JP2805519B2 - Antistatic agent for synthetic resin - Google Patents
Antistatic agent for synthetic resinInfo
- Publication number
- JP2805519B2 JP2805519B2 JP2040075A JP4007590A JP2805519B2 JP 2805519 B2 JP2805519 B2 JP 2805519B2 JP 2040075 A JP2040075 A JP 2040075A JP 4007590 A JP4007590 A JP 4007590A JP 2805519 B2 JP2805519 B2 JP 2805519B2
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- antistatic agent
- ester
- antistatic
- acid
- 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
- 229920003002 synthetic resin Polymers 0.000 title claims description 30
- 239000000057 synthetic resin Substances 0.000 title claims description 30
- 239000002216 antistatic agent Substances 0.000 title claims description 29
- 150000002148 esters Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 22
- 229930195729 fatty acid Natural products 0.000 description 22
- 239000000194 fatty acid Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- -1 glycerin fatty acid ester Chemical class 0.000 description 20
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 16
- 150000004665 fatty acids Chemical class 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 1
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 1
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000009474 immediate action Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 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 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は合成樹脂用帯電防止剤に関するものであり、
更に詳しくは、帯電防止性能の即効性、持続性、経日安
定性に優れ、さらに耐熱性に優れた合成樹脂用帯電防止
剤に関する。The present invention relates to an antistatic agent for a synthetic resin,
More specifically, the present invention relates to an antistatic agent for a synthetic resin, which is excellent in immediate action, durability, and chronological stability of antistatic performance, and further has excellent heat resistance.
［従来の技術］ 近年、合成樹脂はフィルム、シート、成形品、繊維等
の形態で広く利用されている。しかしながら、これら合
成樹脂製品は優れた電気絶縁性を有している反面、静電
気を発生し易く、加工性の低下や汚れ付着による商品価
値の著しい低下、人体への不快な電撃、更には発生した
静電気の放電による火災、爆発等の災害を引き起こす危
険性もある。この為、従来より合成樹脂用の種々の帯電
防止剤が検討されており、例えばグリセリン脂肪酸エス
テル、ソルビタン脂肪酸エステル、アルキルアルカノー
ルアミド、アルキルアルカノールアミン等の非イオン界
面活性剤、アルキルスルホン酸塩等のアニンオン界面活
性剤、各種の第４級アンモニウム化合物、及びこれらの
混合物が合成樹脂に配合され、静電気の発生が防止され
ている。[Related Art] In recent years, synthetic resins have been widely used in the form of films, sheets, molded articles, fibers and the like. However, while these synthetic resin products have excellent electrical insulation properties, they are liable to generate static electricity, resulting in a decrease in workability and a marked decrease in commercial value due to adhesion of dirt, unpleasant electric shock to human bodies, and furthermore, occurrence of electric shock. There is also a danger of causing fires, explosions, and other disasters due to the discharge of static electricity. For this reason, various antistatic agents for synthetic resins have been conventionally studied, for example, nonionic surfactants such as glycerin fatty acid ester, sorbitan fatty acid ester, alkyl alkanolamide and alkyl alkanolamine, and alkyl sulfonic acid salts and the like. An anion-on surfactant, various quaternary ammonium compounds, and a mixture thereof are compounded in a synthetic resin to prevent generation of static electricity.
［発明が解決しようとする問題点］ しかしながら、一般にこれらの帯電防止剤は成形直後
の帯電防止効果、所謂即効性が充分で無い、或いは持続
性に乏しい、熱安定定性が悪く樹脂の耐熱性を阻害する
等の問題を有しており、未だ満足すべきものが見出され
ていない。[Problems to be Solved by the Invention] However, in general, these antistatic agents do not have sufficient antistatic effect immediately after molding, so-called immediate effect, or have poor sustainability, poor heat stability and poor heat resistance of resin. It has problems such as inhibition, and no satisfactory product has yet been found.
本発明は上記の点に着目し成されたもので、合成樹脂
に優れた帯電防止効果を付与し、しかもその効果を長時
間継続することが出来、耐熱性等の合成樹脂の物理的性
質が低下することの無い合成樹脂用帯電防止剤を提供す
ることを目的とする。The present invention has been made by paying attention to the above points, and imparts an excellent antistatic effect to a synthetic resin, and furthermore, the effect can be continued for a long time, and the physical properties of the synthetic resin such as heat resistance are improved. An object of the present invention is to provide an antistatic agent for a synthetic resin that does not decrease.
［問題点を解決するための手段］ 上記の問題点を解決するために、本発明者らは鋭意検
討の結果、特定のポリグリセリン脂肪酸エステルと第４
級アンモニウム化合物を組み合わせる事により、極めて
高い帯電防止効果を合成樹脂に付与することが出来ると
共に、その即効性、持続性も極めて高く、かつ合成樹脂
の耐熱性を低下させることのない合成樹脂用帯電防止剤
を見出し、本発明を完成するに至った。[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted intensive studies and as a result, have found that a specific polyglycerin fatty acid ester and
By combining a quaternary ammonium compound, a very high antistatic effect can be imparted to the synthetic resin, and its immediate effect and durability are extremely high, and the charge for the synthetic resin does not reduce the heat resistance of the synthetic resin. They have found an inhibitor and have completed the present invention.
即ち本発明は、（Ａ）下記一般式（Ｉ） （但し、式中Ｒは炭素数11〜21のアルキル基またはアル
ケニル基、ｍは２または３、ｎは１〜５、Ｒ′はメチル
基またはエチル基）で示される第４級アンモニウム化合
物と、（Ｂ）重合度２〜７のポリグリセリンと炭素数12
〜22の飽和または不飽和脂肪酸とより得られるエステル
とを、（Ａ）：（Ｂ）＝10〜70:90〜30の重量比で含有
する合成樹脂用帯電防止剤である。That is, the present invention relates to (A) the following general formula (I) (Where R is an alkyl or alkenyl group having 11 to 21 carbon atoms, m is 2 or 3, n is 1 to 5, R 'is a methyl group or an ethyl group), (B) polyglycerin having a degree of polymerization of 2 to 7 and 12 carbon atoms
(A): (B) = 10 to 70:90 to 30 in a weight ratio of a saturated or unsaturated fatty acid of about 22 to an ester obtained therefrom.
本発明に用いる第４級アンモニウム化合物としては下
記一般式（Ｉ） で示される化合物が挙げられ、式中のＲは炭素数11〜21
のアルキル基またはアルケニル基が好ましい。式中Ｒの
炭素数が11に満たない第４級アンモニウム化合物は、合
成樹脂中に添加した場合にブリ−ドアウトを起こし好ま
しくない。また、Ｒの炭素数が21を超える第４級アンモ
ニウム化合物は、帯電防止効果そのものが低く実用的で
ない。The quaternary ammonium compound used in the present invention is represented by the following general formula (I) Wherein R represents 11 to 21 carbon atoms.
Are preferred. A quaternary ammonium compound having less than 11 carbon atoms of R in the formula is not preferred because it causes bleed-out when added to a synthetic resin. A quaternary ammonium compound having more than 21 carbon atoms in R has a low antistatic effect and is not practical.
一般式（Ｉ）で示される第４級アンモニウム化合物
は、例えば次の様にして合成することができる。まず、
炭素数12〜22の飽和または不飽和脂肪酸またはその低級
アルコールエステル１モルと、ジアルキルアミノアルキ
ルアミン0.8〜３モルとを、常法に従い縮合反応を行な
ってアミド化合物を得る。ここに用いる炭素数12〜22の
脂肪酸としてはラウリン酸、ミリスチン酸、パルミチン
酸、ステアリン酸、アラキン酸、オレイン酸、エライジ
ン酸、リノール酸、リノレン酸、リシノール酸、アラキ
ドン酸、エイコサペンタエン酸、エルカ酸等が挙げら
れ、これらの脂肪酸は単独でも、また２種以上を混合し
たものであっても良い。２種以上を混合した脂肪酸とし
ては、動植物油脂、あるいはこれらの動植物油脂を水素
添加した水添硬化油脂等の油脂類を、常法に従って高圧
分解あるいは油脂分解酵素を用いて分解して得られる脂
肪酸が挙げられる。上記ジアルキルアミノアルキルアミ
ンとしては、ジメチルアミノプロピルアミン、ジエチル
アミノプロピルアミン、ジメチルアミノエチルアミン、
ジエチルアミノエチルアミン等が挙げられる。The quaternary ammonium compound represented by the general formula (I) can be synthesized, for example, as follows. First,
An amide compound is obtained by subjecting 1 mol of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or a lower alcohol ester thereof to 0.8 to 3 mol of a dialkylaminoalkylamine according to a conventional method. The fatty acids having 12 to 22 carbon atoms used herein include lauric acid, myristic acid, palmitic acid, stearic acid, arachinic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, arachidonic acid, eicosapentaenoic acid, elca And the like. These fatty acids may be used alone or as a mixture of two or more. Fatty acids obtained by mixing animal or vegetable fats or oils such as hydrogenated hydrogenated fats or the like obtained by hydrogenating these animal or vegetable fats and oils in accordance with a conventional method under high pressure or using a fat and oil degrading enzyme are used as fatty acids obtained by mixing two or more kinds of fatty acids. Is mentioned. As the dialkylaminoalkylamine, dimethylaminopropylamine, diethylaminopropylamine, dimethylaminoethylamine,
And diethylaminoethylamine.
上記アミド化合物１モルとアルキレンオキサイドと
を、水の存在下にて付加反応を行なって４級アンモニウ
ムヒドロキシド化合物とし、ついで過塩素酸で中和する
ことにより一般式（Ｉ）の化合物を得る。上記アルキレ
ンオキサイドとしてはエチレンオキサイド、プロピレン
オキサイドが挙げられ、その付加モル数は１〜５モルが
好ましい。One mole of the amide compound and an alkylene oxide are subjected to an addition reaction in the presence of water to form a quaternary ammonium hydroxide compound, and then neutralized with perchloric acid to obtain a compound of the general formula (I). Examples of the alkylene oxide include ethylene oxide and propylene oxide, and the number of moles added is preferably 1 to 5 mol.
本発明に用いるエステル（Ｂ）としては、ポリグリセ
リンと脂肪酸とから得られるポリグリセリン脂肪酸エス
テルが挙げられる。ここに用いるポリグリセリンはグリ
セリンを脱水縮合して得られ、重合度２〜７のものが好
ましい。グリセリンの脂肪酸エステルは効果の持続性が
乏しく、重合度が７を越えるポリグリセリンの脂肪酸エ
ステルは樹脂との相溶性が不足する為、フィルムの表面
がべたつく等の問題を生じ好ましくない。Examples of the ester (B) used in the present invention include a polyglycerin fatty acid ester obtained from polyglycerin and a fatty acid. The polyglycerin used here is obtained by dehydrating and condensing glycerin, and preferably has a degree of polymerization of 2 to 7. Fatty acid esters of glycerin have poor persistence of effect, and fatty acid esters of polyglycerin having a degree of polymerization of more than 7 have insufficient compatibility with the resin, which is undesirable because they cause problems such as stickiness of the film surface.
またエステル（Ｂ）に用いられる脂肪酸は、炭素数12
〜22の、飽和または不飽和脂肪酸が好ましい。炭素数が
12に満たない脂肪酸のエステルは、樹脂との相溶性が不
足する為、フィルムの表面がべたつく等の問題を生じ、
炭素数22を越える脂肪酸のエステルは、帯電防止効果そ
のものが低下し実用的でない。The fatty acid used for the ester (B) has 12 carbon atoms.
~ 22 saturated or unsaturated fatty acids are preferred. Carbon number
Fatty acid esters less than 12 cause problems such as stickiness of the film surface due to insufficient compatibility with the resin,
Esters of fatty acids having more than 22 carbon atoms are not practical because the antistatic effect itself is reduced.
上記脂肪酸としては、（Ａ）の第４級アンモニウム化
合物において列挙した脂肪酸が挙げられる。またエステ
ル（Ｂ）は前記ポリグリセリンと脂肪酸とを用いて、常
法に従いエステル化反応を行なうことにより得られる
が、このエステル化反応においてはモノ脂肪酸エステル
と、脂肪酸残基を２ケ以上含むエステルとの混合物が得
られる場合があり、本発明に用いるエステル（Ｂ）とし
ては、モノ脂肪酸エステルを50重量％以上含有するエス
テルを用いることが好ましい。Examples of the fatty acid include the fatty acids listed in the quaternary ammonium compound (A). The ester (B) is obtained by carrying out an esterification reaction using the polyglycerin and the fatty acid according to a conventional method. In this esterification reaction, a monofatty acid ester and an ester containing two or more fatty acid residues are used. In some cases, an ester containing 50% by weight or more of a monofatty acid ester is preferably used as the ester (B) used in the present invention.
本発明の合成樹脂用帯電防止剤は、前記（Ａ）の第４
級アンモニウム化合物と（Ｂ）のエステルとを（Ａ）：
（Ｂ）＝10〜70:90〜30の重量比にて含有する時、相乗
効果によって優れた即効性、持続性を有する実用的な帯
電防止効果が得られる。（Ａ）の第４級アンモニウム化
合物と（Ｂ）のエステル化合物の配合比は、（Ａ）が70
重量％を越え、（Ｂ）が30重量％に満たない場合には、
即効性は認められるが、持続性に乏しく、更に成形品の
着色や過度のブリードによる成形品表面のベトツキ等の
問題が起こり、また（Ｂ）が90重量％を越え、（Ａ）が
10重量％に満たない場合には、即効性が乏しく、更に帯
電防止効果そのものが不十分であり、実用的でない。The antistatic agent for a synthetic resin of the present invention is preferably the fourth antistatic agent of the above (A).
The quaternary ammonium compound and the ester of (B) are (A):
When (B) is contained in a weight ratio of 10 to 70:90 to 30, a practical antistatic effect having excellent immediate effect and durability can be obtained by a synergistic effect. The mixing ratio of the quaternary ammonium compound (A) and the ester compound (B) is such that (A) is 70%.
% By weight and (B) less than 30% by weight,
Immediate effect is recognized, but the durability is poor, and furthermore, problems such as coloring of the molded article and stickiness of the molded article surface due to excessive bleeding occur, and (B) exceeds 90% by weight and (A)
When the amount is less than 10% by weight, the immediate effect is poor, and the antistatic effect itself is insufficient, which is not practical.
本発明の合成樹脂用帯電防止剤は必要に応じ、本発明
の目的を阻害しない範囲内でブロッキング防止剤、酸化
防止剤、紫外線吸収剤、滑剤等の各種添加剤を配合する
ことも出来、また、従来公知の各種の帯電防止剤を併用
することも出来る。The antistatic agent for a synthetic resin of the present invention can be blended with various additives such as an antiblocking agent, an antioxidant, an ultraviolet absorber, and a lubricant as long as the object of the present invention is not impaired. Various conventionally known antistatic agents can be used in combination.
本発明の合成樹脂用帯電防止剤は、各種合成樹脂より
なるフィルム、シート、成形品、繊維等の帯電防止剤と
して用いることが出来るが、特に塩化ビニル樹脂、塩化
ビニル−酢酸ビニルコポリマー、エチレン−酢酸ビニル
コポリマー等のビニル系樹脂の帯電防止剤として好適で
ある。The antistatic agent for a synthetic resin of the present invention can be used as an antistatic agent for films, sheets, molded articles, fibers, etc. made of various synthetic resins, and particularly, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, ethylene- It is suitable as an antistatic agent for vinyl resins such as vinyl acetate copolymers.
また本発明の合成樹脂用帯電防止剤は、従来公知の方
法、例えば本発明の合成樹脂用帯電防止剤と合成樹脂ペ
レットをヘンシェルミキサー、スーパーミキサー、タン
ブラー等により混合し、押し出し機、射出成形機等によ
り樹脂中に混合し、フィルム、シート、成形品、繊維等
とすることにより使用することが出来る。The antistatic agent for a synthetic resin of the present invention can be prepared by a conventionally known method, for example, mixing the antistatic agent for a synthetic resin of the present invention and a synthetic resin pellet with a Henschel mixer, a super mixer, a tumbler, or the like, and extruding an injection molding machine. It can be used by mixing it with a resin to form a film, sheet, molded product, fiber or the like.
本発明の帯電防止剤の添加量は一般に合成樹脂に対し
て0.05〜５重量％の範囲が好ましい。The amount of the antistatic agent of the present invention is generally preferably in the range of 0.05 to 5% by weight based on the synthetic resin.
［実施例］ 以下、実施例を挙げて本発明を詳細に説明するが、本
発明はその要旨を越えない限り、以下の例に限定される
ものではない。EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist is not exceeded.
第４級アンモニウム化合物の調製 ラウリン酸メチルエステル214gにジメチルアミノプロ
ピルアミン112gを添加し、触媒としてナトリウムメトキ
サイド0.2gを加え、100℃にて５時間加熱撹拌してアミ
ド化合物を行ない、さらに過剰のアミンを減圧にて除去
し、アミド化合物282gを得た。次にこのアミド化合物10
0gにイソプロピルアルコール50gと水50gを加え、20℃に
てエステルオキサイド31gを付加反応し、４級化反応を
行なった。得られた４級アンモニウム化合物に過塩素酸
の30％水溶液118gを加えて炭素数11のアルキル基を有す
る（Ｉ）式の第４級アンモニウム化合物を含む溶液を得
た。これを帯電防止剤No.1〜３、５、７〜９、12に用い
た。また、ステアリン酸メチルエステル298gとジメチル
アミノエチルアミン97gとナトリウムメトキサイド0.2g
を用いて上記と同様に反応してアミド化合物354gを得、
次いでこのアミド化合物100gにイソプロピルアルコール
50gと水50gを加え、20℃にてエステルオキサイド25gを
付加反応し、４級化反応を行ない、次にこれに過塩素酸
の30％水溶液94gを加えて中和して、炭素数17のアルキ
ル基を有する（Ｉ）式の第４級アンモニウム化合物を含
む溶液を調製し、これを帯電防止剤No.4、６、11に用い
た。Preparation of quaternary ammonium compound 112 g of dimethylaminopropylamine was added to 214 g of lauric acid methyl ester, 0.2 g of sodium methoxide was added as a catalyst, and the mixture was heated and stirred at 100 ° C. for 5 hours to perform an amide compound. The amine was removed under reduced pressure to obtain 282 g of the amide compound. Next, this amide compound 10
To 0 g, 50 g of isopropyl alcohol and 50 g of water were added, and 31 g of ester oxide was added at 20 ° C. to perform a quaternization reaction. 118 g of a 30% aqueous solution of perchloric acid was added to the obtained quaternary ammonium compound to obtain a solution containing a quaternary ammonium compound of the formula (I) having an alkyl group having 11 carbon atoms. This was used for antistatic agents Nos. 1-3, 5, 7-9 and 12. In addition, stearic acid methyl ester 298 g, dimethylaminoethylamine 97 g and sodium methoxide 0.2 g
Using the same reaction as above to obtain amide compound 354g,
Then add 100 g of this amide compound to isopropyl alcohol
50 g and 50 g of water were added, and an addition reaction of 25 g of ester oxide was carried out at 20 ° C. to carry out a quaternization reaction. A solution containing a quaternary ammonium compound of the formula (I) having an alkyl group was prepared and used for antistatic agents Nos. 4, 6, and 11.
ポリグリセリン脂肪酸エステルの調製 重合度２のポリグリセリン166gにラウリン酸240gを添
加し、230℃で１時間エステル化反応を行なった。得ら
れた反応物を分子蒸留し、モノ脂肪酸エステル（以下
［Ｍ］と略す）96％、ジ脂肪酸エステル（以下［Ｄ］と
略す）４％を含む留分を得て、これを帯電防止剤No.1、
８に用いた。以下グリセリン、重合度２、３、５のポリ
グリセリン及びラウリン酸、ステアリン酸を用いて上記
と同様にエステル化反応を行ない、表−１のエステル
（Ｂ）に示す組成のエステルを調製した。なお、重合度
３、５のポリグリセリンを用いたエステル（Ｂ）は、分
子蒸留をせずにそのまま用いた。Preparation of Polyglycerin Fatty Acid Ester 240 g of lauric acid was added to 166 g of polyglycerin having a polymerization degree of 2, and an esterification reaction was performed at 230 ° C. for 1 hour. The obtained reaction product was subjected to molecular distillation to obtain a fraction containing 96% of a monofatty acid ester (hereinafter abbreviated as [M]) and 4% of a difatty acid ester (hereinafter abbreviated as [D]). No.1,
8 was used. Thereafter, esterification was carried out in the same manner as described above using glycerin, polyglycerin having a polymerization degree of 2, 3, and 5, lauric acid, and stearic acid, to prepare an ester having a composition shown in Ester (B) in Table 1. The ester (B) using polyglycerin having a polymerization degree of 3 or 5 was used without molecular distillation.
実施例１〜７、比較例１〜６ 所定量の第４級アンモニウム化合物を含む水−アルコ
ール溶液に、ポリグリセリン脂肪酸エステルを添加し、
水−アルコールを濃縮除去して得た帯電防止剤（表−
１、No.1〜９、12）、第４級アンモニウム化合物を含む
水−アルコール溶液を濃縮して得た帯電防止剤（表−
１、No.11）、グリセリンまたはポリグリセリンの脂肪
酸エステルのみからなる帯電防止剤（表−１、No.10、1
3）を調製し、これを用いて、下記の重量割合で配合し
た塩化ビニル樹脂組成物を、180℃に加熱されたカレン
ダーロールに供給し、混練した後、常法により厚さ0.5m
mのシートを作成した。Examples 1 to 7, Comparative Examples 1 to 6 To a water-alcohol solution containing a predetermined amount of a quaternary ammonium compound, a polyglycerin fatty acid ester was added,
Antistatic agents obtained by concentrating and removing water-alcohol (Table-
Antistatic agents obtained by concentrating a water-alcohol solution containing a quaternary ammonium compound (Table 1, Nos. 1 to 9, 12)
1, No. 11), an antistatic agent consisting of only a fatty acid ester of glycerin or polyglycerin (Table 1, No. 10, 1)
3) was prepared, and using this, the vinyl chloride resin composition blended in the following weight ratio was supplied to a calender roll heated to 180 ° C., and after kneading, the thickness was 0.5 m by a conventional method.
m sheets were created.
ポリ塩化ビニル樹脂（Ｐ＝1050） 100部 ジオクチルフタレート ２部 ジブチル錫マレエート １部 合成樹脂用帯電防止剤 １部 このシートの耐熱性の評価結果と表面固有抵抗を経日
的に測定した結果を表−２に示す。Polyvinyl chloride resin (P = 1050) 100 parts Dioctyl phthalate 2 parts Dibutyltin maleate 1 part Antistatic agent for synthetic resins 1 part Table showing the evaluation results of heat resistance of this sheet and the results of daily measurement of surface resistivity. -2.
なお、シートの耐熱性試験、表面固有抵抗の測定試験
は次の様に行なった。The heat resistance test of the sheet and the measurement test of the surface resistivity were performed as follows.
シートの耐熱性試験 合成樹脂用帯電防止剤を配合したシート（横50mm×縦
50mm×厚み0.5mm、各試料につき５枚）を230℃のギアオ
ーブン中で加熱し、目視にて色相を経時的に観察し、シ
ートが黒褐色に着色するまでの時間（分）を測定した。Heat resistance test of sheet Sheet containing antistatic agent for synthetic resin (width 50mm x length)
(50 mm × 0.5 mm thick, 5 sheets for each sample) was heated in a gear oven at 230 ° C., the hue was visually observed over time, and the time (minute) until the sheet was colored black-brown was measured.
表面固有抵抗の測定試験 合成樹脂用帯電防止剤を配合したシート（横50mm×縦
50mm×厚み0.5mm、各試料につき５枚）を20℃50％RHの
恒温恒湿室に３時間静置し、調湿した後、同じく20℃50
％RHの測定条件下にて、JISK−6911に準じて測定した。
さらに20℃50％RHの条件下に静置し、成形１週間後と１
年後の性能を測定した。Measurement test of surface specific resistance Sheet containing synthetic resin antistatic agent (width 50 mm × length
(50 mm x 0.5 mm, 5 sheets for each sample) was allowed to stand in a constant temperature / humidity room at 20 ° C and 50% RH for 3 hours.
It measured according to JISK-6911 under the measurement condition of% RH.
Furthermore, it was allowed to stand still at 20 ° C. and 50% RH, and one week after molding and
Years later performance was measured.
