JP2005213193A - New quaternary ammonium sulfonate - Google Patents
New quaternary ammonium sulfonate Download PDFInfo
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- JP2005213193A JP2005213193A JP2004021321A JP2004021321A JP2005213193A JP 2005213193 A JP2005213193 A JP 2005213193A JP 2004021321 A JP2004021321 A JP 2004021321A JP 2004021321 A JP2004021321 A JP 2004021321A JP 2005213193 A JP2005213193 A JP 2005213193A
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- quaternary ammonium
- ammonium salt
- hydroxyethyl
- bis
- aminoethylsulfonic acid
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- 125000001453 quaternary ammonium group Chemical group 0.000 title abstract description 10
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 26
- -1 N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid quaternary ammonium salt Chemical class 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- AJTVSSFTXWNIRG-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanesulfonic acid Chemical compound OCC[NH+](CCO)CCS([O-])(=O)=O AJTVSSFTXWNIRG-UHFFFAOYSA-N 0.000 claims description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- RAMAMEQGRQWGRX-UHFFFAOYSA-N 2-[bis(2-hydroxypropyl)amino]ethanesulfonic acid Chemical compound CC(O)CN(CC(C)O)CCS(O)(=O)=O RAMAMEQGRQWGRX-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- BGEYRKOSWRWIRS-UHFFFAOYSA-N 2-[bis(2-hydroxybutyl)amino]ethanesulfonic acid Chemical compound CCC(O)CN(CCS(O)(=O)=O)CC(O)CC BGEYRKOSWRWIRS-UHFFFAOYSA-N 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 239000000543 intermediate Substances 0.000 abstract description 4
- 239000012450 pharmaceutical intermediate Substances 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 description 51
- 229960003080 taurine Drugs 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 23
- 239000002994 raw material Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 229920003009 polyurethane dispersion Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- BQEUPQCYGGWDEK-UHFFFAOYSA-N 2-amino-4-hydroxybutane-1-sulfonic acid Chemical compound OCCC(N)CS(O)(=O)=O BQEUPQCYGGWDEK-UHFFFAOYSA-N 0.000 description 2
- 0 C*(C)**N=O Chemical compound C*(C)**N=O 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- YWXKXCKOEHFKFL-UHFFFAOYSA-N 2-hydroxyethyl sulfamate Chemical compound NS(=O)(=O)OCCO YWXKXCKOEHFKFL-UHFFFAOYSA-N 0.000 description 1
- OTTPFCJTQXRWHO-UHFFFAOYSA-N 3-(2,3-dichloroanilino)cyclohex-2-en-1-one Chemical class ClC1=CC=CC(NC=2CCCC(=O)C=2)=C1Cl OTTPFCJTQXRWHO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPBXUMGWBOLUGV-UHFFFAOYSA-N O[N+](O)(O)[O-] Chemical class O[N+](O)(O)[O-] JPBXUMGWBOLUGV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 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 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000000243 solution Substances 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
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、新規なスルホン酸４級アンモニウム塩に関するものである。詳しくは本発明は界面活性剤原料、医薬中間体、有機薬品中間体、ポリウレタン原料、ポリエステル原料などに有用なスルホン酸４級アンモニウム塩に関する。特に本発明は、水性又は水溶性のポリマー成分として効果的にスルホン酸基を導入することのでき、ポリウレタン合成反応等において有機溶媒に可溶であり、さらに液状で取り扱いのしやすい新規スルホン酸基含有成分として有用なＮ，Ｎ‐ビス（２‐ヒドロキシエチル）アミノエチルスルホン酸４級アンモニウム塩及びその製造方法に関する。 The present invention relates to a novel sulfonic acid quaternary ammonium salt. Specifically, the present invention relates to a sulfonic acid quaternary ammonium salt useful for a surfactant raw material, a pharmaceutical intermediate, an organic chemical intermediate, a polyurethane raw material, a polyester raw material and the like. In particular, the present invention can effectively introduce a sulfonic acid group as an aqueous or water-soluble polymer component, is soluble in an organic solvent in a polyurethane synthesis reaction or the like, and is also a liquid and easy to handle. The present invention relates to a quaternary ammonium salt of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid useful as a component and a method for producing the same.
水性ポリウレタンを製造する方法として重合体中にスルホン酸基を導入する方法が知られている。例えば、ポリオール成分としてＮ，Ｎ‐ビス（２‐ヒドロキシエチル）アミノエチルスルホン酸テトラアルキル４級アンモニウム塩を使用する方法である（特許文献１参照）。しかしながらビス（２‐ヒドロキシエチル）アミノエチルスルホン酸テトラメチル４級アンモニウム塩等のテトラアルキルアンモニウム塩は、常温固体の形状であって、反応原料として使用するためには粉体化等の特別な工程が必要であり、取り扱いにくい。また溶媒への溶解度もそれほど高くないため、実用上の問題があった。さらには４級アンモニウム塩の製法が電解法など特殊な製法によるため高価でもあった。また、１分子中に存在する水酸基の個数は２個に限定され、生成する重合体の分子設計の自由度にいま一つの欠点があった。
本発明の目的は、常温液体の形状であって取扱いやすく、アルキレンオキシドの付加反応で容易に製造でき、かつ１分子中に３個以上の水酸基を有する
機能的で多方面の応用が期待できるＮ，Ｎ‐ビス（２‐ヒドロキシエチル）アミノエチルスルホン酸４級アンモニウム塩を提供することにある。
The object of the present invention is a liquid at room temperature, which is easy to handle, can be easily produced by an addition reaction of alkylene oxide, and can be expected to have functional and versatile applications having three or more hydroxyl groups in one molecule. , N-bis (2-hydroxyethyl) aminoethylsulfonic acid quaternary ammonium salt.
本発明者は、種々検討を行った結果、アミノ基側に２個の水酸基を導入することに加えて、アンモニウム塩側にも少なくとも１個の２−ヒドロキシアルキル基を導入することにより１分子中に少なくとも３個の水酸基を有し、常温液体の形状であって取扱いやすい新規なＮ，Ｎ‐ビス（２‐ヒドロキシエチル）アミノエチルスルホン酸４級アンモニウム塩及びその製造方法を見出し本発明に到達した。 As a result of various studies, the present inventor has introduced two hydroxyl groups on the amino group side, and also introduces at least one 2-hydroxyalkyl group on the ammonium salt side into one molecule. Has found a novel N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid quaternary ammonium salt having at least three hydroxyl groups in the form of a liquid at room temperature and easy to handle, and has reached the present invention. did.
