JP4889895B2 - Surfactant - Google Patents
Surfactant Download PDFInfo
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- JP4889895B2 JP4889895B2 JP2001297471A JP2001297471A JP4889895B2 JP 4889895 B2 JP4889895 B2 JP 4889895B2 JP 2001297471 A JP2001297471 A JP 2001297471A JP 2001297471 A JP2001297471 A JP 2001297471A JP 4889895 B2 JP4889895 B2 JP 4889895B2
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- surfactant
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- polyglycerin
- Prior art date
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- 239000004094 surface-active agent Substances 0.000 title claims description 21
- -1 polyglycerin Chemical compound 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002216 antistatic agent Substances 0.000 claims description 13
- 150000005846 sugar alcohols Polymers 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 7
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 16
- 150000005690 diesters Chemical group 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 150000005691 triesters Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 5
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 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 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([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])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ORJDWQVKIMZEMX-UHFFFAOYSA-N (2-nonylphenyl) hydrogen sulfate Chemical compound CCCCCCCCCC1=CC=CC=C1OS(O)(=O)=O ORJDWQVKIMZEMX-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RTGLJCSUKOLTEM-UHFFFAOYSA-N 2-ethylhexyl carbonochloridate Chemical compound CCCCC(CC)COC(Cl)=O RTGLJCSUKOLTEM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([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])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])[H] 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([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])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])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([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])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Biological Depolymerization Polymers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、生分解性の界面活性剤あるいは帯電防止剤の有効成分として有用な新規カーボネート化合物に関する。
【０００２】
【従来の技術】
