ラウロイルパーオキサイド2.4ｇを混合
溶解した後窒素雰囲気下70℃で４時間塊状重合さ
せ、共重合体(B)を得た。Ｂにはβ−メチルグリシ
ジルアクリレートが33.3重量％含まれていた。Ｂ
を粉砕後、実施例１と同じメタクリル樹脂にベヘ
ニン酸モノグリセライドとを混合し、実施例１と
同様にして50×50×３mmの平板を得た。帯電防止
性能を実施例１と同様に測定して結果を第２表に
示した。[Table] In Comparative Examples 1 and 2, there was antistatic performance before washing with water, but it completely disappeared after washing with water. In Comparative Example 3, clouding of the molded product was observed. Examples 5 to 7, Comparative Example 4 After mixing and dissolving 200 g of β-methylglycidyl acrylate, 400 g of methyl methacrylate, 24 g of lauryl mercaptan, and 2.4 g of lauroyl peroxide, bulk polymerization was carried out at 70°C for 4 hours in a nitrogen atmosphere to obtain a copolymer ( B) was obtained. B contained 33.3% by weight of β-methylglycidyl acrylate. B
After pulverizing, behenic acid monoglyceride was mixed with the same methacrylic resin as in Example 1, and a flat plate of 50 x 50 x 3 mm was obtained in the same manner as in Example 1. The antistatic performance was measured in the same manner as in Example 1, and the results are shown in Table 2.
【表】
〔〕 効果
本発明により得られたメタクリル樹脂組成物は
表面固有抵抗値が低く、帯電減衰半減期が短か
く、かつこの性能が長期に亘つて保持され水洗す
ることによつても低下しない。
本発明の組成物は、かかる利点を有することか
ら、照明用器具、電気計器、電子機器のカバーや
部品、メーターカバー、日用品、フイルムシー
ト、パネル等に顕著な効果を発揮する。[Table] [] Effects The methacrylic resin composition obtained by the present invention has a low surface resistivity value and a short charge decay half-life, and this performance is maintained for a long period of time and does not deteriorate even when washed with water. do not. Since the composition of the present invention has such advantages, it exhibits remarkable effects on lighting equipment, electric meters, covers and parts of electronic devices, meter covers, daily necessities, film sheets, panels, and the like.
Claims (1)
モノ脂肪酸エステル0.8〜15重量％およびエポキ
シ基を含有するビニル系重合体より成る樹脂組成
物において、該樹脂組成物中のエポキシ基含有単
量体成分が0.05〜15重量％であることを特徴とす
る帯電防止性能に優れたメタクリル樹脂組成物。 ２ エポキシ基を含有するビニル系重合体がグリ
シジルアクリレート、グリシジルメタクリレー
ト、β−メチルグリシジルアクリレートおよびβ
−メチルグリシジルメタクリレートよりなる群か
ら選ばれる少くとも１種の単量体成分を少なくと
も５重量％含む重合体であることを特徴とする特
許請求の範囲第１項記載のメタクリル樹脂組成
物。[Scope of Claims] 1. A resin composition comprising 70 to 99.4% by weight of a methacrylic resin, 0.8 to 15% by weight of a glycerin monofatty acid ester, and a vinyl polymer containing an epoxy group, wherein the resin composition contains an epoxy group. A methacrylic resin composition with excellent antistatic performance, characterized in that the monomer component is 0.05 to 15% by weight. 2 Vinyl polymers containing epoxy groups include glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, and β-methylglycidyl acrylate.
2. The methacrylic resin composition according to claim 1, which is a polymer containing at least 5% by weight of at least one monomer component selected from the group consisting of -methylglycidyl methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17261184A JPS6151048A (en) | 1984-08-20 | 1984-08-20 | Methacrylate resin composition having excellent antistatic performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17261184A JPS6151048A (en) | 1984-08-20 | 1984-08-20 | Methacrylate resin composition having excellent antistatic performance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6151048A JPS6151048A (en) | 1986-03-13 |
| JPH0517938B2 true JPH0517938B2 (en) | 1993-03-10 |
Family
ID=15945080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17261184A Granted JPS6151048A (en) | 1984-08-20 | 1984-08-20 | Methacrylate resin composition having excellent antistatic performance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6151048A (en) |
-
1984
- 1984-08-20 JP JP17261184A patent/JPS6151048A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6151048A (en) | 1986-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR910007310B1 (en) | Antistatic thermoplastic resin compositions | |
| CN101353390B (en) | Acrylic ester and unsaturated quaternary ammonium salt random copolymerization anstatic agent and preparation thereof | |
| JPH0254382B2 (en) | ||
| JP6751972B1 (en) | Antistatic acrylic resin and its manufacturing method | |
| JPH0517938B2 (en) | ||
| GB2031449A (en) | Antistatic resin composition | |
| JPS6038415B2 (en) | Methacrylic resin composition with excellent antistatic properties | |
| JPH032456B2 (en) | ||
| KR100931650B1 (en) | Preparation of Polymethylmethacrylate Copolymerized with Permanent Antistatic Agent | |
| JP2776537B2 (en) | Antistatic thermoplastic resin composition | |
| JPS5949935B2 (en) | Method for producing methacrylic resin composition with excellent antistatic properties | |
| JP3147385B2 (en) | Antistatic acrylic resin composition | |
| JPS5938982B2 (en) | Methacrylic resin composition with excellent antistatic properties | |
| JPS6326125B2 (en) | ||
| US5302668A (en) | Permanently antistatic polyacrylate articles and process for making them | |
| JPS5839860B2 (en) | Antistatic resin composition | |
| KR20010109514A (en) | A manufacturing method of acryl pannel with prevention of static electricity | |
| JPH01135857A (en) | Antistatic methacrylate resin composition | |
| JPS60144314A (en) | Production of matting/antistatic resin | |
| KR840001692B1 (en) | Antistatic resin compositi | |
| JPS6368614A (en) | Production of methacrylic resin cast plate excellent in antistatic property | |
| JP2001123151A (en) | Antistatic agent and thermoplastic resin composition comprising the same | |
| JP2865450B2 (en) | Antistatic agent for thermoplastic resin | |
| JPH08157682A (en) | Transparent and permanently antistatic resin composition | |
| JPS63339A (en) | Antistatic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |