JP6448939B2 - Purification method for betaine surfactant - Google Patents
Purification method for betaine surfactant Download PDFInfo
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- JP6448939B2 JP6448939B2 JP2014151321A JP2014151321A JP6448939B2 JP 6448939 B2 JP6448939 B2 JP 6448939B2 JP 2014151321 A JP2014151321 A JP 2014151321A JP 2014151321 A JP2014151321 A JP 2014151321A JP 6448939 B2 JP6448939 B2 JP 6448939B2
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- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims description 54
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title claims description 54
- 229960003237 betaine Drugs 0.000 title claims description 54
- 239000004094 surface-active agent Substances 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 39
- 238000000746 purification Methods 0.000 title claims description 37
- 150000002500 ions Chemical class 0.000 claims description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000003729 cation exchange resin Substances 0.000 claims description 15
- 239000003957 anion exchange resin Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 238000005342 ion exchange Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000012535 impurity Substances 0.000 description 12
- 229920001429 chelating resin Polymers 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- DHYWSAPLZYWZSZ-UHFFFAOYSA-N 2-(dimethylazaniumyl)hexadecanoate Chemical compound CCCCCCCCCCCCCCC(N(C)C)C(O)=O DHYWSAPLZYWZSZ-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 101000714168 Homo sapiens Testisin Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 102100036494 Testisin Human genes 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- -1 battery Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- WWVIUVHFPSALDO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCN(C)C WWVIUVHFPSALDO-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 102220091827 rs1059046 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
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- DZUJSXDQZILVCD-UHFFFAOYSA-N tetradecyl 2-(dimethylamino)acetate Chemical compound CCCCCCCCCCCCCCOC(=O)CN(C)C DZUJSXDQZILVCD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、ベタイン型界面活性剤の精製処理方法に関する。ベタイン型界面活性剤を、インクジェットノズル、電子、半導体及び精密加工等の分野で支障なく使用するためには、かかるベタイン型界面活性剤に含まれる不純物としてのＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ以下に低減する必要がある。本発明は、ベタイン型界面活性剤に含まれる不純物としてのＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ（１ｍｇ／ｋｇ）以下に低減することができるベタイン型界面活性剤の精製処理方法に関する。 The present invention relates to a purification process how betaine type surfactants. In order to use a betaine type surfactant without any trouble in the fields of inkjet nozzles, electronics, semiconductors, precision processing, etc., Cl, Na, Ca, Mg, Fe as impurities contained in the betaine type surfactant are included. It is necessary to reduce each ion concentration of Si to 1 ppm or less. The present invention provides a betaine-type surface active that can reduce each ion concentration of Cl, Na, Ca, Mg, Fe and Si as impurities contained in the betaine-type surfactant to 1 ppm ( 1 mg / kg) or less. about the purification process how the agent.
従来、インクジェットノズル、電子、半導体及び精密加工等、様々な分野で、不純物としてのＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を低減した界面活性剤が使用されており、かかる界面活性剤を得るための精製処理方法も提案されている。例えば、アニオン型界面活性剤については、一般的な濃縮、晶析、抽出による方法の他に、逆浸透膜や限外濾過膜による方法（例えば特許文献１参照）、イオン交換膜を用いた電気透析による方法（例えば特許文献２参照）等が提案されている。 Conventionally, surfactants with reduced ion concentrations of Cl, Na, Ca, Mg, Fe, and Si as impurities have been used in various fields such as inkjet nozzles, electronics, semiconductors, and precision processing. A purification method for obtaining an activator has also been proposed. For example, for an anionic surfactant, in addition to the general methods of concentration, crystallization, and extraction, a method using a reverse osmosis membrane or an ultrafiltration membrane (see, for example, Patent Document 1), an electricity using an ion exchange membrane A dialysis method (see, for example, Patent Document 2) has been proposed.
しかし、前記のような従来法によると、精製の対象がベタイン型界面活性剤である場合には、望まれるレベルにまで不純物としての各イオン濃度を低減したもの、より具体的にはベタイン型界面活性剤に含まれる不純物としてのＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を５ｐｐｍ以下にまで低減したものを得ることが難しいという問題がある。 However, according to the conventional method as described above, when the target of purification is a betaine type surfactant, the concentration of each ion as an impurity is reduced to a desired level, more specifically, a betaine type interface. There is a problem that it is difficult to obtain a product in which each ion concentration of Cl, Na, Ca, Mg, Fe and Si as impurities contained in the activator is reduced to 5 ppm or less.