従来、環境への残留が少ない非イオン性界面活性剤として、例えば、グリセリン、ポリグリセリン、ペンタエリスリット、ソルビタン、蔗糖、ポリアルキレングリコール等の多価アルコールの脂肪酸エステルが知られている。これらの非イオン性界面活性剤は高い界面活性能を有するが、エステル基を含有するために加水分解を受けやすく、含水系で使用する場合には徐々に加水分解を受け、長期間の保存安定性に欠けるという欠点があった。
【０００３】
【発明が解決しようとする課題】
従って、本発明が解決しようとする課題は、良好な加水分解安定性を有し、且つ生分解性の高い非イオン性界面活性剤とすることのできる新規なカーボネート化合物を提供することにある。また、そのような非イオン性界面活性剤を提供することにある。また、このような非イオン性界面活性剤を用いた帯電防止剤を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者らは上記に鑑み鋭意研究の結果本発明に到達した。即ち本発明は、次式（３）
【化４】
【０００５】
また、本発明は、次式（１）
【化５】
【０００６】
また、本発明は、Ｒ1が、炭素原子数６〜２４の直鎖又は分岐鎖の、アルキル基若しくはアルケニル基である上記の界面活性剤である。
【０００７】
また、本発明は、ポリグリセリンが次式（２）
【化６】
【０００８】
また、本発明は、上記の界面活性剤を必須の成分とすることを特徴とする帯電防止剤である。
【０００９】
【発明の実施の形態】
上記式（１）で示される本発明の新規なカーボネート化合物（以下化合物（１）という）において、Ｒ1は、炭素原子数４〜３２、好ましくは６〜２４のアルキル基若しくはアルケニル基である。化合物（１）は界面活性剤として有用であるが、特に、Ｒ1が炭素原子数６〜２４の直鎖又は分岐鎖の、アルキル基若しくはアルケニル基であると、生分解性が高く好ましい界面活性剤あるいは、好ましい帯電防止剤の有効成分となる。
【００１０】
このようなＲ1としては例えば、ヘキシル基、２級ヘキシル基、ヘプチル基、２級ヘプチル基、オクチル基、２−エチルヘキシル基、２級オクチル基、ノニル基、２級ノニル基、デシル基、２級デシル基、ウンデシル基、２級ウンデシル基、ドデシル基、２級ドデシル基、トリデシル基、イソトリデシル基、２級トリデシル基、テトラデシル基、２級テトラデシル基、ヘキサデシル基、２級ヘキサデシル基、ステアリル基、イソステアリル基、エイコシル基、ドコシル基、テトラコシル基、２−ブチルオクチル基、２−ブチルデシル基、２−ヘキシルオクチル基、２−ヘキシルデシル基、２−オクチルデシル基、２−ヘキシルドデシル基、２−オクチルドデシル基、２−デシルテトラデシル基、２−ドデシルヘキサデシル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、オレイル基等を挙げることができる。
【００１１】
化合物（１）において、Ａは、ｍ価の多価アルコール残基である。ここで、ｍは３〜１６、さらに好ましくは３〜８である。Ａとして、ソルビトールを挙げることができ、また上記式（２）で示されるグリセリン或いはポリグリセリンも挙げることができる。
【００１２】
これらの中でも、上記式（２）で示されるポリグリセリンの残基であると、帯電防止剤の有効成分として好ましい界面活性剤となり、より好ましくは上記式（２）においてｋ＝２〜６であることがよい。
【００１３】
本発明の化合物（１）は上記の通りｎ＝１〜〔ｍ−１〕の数である。従って、Ａの多価アルコール残基には１個以上の水酸基が残存しているものである。このことにより、本発明の化合物（１）は良好な界面活性剤として機能しうるものである。
【００１４】
本発明の化合物（１）からなる界面活性剤は、Ａの多価アルコール残基中の水酸基の数及び上記Ｒ1（疎水基として機能する）の種類（炭素原子数などに起因する疎水性の大小）の選択によって種々の用途に使用できる。例えば、保湿剤、乳化剤、分散剤、可溶化剤、湿潤剤、浸透剤、展着剤、起泡剤、消泡剤、平滑剤、防錆剤、帯電防止剤、摩擦調整剤等として、化粧品、洗浄剤、洗剤、フィルムの結露防止剤、農薬乳化剤、繊維油剤、塗料添加剤、合成樹脂添加剤、潤滑油添加剤等に好適に使用できる。
【００１５】
このなかで特に、上記式（１）におけるＲ1が炭素原子数６〜２４の直鎖又は分岐鎖の、アルキル基若しくはアルケニル基であると、生分解性が高く好ましい界面活性剤となる。
【００１６】
本発明の上記化合物（１）は、このような優れた界面活性剤として広く使用できるが、特に、Ａが次式（２）
【化７】
【００１７】
次に、本発明の化合物の製法について説明する。本発明の化合物は、種々の公知の反応若しくはそれらの組合せにより得ることができるが、例えば、（ａ）対応する塩化アルコキシカルボニルと多価アルコールを反応させる方法、（ｂ）対応するカーボネート化合物と多価アルコールをエステル交換反応させる方法、（ｃ）対応するアルキルカーボネートアルカリ金属塩とハロゲン化アルキルを反応させる方法、（ｄ）対応するホスゲンと多価アルコールを反応させる方法等を例示することができ、この中でも、（ａ）又は（ｂ）の方法によるのが工業化適性の点から好ましい。
【００１８】
これらの反応自体は公知であるので常法にしたがえばよいが、例えば、（ａ）の方法について具体的に説明すると、次式（３）
【化８】
