JP5090666B2 - Surfactant composition - Google Patents
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Description
本発明は、α−スルホ脂肪酸エステル塩を高濃度に含有する界面活性剤組成物に関する。 The present invention relates to a surfactant composition containing an α-sulfo fatty acid ester salt in a high concentration.
α−スルホ脂肪酸エステル塩からなるアニオン界面活性剤は、洗浄剤、例えば、食器用洗剤、シャンプー、衣料用洗剤等の主活性剤として広く使用されている。
α−スルホ脂肪酸エステル塩組成物は、通常、水を含有するペースト状又は液状の組成物として製造され、流通されるが、その有効成分濃度は、取り扱い性、生産効率、製品輸送のコストなどを考慮すればできるだけ高濃度であることが望ましい。α−スルホ脂肪酸エステル塩組成物の流動性は、原料油脂の化学構造、製造に際しての未反応物や副生物等にも影響されるが、有効成分が同じであっても濃度によってその流動性は著しく異なり、また一般に４０質量％以上で急激に流動性が低下する。例えば、ドラム缶からα−スルホ脂肪酸エステル塩組成物の抜き出しが困難になる程流動性が低下することがあることも知られている。
したがって、α−スルホ脂肪酸エステル塩組成物の濃度を下げることなく流動性を改善できれば、生産効率が向上すると共に輸送コストが減少し、工業的に極めて有利となる。
Anionic surfactants composed of α-sulfo fatty acid ester salts are widely used as main active agents for detergents such as dishwashing detergents, shampoos and clothing detergents.
The α-sulfo fatty acid ester salt composition is usually manufactured and distributed as a paste-like or liquid composition containing water, and its active ingredient concentration has a handling property, production efficiency, cost of product transportation, etc. Considering it, it is desirable that the concentration be as high as possible. The fluidity of the α-sulfo fatty acid ester salt composition is affected by the chemical structure of the raw oil and fat, unreacted products and by-products during production, but even if the active ingredients are the same, the fluidity depends on the concentration. The fluidity is remarkably different, and generally the fluidity is drastically lowered at 40% by mass or more. For example, it is also known that the fluidity may decrease as it becomes difficult to extract the α-sulfo fatty acid ester salt composition from the drum.
Therefore, if the fluidity can be improved without reducing the concentration of the α-sulfo fatty acid ester salt composition, the production efficiency is improved and the transportation cost is reduced, which is extremely advantageous industrially.
流動性を向上させたアニオン界面活性剤組成物としては、例えば（i）アルキルサルフェートと、ポリアルキレンエーテルグリコールジ硫酸エステルのモノ及び／又はジ塩を粘度調整剤として含有する組成物（特許文献１参照）、及び（ii）高級アルコール硫酸化物の中和工程時又は中和後に、平均分子量３００〜６０００のポリエチレングリコールを０．１〜２５重量％の割合で添加した低粘度界面活性剤（特許文献２参照）が知られている。しかしながら、これらの界面活性剤組成物は未だ流動性が不十分であり、到底満足し得るものではない。 As an anionic surfactant composition with improved fluidity, for example, (i) a composition containing an alkyl sulfate and a mono- and / or di-salt of polyalkylene ether glycol disulfate as a viscosity modifier (Patent Document 1) And (ii) a low-viscosity surfactant in which polyethylene glycol having an average molecular weight of 300 to 6000 is added at a ratio of 0.1 to 25% by weight during or after the neutralization step of the higher alcohol sulfate (Patent Document) 2) is known. However, these surfactant compositions still have insufficient fluidity and are not satisfactory.
本発明は、α−スルホ脂肪酸エステル塩を高濃度に含有しても流動性、希釈性及び溶解性に優れる界面活性剤組成物を提供することを課題とする。 This invention makes it a subject to provide the surfactant composition which is excellent in fluidity | liquidity, dilution property, and solubility, even if it contains alpha-sulfo fatty acid ester salt in high concentration.
本発明者らは、α−スルホ脂肪酸エステル塩に対して特定割合の無機塩化物塩を含有することにより、上記課題を解決しうることを見出した。
すなわち、本発明は、α−スルホ脂肪酸エステル塩４０質量％以上と無機塩化物塩とを含む界面活性剤組成物であって、〔α−スルホ脂肪酸エステル塩：無機塩化物塩〕の質量比が９９：１〜９０：１０である界面活性剤組成物を提供する。
The present inventors have found that the above problem can be solved by containing a specific proportion of an inorganic chloride salt relative to the α-sulfo fatty acid ester salt.
That is, the present invention is a surfactant composition comprising 40% by mass or more of an α-sulfo fatty acid ester salt and an inorganic chloride salt, wherein the mass ratio of [α-sulfo fatty acid ester salt: inorganic chloride salt] is A surfactant composition is provided that is 99: 1 to 90:10.
本発明の界面活性剤組成物は、α−スルホ脂肪酸エステル塩の濃度が４０質量％以上でも濃度増加に伴う粘度変化が緩慢であり、流動性、希釈性及び溶解性が良好でハンドリング性が極めて優れている。 In the surfactant composition of the present invention, even when the concentration of the α-sulfo fatty acid ester salt is 40% by mass or more, the viscosity change accompanying the increase in the concentration is slow, the fluidity, the dilutability and the solubility are good, and the handling property is extremely high. Are better.
本発明の界面活性剤組成物は、α−スルホ脂肪酸エステル塩４０質量％以上と無機塩化物塩とを含む界面活性剤組成物であって、〔α−スルホ脂肪酸エステル塩：無機塩化物塩〕の質量比が９９：１〜９０：１０であることが特徴である。
本発明におけるα―スルホ脂肪酸エステル塩としては、下記一般式（１）で表される化合物が好ましい。
The surfactant composition of the present invention is a surfactant composition containing 40% by mass or more of an α-sulfo fatty acid ester salt and an inorganic chloride salt, [α-sulfo fatty acid ester salt: inorganic chloride salt]. The mass ratio is from 99: 1 to 90:10.
The α-sulfo fatty acid ester salt in the present invention is preferably a compound represented by the following general formula (1).
（式中、Ｒ1は、炭素数６〜２２の炭化水素基、好ましくは直鎖状又は分岐鎖状のアルキル基又はアルケニル基を示し、Ｒ2は、炭素数１〜５の炭化水素基、好ましくは直鎖状又は分岐鎖状のアルキル基又はアルケニル基を示し、Ｍは、アルカリ金属又はアンモニウムを示す。）
一般式（１）で表される化合物は、単一化合物である必要はなく、Ｒ1、Ｒ2がそれぞれ異なるものの混合物であってもよい。
(In the formula, R 1 represents a hydrocarbon group having 6 to 22 carbon atoms, preferably a linear or branched alkyl group or alkenyl group, and R 2 represents a hydrocarbon group having 1 to 5 carbon atoms, Preferably, it represents a linear or branched alkyl group or alkenyl group, and M represents an alkali metal or ammonium.)
The compound represented by the general formula (1) does not need to be a single compound, and may be a mixture in which R 1 and R 2 are different from each other.
一般式（１）において、Ｒ1で示される炭素数６〜２２の直鎖状又は分岐鎖状のアルキル基としては、各種ヘキシル基、各種オクチル基、各種デシル基、各種ドデシル基、各種テトラデシル基、各種ヘキサデシル基、各種オクタデシル基、各種エイコシル基、各種ドコシル基等が挙げられる。また、炭素数６〜２２の直鎖状もしくは分岐鎖状のアルケニル基としては、各種ヘキセニル基、各種オクテニル基、各種デセニル基、各種ドデセニル基、各種ヘキサデセニル基、各種オクタデセニル基等が挙げられる。
これらの中では、Ｒ1は、好ましくは炭素原子数１０〜２２、より好ましくは１２〜１８、更に好ましくは１４〜１８の直鎖状又は分岐鎖状のアルキル基又はアルケニル基であり、特に好ましくは、炭素原子数１４〜１８の直鎖状又は分岐鎖状のアルキル基、なかんずく、直鎖状のアルキル基である。
In the general formula (1), the linear or branched alkyl group having 6 to 22 carbon atoms represented by R 1 includes various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, and various tetradecyl groups. , Various hexadecyl groups, various octadecyl groups, various eicosyl groups, various docosyl groups, and the like. Moreover, as a C6-C22 linear or branched alkenyl group, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various hexadecenyl groups, various octadecenyl groups, etc. are mentioned.
Among these, R 1 is preferably a linear or branched alkyl or alkenyl group having 10 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, still more preferably 14 to 18 carbon atoms, and particularly preferably. Is a linear or branched alkyl group having 14 to 18 carbon atoms, especially a linear alkyl group.
一般式（１）において、Ｒ2で示される炭素数１〜５の直鎖状又は分岐鎖状のアルキル基又はアルケニル基としては、メチル基、エチル基、プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、ビニル基、アリル基、各種ブテニル基、各種ペンチル基が挙げられる。これらの中では、Ｒ2は、好ましくは炭素原子数１〜４、更に好ましくは炭素数１〜３の直鎖状又は分岐鎖状のアルキル基又はアルケニル基であり、特に好ましくは、メチル基、エチル基、プロピル基、イソプロピル基である。
Ｍのアルカリ金属としては、例えば、ナトリウム、カリウム、リチウム等が挙げられ、これらの中ではナトリウム及びカリウムが好ましく、ナトリウムが特に好ましい。
In the general formula (1), examples of the linear or branched alkyl group or alkenyl group having 1 to 5 carbon atoms represented by R 2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, various butyl groups, Examples include various pentyl groups, vinyl groups, allyl groups, various butenyl groups, and various pentyl groups. Among these, R 2 is preferably a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably a methyl group, An ethyl group, a propyl group, and an isopropyl group;
Examples of the alkali metal of M include sodium, potassium, lithium and the like. Among these, sodium and potassium are preferable, and sodium is particularly preferable.