本発明が解決しようとする課題は、ベタイン型界面活性剤に含まれるＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ以下にまで低減することができるベタイン型界面活性剤の精製処理方法を提供するところにある。 The problem to be solved by the present invention is that of a betaine surfactant that can reduce each ion concentration of Cl, Na, Ca, Mg, Fe and Si contained in the betaine surfactant to 1 ppm or less. It is to provide a purification process how.
本発明者らは、前記の課題を解決するべく研究した結果、不純物として各種イオンを相応に高濃度で含有し、所定の溶媒で希釈したベタイン型界面活性剤を特定のカチオン交換樹脂とアニオン交換樹脂とを所定の割合で混合した混合樹脂を用いたイオン交換法に供して精製処理すると、ベタイン型界面活性剤に含まれる不純物としてのＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ以下にまで低減することができることを見出した。 As a result of researches to solve the above problems, the present inventors have found that a betaine surfactant containing various ions as impurities and correspondingly diluted in a predetermined solvent is subjected to anion exchange with a specific cation exchange resin. When subjected to a purification treatment using an ion exchange method using a mixed resin in which a resin is mixed at a predetermined ratio, each ion concentration of Cl, Na, Ca, Mg, Fe and Si as impurities contained in the betaine-type surfactant Has been found to be able to be reduced to 1 ppm or less.
すなわち本発明は、ベタイン型界面活性剤を、水、炭素数１〜４の低級アルコール及び炭素数２〜４のグリコールのなかから選ばれる一つ又は二つ以上の溶媒で希釈して濃度５〜５０質量％の溶液とし、この溶液を強酸性カチオン交換樹脂と強アルカリ性アニオン交換樹脂とを前者／後者＝１／１．５〜１／２．５（容量比）となる割合で混合した混合樹脂を用いたイオン交換法に供し、ベタイン型界面活性剤に含まれるＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ以下となるように精製処理することを特徴とするベタイン型界面活性剤の精製処理方法に係る。 That is, in the present invention, a betaine surfactant is diluted with one or two or more solvents selected from water, a lower alcohol having 1 to 4 carbon atoms, and a glycol having 2 to 4 carbon atoms. A mixed resin in which a 50% by mass solution was mixed with a strongly acidic cation exchange resin and a strong alkaline anion exchange resin at a ratio of 1 / 1.5 to 1 / 2.5 (volume ratio). A betaine type, characterized by being subjected to an ion exchange method using a silane, and being purified so that each ion concentration of Cl, Na, Ca, Mg, Fe and Si contained in the betaine type surfactant is 1 ppm or less The present invention relates to a method for purifying a surfactant .
先ず、本発明に係るベタイン型界面活性剤の精製処理方法（以下、単に本発明の精製処理方法という）について説明する。本発明の精製処理方法は、不純物として各種イオンを相応に高濃度で含有し、所定の溶媒で希釈したベタイン型界面活性剤を、強酸性カチオン交換樹脂と強アルカリ性アニオン交換樹脂とを所定の割合で混合した混合樹脂を用いたイオン交換法に供し、ベタイン型界面活性剤に含まれるＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ以下となるよう精製処理する方法である。 First, a method for purifying a betaine surfactant according to the present invention (hereinafter simply referred to as the purification method of the present invention) will be described. The purification treatment method of the present invention comprises a betaine surfactant containing various ions as impurities in a correspondingly high concentration and diluted with a predetermined solvent, and a strong acid cation exchange resin and a strong alkaline anion exchange resin in a predetermined ratio. This is a method of subjecting to an ion exchange method using a mixed resin mixed in 1) and purifying so that each ion concentration of Cl, Na, Ca, Mg, Fe and Si contained in the betaine-type surfactant is 1 ppm or less. .