で示される塩化アルコキシカルボニル等を反応容器に仕込み、溶媒兼塩素捕捉剤としてピリジン（溶媒としてのＴＨＦ或いはジオキサンと、塩素捕捉剤としてのトリエタノールアミン、ジメチルアミン、ジエチルアミン等を併用してもよい）を加え、反応系を０℃〜４０℃として上記多価アルコールを徐々に加える。適度に熟成させるなどして反応を完結させた後、ピリジン塩酸塩を濾過して除き、濾過液を減圧下、６０〜１００℃程度で残留するピリジンを除去すればよい。
【００１９】
ここで、本発明の化合物は上記の通り、多価アルコール残基に最低１つの水酸基が残存しているものであり、塩化アルコキシカルボニルと多価アルコールの割合は、得ようとする化合物にいくつの水酸基を残存させるかによって、又、用いる多価アルコールの価数によって、適宜選択すればよい。
但し、この種の反応はある程度の分布を示すのが通常であるので、場合によっては水酸基を含有しない化合物も副生する可能性があるが、蒸留、クロマトグラフ等公知の手法によってこのような副生成物を除去することができる。また、界面活性剤や帯電防止剤の用途によっては上記水酸基を含有しない副生成物が混合されていても支障のない場合があり、このような場合はそのまま混合物として用いることもできる。
【００２０】
【実施例】
以下、実施例を挙げ更に本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
〔実施例１〕
攪拌機、窒素導入管、温度計を備えた３００ｍＬの４つ口フラスコに、グリセリン９．２ｇ（０．１モル）及び、ピリジン８０ｇを仕込み、氷浴中で攪拌しながら２−エチルヘキシルクロロホルメート１９．２ｇ（０．１モル）を１時間かけて徐々に滴下した。滴下終了後、室温にて２時間攪拌して反応を完結させた。フラスコ中のピリジン塩酸塩を濾過して除き、濾液を８０℃、１ｋＰａにて１時間蒸留して残留ピリジンを除去し、淡い黄色油状の生成物２６．４ｇを得た。
得られた生成物をヘキサン／アセトン混合溶媒によるシリカゲルカラムクロマトグラフィーで精製して、1Ｈ−ＮＭＲ分析した結果、４．１２ｐｐｍ付近にカーボネートのα位のメチレンのピーク、４．２０ｐｐｍ付近にカーボネートのもう一方のα位のメチレンピーク、３．３１〜３．３８ｐｐｍ付近グリセリン残基のメチン、メチレンのピーク、１．６５ｐｐｍ付近にアルキルメチレン及びメチンのピーク、０．８９ｐｐｍ付近にアルキルのω位メチルのピークが検出されまた、元素分析の結果はＣ ５８．２４％、Ｈ ９．６８％、Ｏ ３２．０２％であり、以下の構造の化合物
【化９】
【００２１】
〔実施例２〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：２７．６重量％
ジエステル体 ：３４．５重量％
トリエステル体：２１．５重量％
【００２２】
〔実施例３〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：４０．９重量％
ジエステル体 ：１９．５重量％
トリエステル体：４．６重量％
【００２３】
〔実施例４〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：３７．０重量％
ジエステル体 ：３０．０重量％
トリエステル体：１２．２重量％
【００２４】
〔実施例５〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：４０．０重量％
ジエステル体 ：１８．２重量％
トリエステル体：４．４重量％
【００２５】
〔実施例６〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：３７．３重量％
ジエステル体 ：２８．０重量％
トリエステル体：１１．２重量％
【００２６】
〔実施例７〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：２９．４重量％
ジエステル体 ：３２．６重量％
トリエステル体：１９．３重量％
【００２７】
〔実施例８〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：３８．６重量％
ジエステル体 ：１９．３重量％
トリエステル体：５．８重量％
【００２８】
〔実施例９〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：２６．９重量％
ジエステル体 ：２９．９重量％
トリエステル体：１９．９重量％
【００２９】
〔実施例１０〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：１２．４重量％
ジエステル体 ：２３．３重量％
トリエステル体：２６．２重量％
【００３０】
〔実施例１１〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：４０．２重量％
ジエステル体 ：２０．１重量％
トリエステル体：５．１重量％
【００３１】
〔実施例１２〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：３９．９重量％
ジエステル体 ：１８．５重量％
トリエステル体：３．６重量％
【００３２】
〔実施例１３〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：３８．８重量％
ジエステル体 ：２０．５重量％
トリエステル体：５．１重量％