すなわち、本発明の要旨は、一般式（１）で示されるＮ，Ｎ−ビス（２−ヒドロキシアルキル）アミノエチルスルホン酸４級アンモニウム塩に存する。
（式中、Ｒ1及びＲ2は、同一又は異なる炭素数２〜４のアルキレン基を示し、Ｒ3〜Ｒ6の少なくとも１つは、同一又は異なる炭素数２〜４の２−ヒドロキシアルキル基を示し、かつ残余は同一又は異なる炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基を示す。）
That is, the gist of the present invention resides in the quaternary ammonium salt of N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid represented by the general formula (1).
Wherein R 1 and R 2 represent the same or different alkylene group having 2 to 4 carbon atoms, and at least one of R 3 to R 6 is the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms. And the remainder represents the same or different linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.)
更に、本発明は、式（２）で示されるＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸トリメチルモノ−２−ヒドロキシエチル４級アンモニウム塩にも存する。 Furthermore, the present invention also resides in an N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethyl mono-2-hydroxyethyl quaternary ammonium salt represented by the formula (2).
本発明によれば、アミノ基側に２個、アンモニウム塩側に少なくとも１個の２−ヒドロキシアルキル基を導入することにより１分子中に少なくとも３個の水酸基を有し、常温液体の形状であって取扱いやすい新規なＮ，Ｎ‐ビス（２‐ヒドロキシアルキル）アミノエチルスルホン酸４級アンモニウム塩及びその製造方法が提供される。界面活性剤原料、医薬中間体、有機薬品中間体、ポリウレタン原料、ポリエステル原料などに有用なスルホン酸４級アンモニウム塩である。 According to the present invention, by introducing two 2-hydroxyalkyl groups on the amino group side and at least one 2-hydroxyalkyl group on the ammonium salt side, the molecule has at least three hydroxyl groups in one molecule and is in the form of a room temperature liquid. A novel N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid quaternary ammonium salt and a process for producing the same are provided. It is a sulfonic acid quaternary ammonium salt useful for surfactant raw materials, pharmaceutical intermediates, organic chemical intermediates, polyurethane raw materials, polyester raw materials and the like.
本発明の一般式（１）において、Ｒ1及びＲ2は、同一又は異なる炭素数２〜４のアルキレン基を示す。具体的には、エチレン基、プロピレン基、ブチレン基等が挙げられる。Ｒ3〜Ｒ6の少なくとも１つは、同一又は異なる炭素数２〜４の２−ヒドロキシアルキル基を示す。かかる２−ヒドロキシアルキル基としては、具体的には、２−ヒドロキシエチル基、２−メチル−２−ヒドロキシエチル基、２−エチル−２−ヒドロキシエチル基等が挙げられる。 In the general formula (1) of the present invention, R 1 and R 2 represent the same or different alkylene groups having 2 to 4 carbon atoms. Specific examples include an ethylene group, a propylene group, and a butylene group. At least one of R 3 to R 6 represents the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms. Specific examples of the 2-hydroxyalkyl group include a 2-hydroxyethyl group, a 2-methyl-2-hydroxyethyl group, and a 2-ethyl-2-hydroxyethyl group.
本発明のスルホン酸４級アンモニウム塩は、一般式（１）のＲ3〜Ｒ6の少なくとも１個が２−ヒドロキシアルキル基である必要がある。Ｒ3〜Ｒ6の４個全てが
２−ヒドロキシアルキル基であるテトラヒドロキシアンモニウム塩でもよく、３個が
２−ヒドロキシアルキル基で残余の１個が炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基であってもよく、２個が２−ヒドロキシアルキル基で残余の２個が同一又は異なる炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基であってもよい。前記アルキル基としては、メチル基、エチル基、ブチル基、オクチル基、ドデシル基、ステアリル基、シクロヘキシル基、シクロヘキシルメチル基、ベンジル基などが挙げられる。
In the sulfonic acid quaternary ammonium salt of the present invention, at least one of R 3 to R 6 in the general formula (1) needs to be a 2-hydroxyalkyl group. A tetrahydroxyammonium salt in which all four of R 3 to R 6 are 2-hydroxyalkyl groups may be used, 3 is a 2-hydroxyalkyl group and the remaining one is a linear or branched chain having 1 to 18 carbon atoms. Alternatively, it may be a cyclic alkyl group, or two may be 2-hydroxyalkyl groups and the remaining two may be the same or different C 1-18 linear, branched or cyclic alkyl groups. . Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, a stearyl group, a cyclohexyl group, a cyclohexylmethyl group, and a benzyl group.
以上のようなスルホン酸アンモニウム塩の好ましい具体例としては、前述の式（２）〜（１１）で示した各種の化合物が例示できるが、更に式（１２）〜（１３）の化合物も挙げられる。 Preferable specific examples of the sulfonic acid ammonium salt as described above include various compounds represented by the above formulas (2) to (11), and further include compounds of the formulas (12) to (13). .
アルキレンオキシドとしてはエチレンオキシドが反応性が高く、生成物中の水酸基の活性も高いので好ましく使用される。アルキレンオキシドは２種以上混合して使用することもできる。反応温度が高すぎると副反応が多くなり、またアルキレンオキシドが３倍モルを超えて使用された場合もホフマン分解反応などの副反応が多くなるので、通常上記の範囲から選択される。 As the alkylene oxide, ethylene oxide is preferably used because of its high reactivity and high activity of hydroxyl groups in the product. A mixture of two or more alkylene oxides can be used. When the reaction temperature is too high, side reactions increase, and when alkylene oxide is used in an amount exceeding 3 moles, side reactions such as Hofmann decomposition reactions increase, so the reaction temperature is usually selected from the above range.
上記反応において、エチレンオキシドを使用する場合は、全てが２−ヒドロキシ体となり１級アルコール性ＯＨ基が生成する。一方、プロピレンオキシドやブチレンオキシドを使用する場合は、殆ど２−メチルまたは２−エチルの２−ヒドロキシ体となり２級アルコール性ＯＨ基が生成するが、１級アルコール性ＯＨ基も少量副生する。
少量副生して混合物になることは、本発明の４級アンモニウム塩をポリウレタン原料などに使用するに当たって特別の支障になるものではない。
In the above reaction, when ethylene oxide is used, all become 2-hydroxy compounds and primary alcoholic OH groups are generated. On the other hand, when propylene oxide or butylene oxide is used, a 2-hydroxy or 2-ethyl 2-hydroxy form is formed, and a secondary alcoholic OH group is produced, but a small amount of primary alcoholic OH group is also produced as a by-product.