本発明の精製処理方法に供するベタイン型界面活性剤としては、いずれも不純物として各種イオンを相応に高濃度で含有するそれ自体は公知のベタイン型界面活性剤が挙げられる。具体的な例としては、いずれも不純物として各種イオンを相応に高濃度で含有する、アルキルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルベタイン、パーム核油脂肪酸アミドプロピルベタイン、ラウリン酸アミドプロピルベタイン、ステアリン酸アミドプロピルベタイン、イソステアリン酸アミドプロピルベタイン、ミリスチン酸アミドプロピルベタイン、オレイン酸アミドプロピルベタイン、アルキルヒドロキシスルホベタイン、ヒドロキシアルキルヒドロキシエチルサルコシン、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン等が挙げられる。市販品では、いずれも不純物として各種イオンを相応に高濃度で含有する、パイオニンＣシリーズ（竹本油脂社製の商品名）、アンヒトールシリーズ（花王社製の商品名）、ソフタゾリンシリーズ（川研ファインケミカル社製の商品名）、アンホレックスシリーズ（ミヨシ油脂社製の商品名）等が挙げられる。 Examples of the betaine-type surfactant to be used in the purification treatment method of the present invention include known betaine-type surfactants that each contain various ions as impurities in a correspondingly high concentration. Specific examples include alkyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, palm kernel fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, stearin, each of which contains various ions as impurities in correspondingly high concentrations. Acid amidopropyl betaine, isostearic acid amidopropyl betaine, myristic acid amidopropyl betaine, oleic acid amidopropyl betaine, alkylhydroxysulfobetaine, hydroxyalkylhydroxyethylsarcosine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium Examples include betaine. Commercially available products all contain various ions as impurities in correspondingly high concentrations, such as the Pionein C series (trade name, manufactured by Takemoto Yushi Co., Ltd.), the Amphitor series (trade name, manufactured by Kao Corporation), the Softazoline series ( The product name of Kawaken Fine Chemicals Co., Ltd.), Anholex series (trade name of Miyoshi Oil & Fats Co., Ltd.), and the like.
本発明の精製処理方法に供するイオン交換樹脂は、強酸性カチオン交換樹脂と強アルカリ性アニオン交換樹脂との混合樹脂である。強酸性カチオン交換樹脂としては、いずれも市販されている商品名で、アンバーライトＩＲ−１２４、ＩＲ−１２０Ｂ、２００ＣＴ、デュオライトＣ２０Ｊ、Ｃ２０ＬＦ、Ｃ２６Ａ、Ｃ２５５ＬＦＨ、ＰＫ２０８、ＰＫ２２８（いずれも米国ダウ・ケミカル社製）、ダイヤイオンＳＫ−１１０、ＳＫ−１Ｂ（共に三菱化学社製）等のスルホン酸型強酸性カチオン交換樹脂が挙げられる。また強アルカリ性アニオン交換樹脂としては、いずれも市販されている商品名で、アンバーライトＩＲＡ−４００Ｊ、ＩＲＡ−４１０Ｊ、ＩＲＡ９００Ｊ、デュオライトＡ１１３ＬＦ、Ａ１１６、Ａ１６１ＪＣＬ（いずれも米国ダウ・ケミカル社製）ダイヤイオンＳＡ１２Ａ、ＳＡ２０Ａ、ＰＡ３０８、ＨＰＡ２５（いずれも三菱化学社製）等の４級アンモニウム塩型強アルカリ性アニオン交換樹脂が挙げられる。 The ion exchange resin used in the purification treatment method of the present invention is a mixed resin of a strong acidic cation exchange resin and a strong alkaline anion exchange resin. Strongly acidic cation exchange resins are all commercially available under the trade names of Amberlite IR-124, IR-120B, 200CT, Duolite C20J, C20LF, C26A, C255LFH, PK208, PK228 (all of which are US Dow Chemical). Sulfonic acid type strongly acidic cation exchange resins such as Diaion SK-110 and SK-1B (both manufactured by Mitsubishi Chemical Corporation). Moreover, as a strong alkaline anion exchange resin, all are the brand names marketed, and Amberlite IRA-400J, IRA-410J, IRA900J, Duolite A113LF, A116, A161JCL (all manufactured by Dow Chemical Co., USA) Diaion. Examples include quaternary ammonium salt type strongly alkaline anion exchange resins such as SA12A, SA20A, PA308, and HPA25 (all manufactured by Mitsubishi Chemical Corporation).
本発明の精製処理方法では、以上説明した強酸性カチオン交換樹脂や強アルカリ性アニオン交換樹脂と共に、いずれも市販されている商品名で、ダイヤイオンＷＫ１１（三菱化学社製）等の弱酸性カチオン交換樹脂、アンバーライトＩＲＡ６７、ＩＲＡ９８（共に米国ダウ・ケミカル社製）、ダイヤイオンＷＡ１０、ＷＡ２０、ＷＡ３０（いずれも三菱化学社製）等の弱アルカリ性カチオン交換樹脂、ダイヤイオンＣＲ１０、ＣＲ１１（共に三菱化学社製）等のキレート樹脂を併用することもできる。 In the purification treatment method of the present invention, a weakly acidic cation exchange resin such as Diaion WK11 (manufactured by Mitsubishi Chemical Corporation) under the commercial name, together with the strong acid cation exchange resin and the strong alkaline anion exchange resin described above. , Amberlite IRA67, IRA98 (both manufactured by Dow Chemical Co., USA), Diaion WA10, WA20, WA30 (all manufactured by Mitsubishi Chemical Co., Ltd.), etc., Diaion CR10, CR11 (both manufactured by Mitsubishi Chemical Co., Ltd.) ) Etc. can also be used together.
本発明の精製処理方法では、強酸性カチオン交換樹脂と強アルカリ性アニオン交換樹脂とが予め混合された状態で市販されているイオン交換樹脂を用いることもできる。かかるイオン交換樹脂としては、いずれも市販されている商品名で、デュオライトＭＢ５１１３、ＵＰ６０００、ＵＰ７０００、アンバーライトＥＧ−２９０−ＨＧ、ＥＧ−４Ａ−ＨＧ、ＭＢ−１、ＭＢ−２、アンバージェットＥＳＰ−２、ＥＳＰ−１（いずれも米国ダウ・ケミカル社製）、ダイヤイオンＳＭＮＵＰ、ＳＭＴ１００Ｌ（共に三菱化学製）等が挙げられる。 In the purification treatment method of the present invention, a commercially available ion exchange resin in which a strong acid cation exchange resin and a strong alkaline anion exchange resin are mixed in advance can also be used. Such ion exchange resins are all commercially available under the trade names, Duolite MB5113, UP6000, UP7000, Amberlite EG-290-HG, EG-4A-HG, MB-1, MB-2, Amberjet ESP. -2, ESP-1 (all manufactured by Dow Chemical Co., USA), Diaion SMNUP, SMT100L (both manufactured by Mitsubishi Chemical), and the like.
本発明の精製処理方法では、ベタイン型界面活性剤を溶媒に溶解した溶液とし、この溶液をイオン交換法に供する。かかる溶媒としては、１）水、２）メタノール、エタノール、１−プロパノール、イソプロピルアルコール（２−プロパノール）、１−ブタノール、２−ブタノール、イソブタノール、ｔ−ブタノール等の炭素数１〜４の低級アルコール、３）エチレングリコール、プロピレングリコール、ジエチレングリコール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール等の炭素数２〜４のグリコール、４）プロピレングリコールモノメチルエーテル、５）乳酸エチル、乳酸メチル、乳酸ブチル等の乳酸エステル等が挙げられる。本発明の精製処理方法では、水、炭素数１〜４の低級アルコール及び炭素数２〜４のグリコールのなかから選ばれる一つ又は二つ以上の溶媒が使用される。これらの溶媒は被精製ベタイン型界面活性剤の均一な溶液が得られる範囲内において、単独で使用することができ、また二種類以上を混合して使用することもできる。なかでも、水、イソプロピルアルコール又はこれらの混合物が好ましい。 In the purification treatment method of the present invention, a solution in which a betaine surfactant is dissolved in a solvent is used, and this solution is subjected to an ion exchange method. Examples of such solvents include 1) water, 2) methanol, ethanol, 1-propanol, isopropyl alcohol (2-propanol), 1-butanol, 2-butanol, isobutanol, t-butanol, and the like having 1 to 4 carbon atoms. Alcohol, 3) ethylene glycol, propylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and other glycols having 2 to 4 carbon atoms, 4) propylene glycol monomethyl ether, 5 ) Lactic acid esters such as ethyl lactate, methyl lactate and butyl lactate. In the purification treatment method of the present invention, one or two or more solvents selected from water, a lower alcohol having 1 to 4 carbon atoms, and a glycol having 2 to 4 carbon atoms are used. These solvents can be used singly within the range in which a uniform solution of the betaine-type surfactant to be purified can be obtained, or two or more types can be mixed and used. Of these, water, isopropyl alcohol or a mixture thereof is preferable.
精製処理方法では、溶媒に溶解したベタイン型界面活性剤の溶液の濃度は１〜７５質量％が挙げられるが、本発明の精製処理方法では、５〜５０質量％とする。 The refining treatment method, concentration of the solution of betaine type surface active agent dissolved in solvent include 1 to 75 wt%, but the purification treatment process of the present invention shall be the 5 to 50 mass%.
本発明の精製処理方法では、溶媒に溶解したベタイン型界面活性剤の溶液をイオン交換処理する具体的な方法として、バッチ法やカラム法が適用できるが、なかでもカラム法が好ましい。 In the purification treatment method of the present invention, a batch method or a column method can be applied as a specific method for ion-exchange treatment of a solution of a betaine surfactant dissolved in a solvent, and the column method is particularly preferred.
精製処理方法として、強酸性カチオン交換樹脂と強アルカリ性アニオン交換樹脂との混合割合は、前者／後者＝１／１〜１／３（容量比）が挙げられるが、本発明の精製処理方法では、強酸性カチオン交換樹脂と強アルカリ性アニオン交換樹脂との混合割合は、前者／後者＝１／１．５〜１／２．５（容量比）とする。 As a purification treatment method, the mixing ratio of the strongly acidic cation exchange resin and the strong alkaline anion exchange resin includes the former / the latter = 1/1 to 1/3 (volume ratio). In the purification treatment method of the present invention, the mixing ratio of the strongly acidic cation exchange resin and a strong alkaline anion exchange resin shall be the former / latter = 1 /1.5～1/2.5 (volume ratio).
本発明の精製処理方法では、溶媒に溶解したベタイン型界面活性剤の溶液を、強酸性カチオン交換樹脂と強アルカリ性アニオン交換樹脂との混合樹脂層に通液してイオン交換処理するのが好ましい。またこの際の空間速度（ＳＶ）は０．０１〜２０．０とするのが好ましく、０．０１〜１０．０とするのがより好ましい。 In the purification treatment method of the present invention, it is preferable that a solution of a betaine surfactant dissolved in a solvent is passed through a mixed resin layer of a strongly acidic cation exchange resin and a strongly alkaline anion exchange resin for ion exchange treatment. In this case, the space velocity (SV) is preferably 0.01 to 20.0, and more preferably 0.01 to 10.0.
本発明の精製処理方法は、メンブレンフィルター等による精密濾過、電気透析又は限外濾過といった他の精製処理方法と組み合わせることもできる。 The purification treatment method of the present invention can be combined with other purification treatment methods such as microfiltration using a membrane filter or the like, electrodialysis, or ultrafiltration.
精製処理方法として、以上説明したイオン交換処理により、ベタイン型界面活性剤に含まれるＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を５ｐｐｍ以下となるような精製処理が挙げられるが、本発明の精製処理方法は、これらの各イオン濃度を１ｐｐｍ以下となるように精製処理する。 As refining treatment method, described above-described ion exchange treatment, Cl contained in the betaine type surfactant, Na, Ca, Mg, although purification treatment such that 5ppm or less of each ion concentration of Fe and Si are mentioned , purification treatment method of the present invention, you purified process each of these ion concentrations such that the 1ppm or less.
本発明の精製処理方法では、Ｃｌのイオン濃度は電位差滴定法又はイオンクロマトグラフ法により、またＮａ、Ｃａ、Ｍｇ、Ｆｅの各イオン濃度は原子吸光分光測定法により、更にＳｉのイオン濃度はＩＣＰ発光分光測定法により測定して求めることができる。なお１ｐｐｍは１ｍｇ／ｋｇの濃度を示す。 In the purification treatment method of the present invention, the Cl ion concentration is determined by potentiometric titration or ion chromatography, the Na, Ca, Mg, and Fe ion concentrations are determined by atomic absorption spectrometry, and the Si ion concentration is determined by ICP. It can be determined by measurement by emission spectroscopy. 1 ppm indicates a concentration of 1 mg / kg.
次に、本発明に係る精製ベタイン型界面活性剤（以下、単に本発明の精製ベタイン型界面活性剤という）について説明する。本発明の精製ベタイン型界面活性剤は、以上説明した本発明の精製処理方法によって得られるものである。 Next, the purified betaine surfactant according to the present invention (hereinafter simply referred to as the purified betaine surfactant of the present invention) will be described. The purified betaine surfactant of the present invention is obtained by the purification treatment method of the present invention described above.
精製ベタイン型界面活性剤として、ベタイン型界面活性剤に含まれるＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を５ｐｐｍ以下にまで低減したものが挙げられる。本発明の精製ベタイン型界面活性剤は、ベタイン型界面活性剤に含まれるＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ以下にまで低減したものである。 As refining betaine type surfactants, Cl contained in the betaine type surfactant, Na, Ca, Mg, include those having a reduced each ion concentration of Fe and Si to the 5ppm or less. The purified betaine-type surfactant of the present invention is one in which each ion concentration of Cl, Na, Ca, Mg, Fe and Si contained in the betaine-type surfactant is reduced to 1 ppm or less.
本発明の精製ベタイン型界面活性剤は、インクジェット用インク、半導体製造プロセスの各工程で用いる洗浄液や表面処理液、ホトレジストプロセスの処理液、剥離液、現像液、洗浄液、及びコート剤、電池、コンデンサ及びキャパシター等の電解液や電極製造組成物、種々のコート剤、インクや塗料における顔料やカーボンブラックの分散剤、ナノテクノロジーにおけるカーボンナノチューブ、フラーレン及び金属ナノ粒子の分散剤、色素増感型太陽電池における酸化チタンの分散剤等、多くの分野において有用である。 The purified betaine-type surfactant of the present invention is an inkjet ink, a cleaning solution or a surface treatment solution used in each step of a semiconductor manufacturing process, a photoresist process treatment solution, a stripping solution, a developing solution, a cleaning solution, and a coating agent, battery, capacitor. Electrolytic solutions such as capacitors, electrode manufacturing compositions, various coating agents, pigments and carbon black dispersants in inks and paints, carbon nanotubes, fullerenes and metal nanoparticle dispersants in nanotechnology, dye-sensitized solar cells It is useful in many fields such as a titanium oxide dispersant.
以上説明した本発明によると、不純物として各種イオンを相応に高濃度で含有するベタイン型界面活性剤からＣｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオンを簡便な作業で効率よく除去して、これらの各イオン濃度を１ｐｐｍ以下にまで低減することができ、得られる精製ベタイン型界面活性剤は、インクジェットノズル、電子、半導体及び精密加工分野等で腐食や汚染等を引き起こすことなく使用することができる。 According to the present invention described above, Cl, Na, Ca, Mg, Fe, and Si ions can be efficiently removed by a simple operation from a betaine surfactant containing various ions as impurities in correspondingly high concentrations. The concentration of each of these ions can be reduced to 1 ppm or less, and the resulting purified betaine surfactant is used without causing corrosion or contamination in the inkjet nozzle, electronic, semiconductor and precision processing fields. be able to.
以下、本発明の構成及び効果をより具体的にするために実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, examples and the like will be described in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
ベタイン型界面活性剤（Ｂ−１）の合成
攪拌機、冷却管、温度計を備えた反応容器に、イソプロピルアルコール１６３ｇ、テトラデシルジメチルアミン２４１．５ｇ（１モル）及びモノクロロ酢酸ナトリウム１２８．１ｇ（１．１モル）を仕込み、温度７５〜７９℃にて１６時間反応を行った。その後、反応液を濾過することにより、反応時に析出した塩を濾別し、濾液４９５．１ｇを得た。濾液から減圧蒸留法によりイソプロピルアルコールを留去し、ベタイン型界面活性剤（Ｂ−１）としてテトラデシルジメチルアミノ酢酸ベタイン２６１．６ｇ（０．９モル）を得た。
Synthesis of Betaine Type Surfactant (B-1) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 163 g of isopropyl alcohol, 241.5 g (1 mol) of tetradecyldimethylamine and 128.1 g of sodium monochloroacetate (1 0.1 mol), and the reaction was conducted at a temperature of 75 to 79 ° C. for 16 hours. Then, the salt which precipitated at the time of reaction was separated by filtering the reaction liquid, and 495.1g of filtrate was obtained. Isopropyl alcohol was distilled off from the filtrate by vacuum distillation to obtain 261.6 g (0.9 mol) of tetradecyldimethylaminoacetic acid betaine as the betaine surfactant (B-1).