【００３３】
〔実施例１４〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：３６．３重量％
ジエステル体 ：１８．１重量％
トリエステル体： ４．９重量％
【００３４】
〔実施例１５〕
実施例１と同様の要領にて、表１に示した原料を表１に示した割合で使用して生成物を得た。得られた生成物の主成分とその割合は以下の通りであった。
モノエステル体：３７．０重量％
ジエステル体 ：１６．５重量％
トリエステル体： ６．３重量％
【００３５】
【表１】
(b)：式（２）中のｋが平均４．５で、ＯＨＶ＝１０４０のポリグリセリン
(c)：式（２）中のｋが平均８．９で、ＯＨＶ＝９０３のポリグリセリン
【００３６】
〔実施例１６〜３０〕
上記実施例１〜１５で得られた本発明の化合物を含有する生成物の０．１重量％水溶液を作成し、その２５℃における表面張力をウイルヘルミ法によって測定した。
また、活性汚泥を使用したＯＥＣＤ−３０１Ｄ法によって生分解性を試験し、２８日目の生分解率を求めた。
結果を表２に示す。いずれも良好な界面活性能及び生分解性を示した。
【００３７】
【表２】
〔実施例３１〜３９、比較例１〜４〕
上記実施例２〜１０で得られた本発明の化合物を含有する生成物、及び比較のため下記比較品１〜４の各１００重量部を、担体であるシリカ粉（トクヤマ製、商品名：トクシールＮＰ）４０重量部に含浸させて各種帯電防止剤を得た。
比較品１：ポリエチレングリコール（分子量４０００）
比較品２：ノニルフェノールサルフェートのエチレンオキサイド３０モル付加物
比較品３：ビスフェノールＡのエチレンオキサイド２０モル付加物
比較品４：グリセリンモノステアレート
ビスフェノールＡ型ポリカーボネートとＡＢＳ樹脂の割合が８：２であるポリマーアロイ１００重量部に、これらの帯電防止剤を５重量部配合し、押し出し機で２８０℃、１５ｒｐｍの条件でペレットを作成した。
【００３９】
このペレットを射出成形機を使用し、２８０℃の条件で、直径１０ｃｍ、厚さ１ｍｍの試験シートを作成した。
この試験シートを用いて、表面固有抵抗値を下記条件にて測定し、帯電防止性を評価した。
測定装置：アドバンテスト社製デジタル超高抵抗計Ｒ８３４０
測定温度：２３℃
測定湿度：６０％
印加電圧：５００Ｖ
印加時間：１分間
【００４０】
尚、測定は、成形加工後、温度２３℃、湿度６０％の条件で２４時間経過後の試験シート、及びこの１日後の試験シートを攪拌された４０℃の水中に１時間浸漬した後、水滴をガーゼで拭取った直後の試験シートの両者について表面固有抵抗値を測定した。結果を表３に示す。本発明の帯電防止剤はいずれも良好な帯電防止能を有し、水洗後であってもしの帯電防止能が劣化することのない良好なものであった。
【００４１】
【表３】
BACKGROUND OF THE INVENTION
The present invention relates to a novel carbonate compound useful as an active ingredient of a biodegradable surfactant or antistatic agent.
[0002]
[Prior art]
Conventionally, fatty acid esters of polyhydric alcohols such as glycerin, polyglycerin, pentaerythritol, sorbitan, sucrose, polyalkylene glycol and the like are known as nonionic surfactants with little residual in the environment. These nonionic surfactants have high surface activity, but are susceptible to hydrolysis because they contain an ester group. When used in a hydrous system, they are gradually hydrolyzed and stable for long-term storage. There was a drawback of lack of nature.
[0003]
[Problems to be solved by the invention]
Therefore, the problem to be solved by the present invention is to provide a novel carbonate compound that has good hydrolysis stability and can be made into a highly biodegradable nonionic surfactant. Another object of the present invention is to provide such a nonionic surfactant. Another object of the present invention is to provide an antistatic agent using such a nonionic surfactant.