By using a small amount of by-product to form a mixture, there is no particular problem in using the quaternary ammonium salt of the present invention as a polyurethane raw material.
上記の反応は無触媒でも進行するが、必要に応じて第３級アミンや水酸化アルカリなど開環付加反応触媒を使用することができる。触媒を使用することによりアルキレンオキシドの付加反応する選択性を高めることができる。反応溶媒としては通常水が用いられるが、必要に応じてメタノール、エタノール、イソプロパノール、トルエンなどを混合し、溶解性を制御することもできる。 Although the above reaction proceeds even without a catalyst, a ring-opening addition reaction catalyst such as a tertiary amine or an alkali hydroxide can be used as necessary. By using a catalyst, the selectivity for the addition reaction of alkylene oxide can be enhanced. As the reaction solvent, water is usually used, but if necessary, methanol, ethanol, isopropanol, toluene and the like can be mixed to control the solubility.
アミノエチルスルホン酸４級アンモニウム塩は、溶媒（水）１００重量部に対して、通常２０〜２５０重量部、好ましくは４０〜２００重量部用いられる。上記以下の少量では反応効率が悪いだけではなく、水とアルキレンオキシドからの反応副生成物が多量に生成し好ましくない。一方、多すぎては反応が不均一になり、また粘度が高くなり、円滑な反応に支障が出る恐れがある。 The aminoethylsulfonic acid quaternary ammonium salt is usually used in an amount of 20 to 250 parts by weight, preferably 40 to 200 parts by weight, per 100 parts by weight of the solvent (water). If the amount is less than the above, the reaction efficiency is not only poor, but a reaction by-product from water and alkylene oxide is generated in a large amount, which is not preferable. On the other hand, if the amount is too large, the reaction becomes non-uniform and the viscosity becomes high, which may hinder smooth reaction.
反応の実施態様を述べると、まず所定量の反応媒体（水）にアミノエチルスルホン酸塩（タウリン塩）を添加しアルキレンオキシドを所定の反応温度下、連続的又は間欠的に添加する。この間の反応圧力には特に限定はないが、通常０．５ＭＰａ以下で充分である。また、反応時間は用いる原料の種類及び反応温度によって異なるが、アルキレンオキシドの添加によって発生する反応圧力が大気圧に戻った時点以降の反応時間も含めて通常１〜５時間で充分である。反応終了後は未反応アルキレンオキシドが残存するならば、反応系を減圧にすることによってこれを除去し、目的物を得ることができる。目的物の形態が水溶液であればこのまま製品化することができ、必要に応じて濃縮することもでき、また有機溶媒などにとって希釈ないし濃度を調整することもできる。 To describe the embodiment of the reaction, first, aminoethyl sulfonate (taurine salt) is added to a predetermined amount of reaction medium (water), and alkylene oxide is added continuously or intermittently at a predetermined reaction temperature. The reaction pressure during this period is not particularly limited, but usually 0.5 MPa or less is sufficient. The reaction time varies depending on the type of raw material used and the reaction temperature, but usually 1 to 5 hours is sufficient, including the reaction time after the reaction pressure generated by the addition of alkylene oxide returns to atmospheric pressure. If unreacted alkylene oxide remains after completion of the reaction, it can be removed by reducing the pressure of the reaction system to obtain the desired product. If the form of the target product is an aqueous solution, it can be commercialized as it is, can be concentrated if necessary, and can be diluted or adjusted for an organic solvent or the like.
なお、アミノエチルスルホン酸４級アンモニウム塩は、アミノエチルスルホン酸（タウリン：Ｈ2ＮＣＨ2ＣＨ2ＳＯ3Ｈ）と、モノアルキルトリ−２−ヒドロキシエチルアンモニウムヒドロキシド、ジアルキルジ−２−ヒドロキシエチルアンモニウムヒドロキシド、トリアルキルモノ−２−ヒドロキシエチルアンモニウムヒドロキシド等との中和反応により合成することができる。また、モノアルキルトリ−２−ヒドロキシエチルアンモニウムヒドロキシドは、例えば、モノメチルアミン水溶液に３倍モルのエチレンオキシドを反応させることによって製造することができる。 In addition, aminoethylsulfonic acid quaternary ammonium salt includes aminoethylsulfonic acid (taurine: H 2 NCH 2 CH 2 SO 3 H), monoalkyltri-2-hydroxyethylammonium hydroxide, dialkyldi-2-hydroxyethylammonium. It can be synthesized by a neutralization reaction with hydroxide, trialkylmono-2-hydroxyethylammonium hydroxide or the like. In addition, monoalkyltri-2-hydroxyethylammonium hydroxide can be produced, for example, by reacting 3 times mole of ethylene oxide with a monomethylamine aqueous solution.
また、タウリンナトリウム塩、カリウム塩、アンモニウム塩等のタウリン塩を原料として、これに２倍モルのエチレンオキシドを付加させてＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸塩とし、しかる後、イオン交換法によって、該スルホン酸塩をモノアルキルトリ−２−ヒドロキシエチルアンモニウム塩、ジアルキルジ−２−ヒドロキシエチルアンモニウム塩とすることもできる。しかし、このイオン交換法は前述した中和法に比較してイオン交換膜等の特別な装置が必要なので経済的にあまり有利ではない。 Further, a taurine salt such as taurine sodium salt, potassium salt, ammonium salt or the like is used as a raw material, and 2-fold moles of ethylene oxide are added thereto to form N, N-bis (2-hydroxyethyl) aminoethyl sulfonate. The sulfonate can be converted into a monoalkyltri-2-hydroxyethylammonium salt or a dialkyldi-2-hydroxyethylammonium salt by an ion exchange method. However, this ion exchange method is not very advantageous economically because a special apparatus such as an ion exchange membrane is required as compared with the neutralization method described above.
Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノスルホン酸塩は、ビニルスルホン酸塩にジエタノールアミンを付加させて製造することができる。また、塩化タウリン塩とジエタノールアミンを脱塩酸反応して製造することもできる。 N, N-bis (2-hydroxyethyl) aminosulfonate can be produced by adding diethanolamine to vinylsulfonate. It can also be produced by dehydrochlorination of taurine chloride and diethanolamine.
次に実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を逸脱しない限りこれら実施例によって制約を受けるものではない。なお、化学分析及び機器分析は下記の方法に従った。
（１）水酸基価
ピリジン溶媒中、微沸下で所定量のサンプルを過剰の無水酢酸と反応させ、生成する酢酸と残存する酢酸を自動滴定装置（京都電子工業社製、ＡＴ−４２０）を使用し、Ｎ／２の水酸化カリウム水溶液で滴定する。ブランクとの差より水酸基価を計算し、ｍｇＫＯＨ／ｇの単位で表示した。
（２）酸価
所定量のサンプルを自動滴定装置（京都電子工業社製、ＡＴ−４２０）を使用しＮ／１０ＨＣｌ水溶液で滴定する。その後、同様にＮ／１０ＫＯＨ水溶液でスルホン酸基を逆滴定する。滴定値より酸価を計算し、ｍｇＫＯＨ／ｇの単位で表示した。
（３）アルカリ価
所定量のサンプルを自動滴定装置（京都電子工業社製、ＡＴ−４２０）を使用しＮ／１０ＨＣｌ水溶液で滴定する。滴定値よりアルカリ価を計算し、ｍｇＫＯＨ／ｇの単位で表示した。
（４）赤外線吸収スペクトル分析
日本分光社製、ＦＴ−ＩＲ−６１０を使用し測定した。
（５）核磁気共鳴分析
日立製作所社製、ＲＳ−ＮＭＲ、Ｒ−１２００を使用し測定した。
EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention will not be restrict | limited by these Examples, unless it deviates from the summary. In addition, chemical analysis and instrumental analysis followed the following method.
(1) Hydroxyl value A predetermined amount of sample is reacted with an excess of acetic anhydride in a pyridine solvent under slight boiling, and the resulting acetic acid and the remaining acetic acid are automatically titrated (AT-420, manufactured by Kyoto Electronics Industry Co., Ltd.). And titrate with an aqueous N / 2 potassium hydroxide solution. The hydroxyl value was calculated from the difference from the blank and displayed in units of mgKOH / g.
(2) Acid value A predetermined amount of the sample is titrated with an N / 10 HCl aqueous solution using an automatic titrator (AT-420, manufactured by Kyoto Electronics Industry Co., Ltd.). Thereafter, the sulfonic acid groups are similarly back titrated with an N / 10 KOH aqueous solution. The acid value was calculated from the titration value and displayed in units of mgKOH / g.
(3) Alkali value A predetermined amount of sample is titrated with an N / 10 HCl aqueous solution using an automatic titration apparatus (AT-420, manufactured by Kyoto Electronics Industry Co., Ltd.). The alkali value was calculated from the titration value and displayed in units of mgKOH / g.
(4) Infrared absorption spectrum analysis It measured using JASCO Corporation FT-IR-610.
(5) Nuclear magnetic resonance analysis It measured using Hitachi Ltd. RS-NMR and R-1200.
［実施例１］
（Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩）
（１）タウリン４級アンモニウム塩の製造
容量１．５Ｌの金属製オートクレーブにモノメチルアミン水溶液（４０％）２００ｇと水３２４ｇとを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド３６４ｇを４．５時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行い、４級アンモニウム塩水溶液８７９ｇが得られた。
[Example 1]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt In a 1.5 L metal autoclave, 200 g of monomethylamine aqueous solution (40%) and 324 g of water were placed and sealed, and then 364 g of ethylene oxide was added while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding over 4.5 hours. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further carried out at the same temperature for 30 minutes to obtain 879 g of a quaternary ammonium salt aqueous solution.
次に、得られた４級アンモニウム水溶液５７９ｇとタウリン２００ｇを容量１Ｌの４つ口フラスコで中和させ、水１４２ｇを添加し、固形分５０％のタウリン４級アンモニウム塩水溶液９１２ｇが得られた。 Next, 579 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized with a 1 L four-necked flask, 142 g of water was added, and 912 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% was obtained.
（２）アルキレンオキシドとの反応
容量１．５Ｌの金属製オートクレーブに上記で製造したタウリン４級アンモニウム塩水溶液６００ｇを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド９６ｇを３時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行った。なお、タウリン塩とアルキレンオキシドとの反応は固形分５０％のタウリン４級アンモニウム塩水溶液６００ｇ（固形分３００ｇ、水３００ｇ）を用いて行われたので、表１中、反応媒体は水３００ｇであると表示した。
(2) Reaction with alkylene oxide After putting 600 g of the taurine quaternary ammonium salt aqueous solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing, 96 g of ethylene oxide was added over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes. The reaction between the taurine salt and the alkylene oxide was performed using 600 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% (solid content: 300 g, water: 300 g). Therefore, in Table 1, the reaction medium is 300 g of water. Is displayed.
その後、反応物中の水分を１１０℃、減圧下（１．３ｋＰａ・ａｂｓ）で脱水し取り除き、常温で液体の製品３８４ｇが得られた。 Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 384 g of a product liquid at room temperature.
製品を化学分析したところ水分０．２％ 水酸基価７２３、酸価１４４、アルカリ価１４４であり、化学分析の結果から計算された純度は９７％であった。 When the product was chemically analyzed, the water content was 0.2%, the hydroxyl value was 723, the acid value was 144, and the alkali value was 144. The purity calculated from the results of the chemical analysis was 97%.
また、赤外吸収スペクトルと１Ｈ−ＮＭＲから、下記式（４）で示されるＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩の構造が同定された。 Further, from the infrared absorption spectrum and 1H-NMR, the structure of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt represented by the following formula (4) was identified. It was done.
ＩＲ（ＫＢｒ）２９４８ｃｍ-1，１１７４ｃｍ-1，１０３８ｃｍ-1，９５１ｃｍ-1，７４１ｃｍ-1
１Ｈ−ＮＭＲ（Ｄ2Ｏ）δ＝３．２〜３．５（ｍ，４Ｈ，−ＳＯ2−ＣＨ2−ＣＨ2−）δ＝３．３（ｓ，３Ｈ，Ｎ+ −ＣＨ3 ）
結果を表１に示した。
IR (KBr) 2948 cm −1 , 1174 cm −1 , 1038 cm −1 , 951 cm −1 , 741 cm −1
1H-NMR (D 2 O) δ = 3.2 to 3.5 (m, 4H, —SO 2 —CH 2 —CH 2 —) δ = 3.3 (s, 3H, N + —CH 3 )
The results are shown in Table 1.
［実施例２］
（Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸ジメチルジ−２−ヒドロキシエチル４級アンモニウム塩）
（１）タウリン４級アンモニウム塩の製造
容量１．５Ｌの金属製オートクレーブにジメチルアミン水溶液（５０％）２００ｇと水２００ｇとを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド２００ｇを３時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行い、４級アンモニウム塩水溶液５９４ｇが得られた。
[Example 2]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt In a 1.5 L metal autoclave, 200 g of dimethylamine aqueous solution (50%) and 200 g of water were placed and sealed, and then 200 g of ethylene oxide was added while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding over 3 hours. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, a further aging reaction was carried out at the same temperature for 30 minutes to obtain 594 g of a quaternary ammonium salt aqueous solution.
次に、得られた４級アンモニウム水溶液４８３ｇとタウリン２００ｇを容量１Ｌの４つ口フラスコで中和させ、水１４２ｇを添加し、固形分５０％のタウリン４級アンモニウム塩水溶液８１７ｇが得られた。 Next, 483 g of the obtained aqueous quaternary ammonium solution and 200 g of taurine were neutralized in a 1 L four-necked flask, 142 g of water was added, and 817 g of an aqueous taurine quaternary ammonium salt solution having a solid content of 50% was obtained.
（２）アルキレンオキシドとの反応
容量１．５Ｌの金属製オートクレーブに上記で製造したタウリン４級アンモニウム塩水溶液６００ｇを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド１０７ｇを３時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行った。
(2) Reaction with alkylene oxide After putting 600 g of the taurine quaternary ammonium salt aqueous solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing, 107 g of ethylene oxide was added over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.
その後、反応物中の水分を１１０℃、減圧下（１．３ｋＰａ・ａｂｓ）で脱水し取り除き、常温で液体の製品３９５ｇが得られた。 Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 395 g of a liquid product at room temperature.
製品を化学分析したところ水酸基価６３３、酸価１５９、アルカリ価１５９であり、化学分析の結果から計算された純度は９９％であった。 Chemical analysis of the product revealed a hydroxyl value of 633, an acid value of 159, and an alkali value of 159, and the purity calculated from the results of chemical analysis was 99%.
また、赤外吸収スペクトルと１Ｈ−ＮＭＲから、下記式（３）で示されるＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸ジメチルジ−２−ヒドロキシエチル４級アンモニウム塩の構造が同定された。 The structure of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt represented by the following formula (3) was identified from the infrared absorption spectrum and 1H-NMR. It was.
ＩＲ（ＫＢｒ）３０３９ｃｍ-1，２９４４ｃｍ-1，１１７２ｃｍ-1，１０３７ｃｍ-1，９５９ｃｍ-1 、７３９ｃｍ-1
１Ｈ−ＮＭＲ（Ｄ2Ｏ）δ＝３．２〜３．５（ｍ，４Ｈ，−ＳＯ2−ＣＨ2−ＣＨ2−）δ＝３．３（ｓ，６Ｈ，Ｎ+ −ＣＨ3 ）
結果を表１に示した。
IR (KBr) 3039cm -1, 2944cm -1, 1172cm -1, 1037cm -1, 959cm -1, 739cm -1
1H-NMR (D 2 O) δ = 3.2 to 3.5 (m, 4H, —SO 2 —CH 2 —CH 2 —) δ = 3.3 (s, 6H, N + —CH 3 )
The results are shown in Table 1.
［実施例３］
（Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸トリメチルモノ−２−ヒドロキシエチル４級アンモニウム塩）
（１）タウリン４級アンモニウム塩の製造
容量１．５Ｌの金属製オートクレーブにトリメチルアミン水溶液（３０％）４００ｇを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド８９ｇを１．５時間かけて連続的にフィードし反応を行った。この間、圧力は１．５気圧以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行い、４級アンモニウム塩水溶液４８５ｇが得られた。
[Example 3]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethyl mono-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt 400 g of trimethylamine aqueous solution (30%) was put in a 1.5 L metal autoclave and sealed, and then 89 g of ethylene oxide was added over 1.5 hours while maintaining the temperature at 45-50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 1.5 atm or less. After completion of the ethylene oxide feed, a ripening reaction was further carried out at the same temperature for 30 minutes to obtain 485 g of a quaternary ammonium salt aqueous solution.
次に、得られた４級アンモニウム水溶液４５３ｇとタウリン２００ｇを容量１Ｌの４つ口フラスコで中和させ、水７７ｇを添加し、固形分５０％のタウリン４級アンモニウム塩水溶液７２２ｇが得られた。 Next, 453 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized in a 1 L four-necked flask, 77 g of water was added, and 722 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% was obtained.
（２）アルキレンオキシドとの反応
容量１．５Ｌの金属製オートクレーブに上記で製造したタウリン４級アンモニウム塩水溶液６００ｇを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド１２２ｇを３時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行った。
(2) Reaction with alkylene oxide After putting 600 g of the taurine quaternary ammonium salt aqueous solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing it, 122 g of ethylene oxide was taken for 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.
その後、反応物中の水分を１１０℃、減圧下（１．３ｋＰａ・ａｂｓ）で脱水し取り除き、常温で液体の製品４０９ｇが得られた。 Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 409 g of a liquid product at room temperature.
製品を化学分析したところ水酸基価５４０、酸価１７３、アルカリ価１７３であり、化学分析の結果から計算された純度は９８％であった。 Chemical analysis of the product revealed a hydroxyl value of 540, an acid value of 173, and an alkali value of 173, and the purity calculated from the results of chemical analysis was 98%.
また、赤外吸収スペクトルと１Ｈ−ＮＭＲから、下記式（２）で示されるＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸トリメチルモノ−２−ヒドロキシエチル４級アンモニウム塩の構造が同定された。 In addition, the structure of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethylmono-2-hydroxyethyl quaternary ammonium salt represented by the following formula (2) was identified from the infrared absorption spectrum and 1H-NMR. It was done.