ベタイン型界面活性剤（Ｂ−２）の合成 テトラデシルジメチルアミンに代えてステアリン酸ジメチルアミノプロピルアミド（パルナーＳＤＰＡ（ミヨシ油脂社製の商品名））を用いたこと以外はベタイン型界面活性剤（Ｂ−１）の合成と同様に行ない、ベタイン型界面活性剤（Ｂ−２）としてステアリン酸アミドプロピルジメチルアミノ酢酸ベタインを得た。 Synthesis of Betaine Type Surfactant (B-2) Betaine Type Surfactant (Parner SDPA (trade name, manufactured by Miyoshi Yushi Co., Ltd.)) was used in place of tetradecyldimethylamine except that stearic acid dimethylaminopropylamide (Parner SDPA (trade name, manufactured by Miyoshi Oil & Fats Co., Ltd.) The synthesis was carried out in the same manner as in B-1) to obtain amidopropyldimethylaminoacetic acid betaine stearate as a betaine surfactant (B-2).
実施例１
ベタイン型界面活性剤（Ｂ−１）３５ｇをイオン交換水１０５ｇに溶解し、濃度２５％水溶液の試料を調製した。強酸性カチオン交換樹脂として予め１Ｎ希塩酸を用いてＨ型に再生しておいたアンバーライト２００ＣＴ（米国ダウ・ケミカル社製の商品名）１７ｍｌと強アルカリ性アニオン交換樹脂として予め１Ｎテトラメチルアンモニウム塩水溶液を用いてＯＨ型に再生しておいたアンバーライトＩＲＡ−９００Ｊ（米国ダウ・ケミカル社製の商品名）３４ｍｌとを均一に混合した混合樹脂を、垂直にセットした内容量１００ｍｌのカラムに充填し、３００ｇのイオン交換水で十分に洗浄した後、２４時間静置した。試料の水溶液及びカラム内の水の温度を１５〜２５℃の範囲内で一定の温度に保温し、空間速度（ＳＶ）０．３で試料の水溶液をカラムに通して、Ｃｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉのイオン濃度を低減した精製ベタイン型界面活性剤溶液を得た。
Example 1
35 g of betaine surfactant (B-1) was dissolved in 105 g of ion-exchanged water to prepare a sample having a 25% concentration aqueous solution. 17 ml of Amberlite 200CT (trade name, manufactured by Dow Chemical Co., USA), which had been regenerated in advance using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin, and a 1N tetramethylammonium salt aqueous solution as a strongly alkaline anion exchange resin. A mixed resin uniformly mixed with 34 ml of Amberlite IRA-900J (trade name manufactured by Dow Chemical Co., Ltd.), which has been regenerated to OH type, is packed into a column with a content volume of 100 ml set vertically, After thoroughly washing with 300 g of ion-exchanged water, it was allowed to stand for 24 hours. The temperature of the aqueous solution of the sample and the water in the column is kept at a constant temperature within a range of 15 to 25 ° C., and the aqueous solution of the sample is passed through the column at a space velocity (SV) of 0.3 to obtain Cl, Na, Ca, A purified betaine surfactant solution with reduced Mg, Fe and Si ion concentrations was obtained.
実施例２〜８、参考例９〜１１
実施例１と同様にして、表１に記載した条件で精製処理を行った。
Examples 2-8 , Reference Examples 9-11
In the same manner as in Example 1, purification treatment was performed under the conditions described in Table 1.
比較例１
イオン交換樹脂として、予め１Ｎ希塩酸を用いてＨ型に再生しておいたアンバーライト２００ＣＴ（米国ダウ・ケミカル社製の商品名）１７ｍｌのみを用い、その他は実施例１と同様に精製処理を行った。
Comparative Example 1
As the ion-exchange resin, only 17 ml of Amberlite 200CT (trade name, manufactured by Dow Chemical Co., USA), which had been regenerated to H type using 1N dilute hydrochloric acid in advance, was used. It was.
比較例２
イオン交換樹脂として、予め１Ｎテトラメチルアンモニウム塩水溶液を用いてＯＨ型に再生しておいたアンバーライトＩＲＡ−９００Ｊ（米国ダウ・ケミカル社製の商品名）３４ｍｌのみを用い、その他は実施例１と同様に精製処理を行った。
Comparative Example 2
As the ion exchange resin, only 34 ml of Amberlite IRA-900J (trade name, manufactured by Dow Chemical Co., USA), which had been regenerated to an OH type using a 1N tetramethylammonium salt aqueous solution in advance, was used. A purification treatment was performed in the same manner.