[0004]
[Means for Solving the Problems]
The present inventors have reached the present invention as a result of intensive studies in view of the above. That is, the present invention provides the following formula ( 3 )
[Formula 4]
[0005]
Further, the present invention provides the following formula (1)
[Chemical formula 5]
[0006]
Moreover, this invention is said surfactant whose R < 1 > is a C6-C24 linear or branched alkyl group or alkenyl group.
[0007]
In the present invention, the polyglycerol is represented by the following formula (2):
[Chemical 6]
[0008]
The present invention also provides an antistatic agent comprising the above surfactant as an essential component.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the novel carbonate compound of the present invention represented by the above formula (1) (hereinafter referred to as compound (1)), R 1 is an alkyl or alkenyl group having 4 to 32 carbon atoms, preferably 6 to 24 carbon atoms. The compound (1) is useful as a surfactant. In particular, when R 1 is a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, high surface biodegradability and preferable surface activity are obtained. Or an active ingredient of a preferred antistatic agent.
[0010]
Examples of such R 1 include hexyl group, secondary hexyl group, heptyl group, secondary heptyl group, octyl group, 2-ethylhexyl group, secondary octyl group, nonyl group, secondary nonyl group, decyl group, 2 Secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, hexadecyl, secondary hexadecyl, stearyl, Isostearyl, eicosyl, docosyl, tetracosyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2- Octyldodecyl group, 2-decyltetradecyl group, 2-dodecylhexadecyl group, hexenyl group, Heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, and oleyl group.
[0011]
In the compound (1), A is an m-valent polyhydric alcohol residue. Here, m is 3-16, More preferably, it is 3-8. As A, there may be mentioned Soviet Rubitoru, and may also be mentioned glycerol or polyglycerol represented by the formula (2).
[0012]
Among these, a polyglycerin residue represented by the above formula (2) is a preferable surfactant as an active ingredient of the antistatic agent, and more preferably k = 2 to 6 in the above formula (2). It is good.
[0013]
The compound (1) of the present invention has a number of n = 1 to [m−1] as described above. Therefore, one or more hydroxyl groups remain in the polyhydric alcohol residue of A. Thus, the compound (1) of the present invention can function as a good surfactant.
[0014]
The surfactant comprising the compound (1) of the present invention has a hydrophobic property due to the number of hydroxyl groups in the polyhydric alcohol residue of A and the type of R 1 (functioning as a hydrophobic group) (the number of carbon atoms). It can be used for various purposes depending on the choice of (large or small). For example, as a moisturizer, emulsifier, dispersant, solubilizer, wetting agent, penetrating agent, spreading agent, foaming agent, antifoaming agent, smoothing agent, rust preventive agent, antistatic agent, friction modifier, etc. , Cleaning agents, detergents, film anti-condensation agents, agricultural chemical emulsifiers, fiber oil agents, paint additives, synthetic resin additives, lubricating oil additives, and the like.
[0015]
Among them, in particular, when R 1 in the above formula (1) is a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, it becomes a preferable surfactant with high biodegradability.
[0016]
The compound (1) of the present invention can be widely used as such an excellent surfactant. In particular, A is represented by the following formula (2).
[Chemical 7]
[0017]
Next, a method for producing the compound of the present invention will be described. The compound of the present invention can be obtained by various known reactions or combinations thereof. For example, (a) a method of reacting a corresponding alkoxycarbonyl chloride with a polyhydric alcohol, (b) a corresponding carbonate compound and a polyvalent alcohol. Examples include a method of transesterifying a monohydric alcohol, (c) a method of reacting a corresponding alkyl carbonate alkali metal salt with an alkyl halide, (d) a method of reacting a corresponding phosgene and a polyhydric alcohol, and the like. Among these, the method (a) or (b) is preferable from the viewpoint of industrialization suitability.