ＩＲ（ＫＢｒ）３０３４ｃｍ-1，２９４８ｃｍ-1，１１７６ｃｍ-1，１０３８ｃｍ-1，９５７ｃｍ-1 、７４２ｃｍ-1
１Ｈ−ＮＭＲ（Ｄ2Ｏ）δ＝３．２〜３．５（ｍ，４Ｈ，−ＳＯ2−ＣＨ2−ＣＨ2−）δ＝３．３（ｓ，９Ｈ，Ｎ+ −ＣＨ3 ）
結果を表１に示した。
IR (KBr) 3034 cm −1 , 2948 cm −1 , 1176 cm −1 , 1038 cm −1 , 957 cm −1 , 742 cm −1
1H-NMR (D 2 O) δ = 3.2 to 3.5 (m, 4H, —SO 2 —CH 2 —CH 2 —) δ = 3.3 (s, 9H, N + —CH 3 )
The results are shown in Table 1.
［実施例４］
（Ｎ，Ｎ−ビス（２−メチル−２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩）
（１）タウリン４級アンモニウム塩の製造
容量１．５Ｌの金属製オートクレーブにモノメチルアミン水溶液（４０％）２００ｇと水３２４ｇとを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド３６４ｇを４．５時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行い、４級アンモニウム塩水溶液８７９ｇが得られた。
[Example 4]
(N, N-bis (2-methyl-2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt In a 1.5 L metal autoclave, 200 g of monomethylamine aqueous solution (40%) and 324 g of water were placed and sealed, and then 364 g of ethylene oxide was added while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding over 4.5 hours. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further carried out at the same temperature for 30 minutes to obtain 879 g of a quaternary ammonium salt aqueous solution.
次に、得られた４級アンモニウム水溶液５７９ｇとタウリン２００ｇを容量１Ｌの４つ口フラスコで中和させ、水１４２ｇを添加し、固形分５０％のタウリン４級アンモニウム塩水溶液９１２ｇが得られた。 Next, 579 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized with a 1 L four-necked flask, 142 g of water was added, and 912 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% was obtained.
（２）アルキレンオキシドとの反応
容量１．５Ｌの金属製オートクレーブに上記で製造したタウリン４級アンモニウム塩水溶液６００ｇを入れ、密封した後、温度を５０〜５５℃に保ちながらプロピレンオキシド１２７ｇを６時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。プロピレンオキシドのフィード終了後、更に同一温度で２時間熟成反応を行った。
(2) Reaction with alkylene oxide After putting 600 g of the aqueous taurine quaternary ammonium salt solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing, 127 g of propylene oxide was kept for 6 hours while maintaining the temperature at 50 to 55 ° C. The reaction was continued by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the propylene oxide feed, an aging reaction was further performed at the same temperature for 2 hours.
その後、反応物中の水分を１１０℃、減圧下（１．３ｋＰａ・ａｂｓ）で脱水し取り除き、常温で液体の製品４１４ｇが得られた。 Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 414 g of a product liquid at room temperature.
製品を化学分析したところ水分０．２％ 水酸基価７２０、酸価１４５、アルカリ価１４６であり、化学分析の結果から計算された純度は９６％であった。 When the product was chemically analyzed, the water content was 0.2%, the hydroxyl value was 720, the acid value was 145, and the alkali value was 146. The purity calculated from the results of the chemical analysis was 96%.
また、赤外吸収スペクトルと１Ｈ−ＮＭＲから、下記式（６）で示されるＮ，Ｎ−ビス（２−メチル−２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩の構造が同定された。 Further, from the infrared absorption spectrum and 1H-NMR, N, N-bis (2-methyl-2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt represented by the following formula (6) The structure of was identified.
ＩＲ（ＫＢｒ）２９６０ｃｍ-1，１１８０ｃｍ-1，１０４１ｃｍ-1，９４８ｃｍ-1 、７４０ｃｍ-1
１Ｈ−ＮＭＲ（Ｄ2Ｏ）δ＝３．２〜３．５（ｍ，４Ｈ，−ＳＯ2−ＣＨ2−ＣＨ2−）δ＝３．３（ｓ，３Ｈ，Ｎ+ −ＣＨ3 ）δ＝２．８（ｄ，６Ｈ，−Ｎ−Ｃ（ＣＨ3）−）
結果を表１に示した。
IR (KBr) 2960cm -1, 1180cm -1, 1041cm -1, 948cm -1, 740cm -1
1H-NMR (D 2 O) δ = 3.2 to 3.5 (m, 4H, —SO 2 —CH 2 —CH 2 —) δ = 3.3 (s, 3H, N + —CH 3 ) δ = 2.8 (d, 6H, -N -C (CH 3) -)
The results are shown in Table 1.
［実施例５］
（Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸トリメチルモノ−２−ヒドロキシプロピル４級アンモニウム塩）
（１）タウリン４級アンモニウム塩の製造
容量１．５Ｌの金属製オートクレーブにトリメチルアミン水溶液（３０％）４００ｇを入れ、密封した後、温度を４５〜５０℃に保ちながらプロピレンオキシド１１８ｇを２時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。プロピレンオキシドのフィード終了後、更に同一温度で２時間熟成反応を行い、４級アンモニウム塩水溶液５１３ｇが得られた。
[Example 5]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethyl mono-2-hydroxypropyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt 400 g of trimethylamine aqueous solution (30%) was placed in a 1.5 L metal autoclave and sealed, and then 118 g of propylene oxide was added over 2 hours while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding. During this time, the pressure was kept at 0.15 MPa or less. After completion of the propylene oxide feed, an aging reaction was further performed at the same temperature for 2 hours to obtain 513 g of a quaternary ammonium salt aqueous solution.
次に、得られた４級アンモニウム水溶液４７０ｇとタウリン２００ｇを容量１Ｌの４つ口フラスコで中和させ、水１０４ｇを添加し、固形分５０％のタウリン４級アンモニウム塩水溶液７６７ｇが得られた。 Next, 470 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized in a 1 L four-necked flask, and 104 g of water was added to obtain 767 g of an aqueous taurine quaternary ammonium salt solution having a solid content of 50%.
（２）アルキレンオキシドとの反応
容量１．５Ｌの金属製オートクレーブに上記で製造したタウリン４級アンモニウム塩水溶液６００ｇを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド１１５ｇを３時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行った。
(2) Reaction with alkylene oxide After placing 600 g of the aqueous taurine quaternary ammonium salt solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing, 115 g of ethylene oxide was added over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.