比較例３
イオン交換処理を行わなかった。
Comparative Example 3
Ion exchange treatment was not performed.
以上の各例の内容を表１にまとめて示した。また以上の各例で得た（精製）ベタイン型界面活性剤について、次のようにイオン濃度を測定し、結果を表２にまとめて示した。 The contents of the above examples are summarized in Table 1. The (purified) betaine surfactants obtained in the above examples were measured for ion concentration as follows, and the results are summarized in Table 2.
（精製）ベタイン型界面活性剤に含まれるＣｌイオン濃度の測定
イオンクロマトグラフ計（ダイオネクス社（現サーモサイエンティフィック社）製の商品名ＤＩＯＮＥＸ ＤＸ３２０）を使用し、イオンクロマトグラフ法によって測定した。
(Purification) Measurement of Cl ion concentration contained in betaine-type surfactant Ion chromatograph (trade name DIONEX DX320 manufactured by Dionex (currently Thermo Scientific)) was used and was measured by ion chromatography.
（精製）ベタイン型界面活性剤に含まれるＮａ、Ｃａ、Ｍｇ及びＦｅイオン濃度の測定
フレーム原子吸光光度計（日立ハイテクノロジー社製の商品名Ｚ−２３１０）を使用し、フレーム原子化法による原子吸光分析法によって測定した。
(Purification) Measurement of Na, Ca, Mg, and Fe ion concentrations contained in betaine surfactants Atom by flame atomization method using flame atomic absorption photometer (trade name Z-2310, manufactured by Hitachi High-Technology Corporation) Measured by absorption spectrometry.
（精製）ベタイン型界面活性剤に含まれるＳｉイオン濃度の測定
ＩＣＰ発光分光光度計（エスアイアイ・ナノテクノロジー社製の商品名ＳＰＳ３１００）を使用し、ＩＣＰ発光分析法によって測定した。
(Purification) Measurement of Si ion concentration contained in betaine-type surfactant An ICP emission spectrophotometer (trade name SPS3100 manufactured by SII NanoTechnology Co., Ltd.) was used and measured by ICP emission analysis.
表１において、
ＳＶ：ベタイン型界面活性剤の水溶液を混合樹脂を充填したカラムに通液してイオン交換処理する際の空間速度
Ｂ−１：テトラデシルジメチルアミノ酢酸ベタイン
Ｂ−２：ステアリン酸アミドプロピルジメチルアミノ酢酸ベタイン
ＣＡ：アンバーライト２００ＣＴ（強酸性カチオン交換樹脂、米国ダウ・ケミカル社製の商品名）
ＡＮ：アンバーライトＩＲＡ−９００Ｊ（強アルカリ性アニオン交換樹脂、米国ダウ・ケミカル社製の商品名）
比較例３：精製処理していない例
In Table 1,
SV: Space velocity when ion exchange treatment is performed by passing an aqueous solution of betaine surfactant through a column packed with mixed resin B-1: Betaine tetradecyldimethylaminoacetate B-2: Amidopropyldimethylaminoacetic acid stearate Betaine CA: Amberlite 200CT (strongly acidic cation exchange resin, trade name manufactured by Dow Chemical, USA)
AN: Amberlite IRA-900J (strong alkaline anion exchange resin, trade name of Dow Chemical Company, USA)
Comparative Example 3: Example without purification treatment
表２において、
ｐｐｍ：ｍｇ／ｋｇの濃度で、（精製）ベタイン型界面活性剤の固形分に含まれる濃度
In Table 2,
ppm: Concentration in the solid content of (purified) betaine surfactant at a concentration of mg / kg
表１に対応する表２の結果からも明らかなように、本発明によれば、Ｃｌ、Ｎａ、Ｃａ、Ｍｇ、Ｆｅ及びＳｉの各イオン濃度を１ｐｐｍ以下にまで低減した精製ベタイン型界面活性剤を得ることができる。
As is clear from the results in Table 2 corresponding to Table 1, according to the present invention, purified betaine-type surface actives in which each ion concentration of Cl, Na, Ca, Mg, Fe and Si is reduced to 1 ppm or less. An agent can be obtained.
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