[0018]
Since these reactions are known per se, they may be followed by conventional methods. For example, the method (a) will be specifically described below.
[Chemical 8]
Is added to the reaction vessel and pyridine as a solvent and chlorine scavenger (THF or dioxane as a solvent and triethanolamine, dimethylamine, diethylamine or the like as a chlorine scavenger may be used in combination). And the polyhydric alcohol is gradually added with the reaction system at 0 ° C to 40 ° C. After the reaction is completed by aging appropriately, pyridine hydrochloride is removed by filtration, and the pyridine remaining in the filtrate is removed at about 60 to 100 ° C. under reduced pressure.
[0019]
Here, as described above, the compound of the present invention is one in which at least one hydroxyl group remains in the polyhydric alcohol residue, and the ratio of alkoxycarbonyl chloride to polyhydric alcohol depends on the number of compounds to be obtained. What is necessary is just to select suitably by the valence of the polyhydric alcohol to be used according to whether a hydroxyl group remains.
However, since this type of reaction usually shows a certain degree of distribution, in some cases, a compound that does not contain a hydroxyl group may be produced as a by-product, but such a by-product may be obtained by a known method such as distillation or chromatography. The product can be removed. Depending on the use of the surfactant or antistatic agent, there may be no problem even if the by-product containing no hydroxyl group is mixed. In such a case, it can be used as it is as a mixture.
[0020]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
[Example 1]
Into a 300 mL four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 9.2 g (0.1 mol) of glycerin and 80 g of pyridine were charged, and 2-ethylhexyl chloroformate 19 was stirred while stirring in an ice bath. 0.2 g (0.1 mol) was gradually added dropwise over 1 hour. After completion of the dropwise addition, the reaction was completed by stirring at room temperature for 2 hours. The pyridine hydrochloride in the flask was removed by filtration, and the filtrate was distilled at 80 ° C. and 1 kPa for 1 hour to remove residual pyridine, thereby obtaining 26.4 g of a pale yellow oily product.
The obtained product was purified by silica gel column chromatography using a mixed solvent of hexane / acetone and analyzed by 1 H-NMR. As a result, the α-methylene peak at the α-position in the vicinity of 4.12 ppm and the carbonate in the vicinity of 4.20 ppm. The other methylene peak at the α-position, methine at the glycerin residue near 3.31-3.38 ppm, the methylene peak, the alkylmethylene and methine peaks near 1.65 ppm, the alkyl ω-position methyl near 0.89 ppm Peaks were detected, and the results of elemental analysis were 58.24% C, 9.68% H, 32.02% O, and a compound having the following structure:
[0021]
[Example 2]
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 27.6% by weight
Diester: 34.5% by weight
Triester: 21.5% by weight
[0022]
Example 3
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 40.9% by weight
Diester: 19.5% by weight
Triester: 4.6% by weight
[0023]
Example 4
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 37.0% by weight
Diester body: 30.0% by weight
Triester: 12.2% by weight
[0024]
Example 5
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester body: 40.0% by weight
Diester: 18.2% by weight
Triester: 4.4% by weight
[0025]
Example 6
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 37.3% by weight
Diester body: 28.0% by weight
Triester body: 11.2% by weight
[0026]
Example 7
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 29.4% by weight
Diester: 32.6% by weight
Triester: 19.3% by weight
[0027]
Example 8
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester body: 38.6% by weight
Diester body: 19.3% by weight
Triester: 5.8% by weight
[0028]
Example 9
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 26.9% by weight
Diester: 29.9% by weight
Triester: 19.9% by weight
[0029]
Example 10
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 12.4% by weight
Diester: 23.3% by weight
Triester: 26.2% by weight
[0030]
Example 11
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester body: 40.2% by weight
Diester body: 20.1% by weight
Triester: 5.1% by weight
[0031]
Example 12
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 39.9% by weight
Diester body: 18.5% by weight
Triester: 3.6% by weight
[0032]
Example 13
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 38.8% by weight
Diester body: 20.5% by weight
Triester: 5.1% by weight
[0033]
Example 14
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 36.3% by weight
Diester: 18.1% by weight
Triester: 4.9% by weight
[0034]
Example 15
In the same manner as in Example 1, the raw materials shown in Table 1 were used in the proportions shown in Table 1 to obtain products. The main components and the ratios of the obtained products were as follows.