その後、反応物中の水分を１１０℃、減圧下（１．３ｋＰａ・ａｂｓ）で脱水し取り除き、常温で液体の製品４０２ｇが得られた。 Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 402 g of a liquid product at room temperature.
製品を化学分析したところ水酸基価５２５、酸価１６４、アルカリ価１６４であり、化学分析の結果から計算された純度は９７％であった。 Chemical analysis of the product revealed a hydroxyl value of 525, an acid value of 164, and an alkali value of 164, and the purity calculated from the results of chemical analysis was 97%.
また、赤外吸収スペクトルと１Ｈ−ＮＭＲから、下記式（１１）で示されるＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸トリメチルモノ−２−ヒドロキシプロピル４級アンモニウム塩の構造が同定された。 Further, from the infrared absorption spectrum and 1H-NMR, the structure of the trimethylmono-2-hydroxypropyl quaternary ammonium salt of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid represented by the following formula (11) was identified. It was done.
ＩＲ（ＫＢｒ）３０３３ｃｍ-1，２９３７ｃｍ-1，１１７３ｃｍ-1，１０３６ｃｍ-1，９７７ｃｍ-1 、７３７ｃｍ-1
１Ｈ−ＮＭＲ（Ｄ2Ｏ）δ＝３．２〜３．５（ｍ，４Ｈ，−ＳＯ2−ＣＨ2−ＣＨ2−）δ＝３．３（ｓ，９Ｈ，Ｎ+ −ＣＨ3 ）δ＝１．３（ｄ，３Ｈ，−Ｎ−Ｃ（ＣＨ3）−）
結果を表１に示した。
IR (KBr) 3033 cm −1 , 2937 cm −1 , 1173 cm −1 , 1036 cm −1 , 977 cm −1 , 737 cm −1
1H-NMR (D 2 O) δ = 3.2 to 3.5 (m, 4H, —SO 2 —CH 2 —CH 2 —) δ = 3.3 (s, 9H, N + —CH 3 ) δ = 1.3 (d, 3H, -N -C (CH 3) -)
The results are shown in Table 1.
（Ｎ，Ｎ−ビス（２−メチル−２−ヒドロキシエチル）アミノエチルスルホン酸テトラメチル４級アンモニウム塩）
（１）タウリン４級アンモニウム塩の製造
４級アンモニウム水溶液（２５％）５８３ｇとタウリン２００ｇを容量１Ｌの４つ口フラスコで中和させ、固形分４１％のタウリン４級アンモニウム塩水溶液７７５ｇが得られた。
(N, N-bis (2-methyl-2-hydroxyethyl) aminoethylsulfonic acid tetramethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt 583 g of quaternary ammonium aqueous solution (25%) and 200 g of taurine are neutralized in a 1 L four-necked flask to obtain 775 g of an aqueous taurine quaternary ammonium salt solution having a solid content of 41%. It was.
（２）アルキレンオキシドとの反応
容量１．５Ｌの金属製オートクレーブに上記で製造したタウリン４級アンモニウム塩水溶液７４１ｇを入れ、密封した後、温度を４５〜５０℃に保ちながらエチレンオキシド１４０ｇを３時間かけて連続的にフィードし反応を行った。この間、圧力は０．１５ＭＰａ以下に保たれた。エチレンオキシドのフィード終了後、更に同一温度で３０分間熟成反応を行った。
(2) Reaction with alkylene oxide After placing 741 g of the aqueous taurine quaternary ammonium salt solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing it, 140 g of ethylene oxide was taken over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.
その後、反応物中の水分を１１０℃、減圧下（１．３ｋＰａ・ａｂｓ）で脱水し取り除き、常温で液体の製品４２７ｇが得られた。 Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 427 g of a product that was liquid at room temperature.
製品を化学分析したところ水分０．２％ 水酸基価３８５、酸価１９２、アルカリ価１９０であり、化学分析の結果から計算された純度は９９％であった。 When the product was chemically analyzed, the water content was 0.2%, the hydroxyl value was 385, the acid value was 192, and the alkali value was 190, and the purity calculated from the results of the chemical analysis was 99%.
反応生成物は融点約７５℃であり、常温固体の形状であった。 The reaction product had a melting point of about 75 ° C. and was in the form of a solid at room temperature.
［参考例１］
撹拌機、温度計、冷却管のついた容量１Ｌの反応容器にポリプロピレングリコール（平均分子量２０００）９０ｇ、ヘキサメチレンジイソシアネート（ＨＤＩ）１５．１ｇ、溶媒（Ｎ−メチルピロリドン）２４４ｇ、および錫系触媒を仕込み、撹拌下６０℃で１２時間反応した。
[Reference Example 1]
In a 1 L reaction vessel equipped with a stirrer, thermometer and condenser, 90 g of polypropylene glycol (average molecular weight 2000), 15.1 g of hexamethylene diisocyanate (HDI), 244 g of solvent (N-methylpyrrolidone), and a tin-based catalyst The reaction was carried out at 60 ° C. for 12 hours with stirring.
次に、実施例１で製造した液状のＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩１６．９ｇを加え、撹拌下６０℃で１２時間反応した。次いで、反応液を３５℃に冷却した後、蒸留水を添加し、さらに３０分撹拌した。 Next, 16.9 g of liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt prepared in Example 1 was added and stirred at 60 ° C. for 12 hours. Reacted. Subsequently, after cooling the reaction liquid to 35 ° C., distilled water was added, and the mixture was further stirred for 30 minutes.
これにより、分散安定性が良好なポリウレタンディスパージョンが得られた。
また、得られたポリウレタンディスパージョンを基材に塗布し、これを乾燥して塗膜が形成することを確認した。
As a result, a polyurethane dispersion having good dispersion stability was obtained.
In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.
［参考例２］
参考例１において使用した、液状のＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩１６．９ｇの代わりに、実施例２で製造したＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸ジメチルジ−２−ヒドロキシエチル４級アンモニウム塩１５．６ｇを使用した以外は参考例１と同様にして分散安定性が良好なポリウレタンディスパージョンが得られた。また、得られたポリウレタンディスパージョンを基材に塗布し、これを乾燥して塗膜が形成することを確認した。
[Reference Example 2]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt 16.9 g used in Reference Example 1, N, A polyurethane dispersion having good dispersion stability was obtained in the same manner as in Reference Example 1 except that 15.6 g of dimethyldi-2-hydroxyethyl quaternary ammonium salt of N-bis (2-hydroxyethyl) aminoethylsulfonic acid was used. It was. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.