［発明の効果］ 以上説明した様に本発明の合成樹脂用帯電防止剤は、
特定の第４級アンモニウム化合物とポリグリセリン脂肪
酸エステルを併用するものであり、従来の帯電防止剤と
比較して、帯電防止効果の即効性、持続性に優れ、長時
間これらの効果を発揮することが出来、また合成樹脂の
耐熱性等の物理的特性を低下することがないので、任意
の量を合成樹脂に配合することにより優れた帯電防止効
果を発揮することが出来ると共に、本発明の合成樹脂用
帯電防止剤は、顔料を加えない製品又は顔料を加えても
淡色に着色した製品に使用した場合、従来の帯電防止剤
と比較して、経日による着色が少なく、また特に耐熱性
を必要とする用途に用いて、合成樹脂の熱による劣化が
起こりにくいと言う効果を有する。 [Effect of the Invention] As described above, the antistatic agent for a synthetic resin of the present invention comprises:
It is a combination of a specific quaternary ammonium compound and a polyglycerin fatty acid ester. Compared with conventional antistatic agents, it is superior in immediate effect and sustainability of antistatic effect, and exhibits these effects for a long time. Can be produced, and the physical properties such as heat resistance of the synthetic resin are not reduced, so that an excellent antistatic effect can be exhibited by adding an arbitrary amount to the synthetic resin, and the synthesis of the present invention can be achieved. Antistatic agents for resins are less colored over time than conventional antistatic agents when used in products without the addition of pigments or in products that are lightly colored even with the addition of pigments. It has an effect that it is hard to be deteriorated by heat of a synthetic resin when used for a required application.
フロントページの続き (72)発明者 大河原 浩 愛知県岩倉市野寄町西出1366 ミヨシ油 脂株式会社名古屋工場内 (72)発明者 守屋 雅文 愛知県岩倉市野寄町西出1366 ミヨシ油 脂株式会社名古屋工場内 審査官 杉原 進 (56)参考文献 特開 昭62−62864（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08K 5/00 - 13/08 C09K 3/16Continued on the front page (72) Inventor Hiroshi Ogawara 1366 Nishiide, Noyoro-cho, Iwakura City, Aichi Prefecture Inside Nagoya Plant of Miyoshi Oil & Fat Co., Ltd. Examiner Susumu Sugihara (56) References JP-A-62-62864 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) C08K 5/00-13/08 C09K 3/16
Claims (1)
ケニル基、ｍは２または３、ｎは１〜５、Ｒ′はメチル
基またはエチル基）で示される第４級アンモニウム化合
物と、（Ｂ）重合度２〜７のポリグリセリンと炭素数12
〜22の飽和または不飽和脂肪酸とより得られるエステル
とを、（Ａ）：（Ｂ）＝10〜70:90〜30の重量比で含有
することを特徴とする合成樹脂用帯電防止剤。(A) The following general formula (I) (Where R is an alkyl or alkenyl group having 11 to 21 carbon atoms, m is 2 or 3, n is 1 to 5, R 'is a methyl group or an ethyl group), (B) polyglycerin having a degree of polymerization of 2 to 7 and 12 carbon atoms
An antistatic agent for a synthetic resin, comprising (A) :( B) = 10 to 70:90 to 30 in a weight ratio of a saturated or unsaturated fatty acid to an ester obtained therefrom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2040075A JP2805519B2 (en) | 1990-02-21 | 1990-02-21 | Antistatic agent for synthetic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2040075A JP2805519B2 (en) | 1990-02-21 | 1990-02-21 | Antistatic agent for synthetic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03243640A JPH03243640A (en) | 1991-10-30 |
| JP2805519B2 true JP2805519B2 (en) | 1998-09-30 |
Family
ID=12570809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2040075A Expired - Fee Related JP2805519B2 (en) | 1990-02-21 | 1990-02-21 | Antistatic agent for synthetic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2805519B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4683605B2 (en) * | 2003-11-26 | 2011-05-18 | 竹本油脂株式会社 | Polyvinyl chloride resin composition |
| WO2014035921A1 (en) * | 2012-08-27 | 2014-03-06 | Pcc Chemax, Inc. | Anti-static agent for polymer resins |
-
1990
- 1990-02-21 JP JP2040075A patent/JP2805519B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03243640A (en) | 1991-10-30 |
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