Monoester: 37.0% by weight
Diester body: 16.5% by weight
Triester: 6.3% by weight
[0035]
[Table 1]
(b) : k in formula (2) has an average of 4.5 and OHV = 1040 polyglycerin
(c) : Polyglycerin in which k in formula (2) averages 8.9 and OHV = 903
[Examples 16 to 30]
A 0.1 wt% aqueous solution of the product containing the compound of the present invention obtained in Examples 1 to 15 was prepared, and the surface tension at 25 ° C. was measured by the Wilhelmy method.
Moreover, biodegradability was tested by the OECD-301D method using activated sludge, and the biodegradation rate on the 28th day was obtained.
The results are shown in Table 2. All showed good surface activity and biodegradability.
[0037]
[Table 2]
[Examples 31-39, Comparative Examples 1-4]
The product containing the compound of the present invention obtained in Examples 2 to 10 above and 100 parts by weight of each of Comparative Products 1 to 4 below for comparison were mixed with silica powder (made by Tokuyama, trade name: Toxeal). NP) 40 parts by weight were impregnated to obtain various antistatic agents.
Comparative product 1: Polyethylene glycol (molecular weight 4000)
Comparative product 2: Ethylene oxide 30 mol adduct of nonylphenol sulfate Comparative product 3: Ethylene oxide 20 mol adduct of bisphenol A Comparative product 4: Polymer having a ratio of glycerol monostearate bisphenol A type polycarbonate to ABS resin of 8: 2. 5 parts by weight of these antistatic agents were blended with 100 parts by weight of the alloy, and pellets were prepared with an extruder at 280 ° C. and 15 rpm.
[0039]
A test sheet having a diameter of 10 cm and a thickness of 1 mm was prepared from the pellets using an injection molding machine at 280 ° C.
Using this test sheet, the surface resistivity was measured under the following conditions to evaluate the antistatic property.
Measuring device: Digital super high resistance meter R8340 manufactured by Advantest Corporation
Measurement temperature: 23 ° C
Measurement humidity: 60%
Applied voltage: 500V
Application time: 1 minute [0040]
In addition, the measurement is performed by immersing the test sheet after 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 60% after molding, and the test sheet after 1 day in 40 ° C. water that has been stirred for 1 hour, The surface specific resistance value was measured for both test sheets immediately after wiping with a gauze. The results are shown in Table 3. All of the antistatic agents of the present invention had good antistatic ability, and even after washing with water, the antistatic ability did not deteriorate.
[0041]
[Table 3]
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2001297471A JP4889895B2 (en) | 2001-09-27 | 2001-09-27 | Surfactant |
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| JP2001297471A JP4889895B2 (en) | 2001-09-27 | 2001-09-27 | Surfactant |
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| JP4889895B2 true JP4889895B2 (en) | 2012-03-07 |
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| DE10323703A1 (en) * | 2003-05-22 | 2004-12-23 | Beiersdorf Ag | Cosmetic or dermatological composition containing a glycerol carbonate, useful for control of body odor, are inhibitors of bacteria and fungi |
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| JPH05255680A (en) * | 1992-01-13 | 1993-10-05 | Mitsui Petrochem Ind Ltd | Polycarbonate and its uses |
| US6147246A (en) * | 1999-12-23 | 2000-11-14 | Condea Vista Company | Process for preparing alkoxylated dialkyl carbonate compounds |
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