［参考例３］
参考例１において使用した、液状のＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩１６．９ｇの代わりに、実施例３で製造したＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸トリメチルモノ−２−ヒドロキシエチル４級アンモニウム塩１１．４ｇを使用した以外は参考例１と同様にして分散安定性が良好なポリウレタンディスパージョンが得られた。また、得られたポリウレタンディスパージョンを基材に塗布し、これを乾燥して塗膜が形成することを確認した。
[Reference Example 3]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt 16.9 g used in Reference Example 1, N, A polyurethane dispersion having good dispersion stability was obtained in the same manner as in Reference Example 1 except that 11.4 g of trimethylmono-2-hydroxyethyl quaternary ammonium salt of N-bis (2-hydroxyethyl) aminoethylsulfonic acid was used. It was. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.
［参考例４］
参考例１において使用した、液状のＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノエチルスルホン酸モノメチルトリ−２−ヒドロキシエチル４級アンモニウム塩１６．９ｇの代わりに、比較例１で製造した常温固体のＮ，Ｎ−ビス（２−メチル−２−ヒドロキシエチル）アミノエチルスルホン酸テトラメチル４級アンモニウム塩１２．９ｇを使用した以外は同様にして、ポリウレタンディスパージョンを得た。ポリウレタン製造反応時に、原料として固体のアンモニウム塩を取り扱う難点があるうえに、溶媒（Ｎ−メチルピロリドン）への溶解性が不足して塗布操作にも難点があった。
[Reference Example 4]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt 16.9 g used in Reference Example 1, a room temperature solid produced in Comparative Example 1 A polyurethane dispersion was obtained in the same manner except that 12.9 g of tetramethyl quaternary ammonium salt of N, N-bis (2-methyl-2-hydroxyethyl) aminoethylsulfonic acid was used. At the time of polyurethane production reaction, there is a difficulty in handling a solid ammonium salt as a raw material, and there is also a difficulty in coating operation due to insufficient solubility in a solvent (N-methylpyrrolidone).
本発明の新規なスルホン酸４級アンモニウム塩は、１分子中に３個以上の水酸基を有しており、界面活性剤原料、医薬中間体、有機薬品中間体、ポリウレタン原料、ポリエステル原料などに利用可能である。
The novel sulfonic acid quaternary ammonium salt of the present invention has three or more hydroxyl groups in one molecule, and is used for surfactant raw materials, pharmaceutical intermediates, organic chemical intermediates, polyurethane raw materials, polyester raw materials, etc. Is possible.
Claims (13)
（式中、Ｒ1及びＲ2は、同一又は異なる炭素数２〜４のアルキレン基を示し、Ｒ3〜Ｒ6の少なくとも１つは、同一又は異なる炭素数２〜４の２−ヒドロキシアルキル基を示し、かつ残余は同一又は異なる炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基を示す。）
Wherein R 1 and R 2 represent the same or different alkylene group having 2 to 4 carbon atoms, and at least one of R 3 to R 6 is the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms. And the remainder represents the same or different linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.)
A quaternary ammonium salt having at least one 2-hydroxyalkyl group on the quaternary ammonium salt side is reacted with an alkylene oxide to form a quaternary N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid. In producing an ammonium salt, quaternary N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid is characterized in that alkylene oxide is continuously or intermittently supplied at 20 to 90 ° C. using water as a reaction medium. A method for producing an ammonium salt.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006213776A (en) * | 2005-02-01 | 2006-08-17 | Yokkaichi Chem Co Ltd | Manufacturing process of crosslinked amphoteric polyurethane elastomer |
| JP2009096798A (en) * | 2007-09-28 | 2009-05-07 | Fujifilm Corp | Sulfonic acid polyol compound, polyurethane resin, polyurethane resin for magnetic recording medium and magnetic recording medium |
| JP2010163376A (en) * | 2009-01-14 | 2010-07-29 | Fujifilm Corp | Method for producing sulfonic acid diol compound and method for producing polyurethane resin |
| JP2010254918A (en) * | 2009-04-28 | 2010-11-11 | Fujifilm Corp | Mixture containing sulfonate group-containing compound and method for producing the same, solution composition, polyurethane resin and method for producing the same, and magnetic recording medium |
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| JP2002128754A (en) * | 2000-10-25 | 2002-05-09 | Nippon Kayaku Co Ltd | Urethane compound, its resin composition and cured product thereof |
| JP2002128857A (en) * | 2000-10-25 | 2002-05-09 | Nippon Kayaku Co Ltd | Urethane oligomer, its resin composition, its cured article |
| JP2003246960A (en) * | 2002-02-25 | 2003-09-05 | Toyo Ink Mfg Co Ltd | Pigment composition and pigment dispersion using the same |
| JP2003292867A (en) * | 2002-03-29 | 2003-10-15 | Toyo Ink Mfg Co Ltd | Pigment composition and pigment dispersion using the same |
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| JPS56151727A (en) * | 1980-04-26 | 1981-11-24 | Nippon Paint Co Ltd | Novel oil free-polyester and its preparation |
| JPH0366660A (en) * | 1989-08-04 | 1991-03-22 | Nisso Yuka Kogyo Kk | Production of n,n-bis(hydroxyalkyl)aminoethylsulfonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006213776A (en) * | 2005-02-01 | 2006-08-17 | Yokkaichi Chem Co Ltd | Manufacturing process of crosslinked amphoteric polyurethane elastomer |
| JP2009096798A (en) * | 2007-09-28 | 2009-05-07 | Fujifilm Corp | Sulfonic acid polyol compound, polyurethane resin, polyurethane resin for magnetic recording medium and magnetic recording medium |
| JP2014088365A (en) * | 2007-09-28 | 2014-05-15 | Fujifilm Corp | Sulfonic acid polyol compound, polyurethane resin, polyurethane resin for magnetic recording medium, and magnetic recording medium |
| JP2010163376A (en) * | 2009-01-14 | 2010-07-29 | Fujifilm Corp | Method for producing sulfonic acid diol compound and method for producing polyurethane resin |
| JP2010254918A (en) * | 2009-04-28 | 2010-11-11 | Fujifilm Corp | Mixture containing sulfonate group-containing compound and method for producing the same, solution composition, polyurethane resin and method for producing the same, and magnetic recording medium |
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