一般式（１）で表されるα―スルホ脂肪酸エステル塩は、特公昭３９−２０８４２号公報、特公昭３９−２８６３５号公報、特公昭４１−９６５号公報等に記載されている公知の方法によって製造することができる。例えば、下記式で示すように、油脂にメタノール等の低級アルコールを反応させて得られた脂肪酸エステル（３）を三酸化イオウ等のスルホン化剤でスルホン化してα―スルホ脂肪酸エステル（２）とし、これを熟成した後に、中和することにより、α―スルホ脂肪酸エステル塩（１）を得ることができる。 The α-sulfo fatty acid ester salt represented by the general formula (1) is obtained by a known method described in JP-B-39-20842, JP-B-39-28635, JP-B-41-965, etc. Can be manufactured. For example, as shown by the following formula, a fatty acid ester (3) obtained by reacting a fat and oil with a lower alcohol such as methanol is sulfonated with a sulfonating agent such as sulfur trioxide to obtain an α-sulfo fatty acid ester (2). The aging is followed by neutralization to obtain the α-sulfo fatty acid ester salt (1).
上記式において、Ｒ1、Ｒ2及びＭは、前記と同じである。
脂肪酸エステル（３）は、牛脂、豚油、魚油等から誘導される動物系脂肪酸エステル、ヤシ油、パ−ム油、パーム核油、大豆油、米ヌカ油等から誘導される植物系脂肪酸エステル、α−オレフィンのオキソ法から誘導される合成脂肪酸アルキルエステル等のいずれでもよく、特に限定されない。例えばラウリン酸、パルミチン酸、ステアリン酸、硬化牛脂脂肪酸、硬化魚油脂肪酸、ヤシ油脂肪酸、パ−ム油脂肪酸、パ−ム核油脂肪酸等の脂肪酸のメチル、エチル又はプロピルエステル等を挙げることができる。これらの脂肪酸エステル（３）は、単独でも混合物でもよいが、着色防止の観点から、そのヨウ素価は、好ましくは０．５以下、より好ましくは０．１以下である。
In the above formula, R 1 , R 2 and M are the same as described above.
The fatty acid ester (3) is an animal fatty acid ester derived from beef tallow, pork oil, fish oil or the like, a plant fatty acid ester derived from coconut oil, palm oil, palm kernel oil, soybean oil, rice bran oil or the like. Any of synthetic fatty acid alkyl esters derived from the α-olefin oxo method may be used without any particular limitation. Examples include methyl, ethyl or propyl esters of fatty acids such as lauric acid, palmitic acid, stearic acid, hydrogenated beef tallow fatty acid, hydrogenated fish oil fatty acid, coconut oil fatty acid, palm oil fatty acid, palm kernel fatty acid and the like. . These fatty acid esters (3) may be used alone or as a mixture, but from the viewpoint of preventing coloring, the iodine value is preferably 0.5 or less, more preferably 0.1 or less.
上記脂肪酸エステル（３）からα―スルホ脂肪酸エステル（２）へのスルホン化に使用する三酸化イオウは、脱湿空気、窒素等で希釈した１．５〜１０容量％のものを用いることができる。
スルホン化反応における〔ＳＯ3／脂肪酸エステル（３）〕モル比は、反応速度の観点から、１．１〜１．３の範囲が好ましい。スルホン化反応温度は、通常５０〜９０℃で行う。
スルホン化反応装置は特に制限されないが、例えば槽型反応装置や薄膜式反応装置等を用いることができる。薄膜式反応装置としては、例えば流下薄膜式反応装置、上昇薄膜型反応装置及び管型気液混合相流反応装置等を用いることができる。
The sulfur trioxide used for sulfonation from the fatty acid ester (3) to the α-sulfo fatty acid ester (2) can be 1.5 to 10% by volume diluted with dehumidified air, nitrogen or the like. .
The [SO 3 / fatty acid ester (3)] molar ratio in the sulfonation reaction is preferably in the range of 1.1 to 1.3 from the viewpoint of the reaction rate. The sulfonation reaction temperature is usually 50 to 90 ° C.
The sulfonation reaction apparatus is not particularly limited, and for example, a tank reaction apparatus, a thin film reaction apparatus, or the like can be used. As the thin film reactor, for example, a falling thin film reactor, a rising thin film reactor, a tubular gas-liquid mixed phase flow reactor, or the like can be used.
薄膜式反応装置でスルホン化反応させた場合は、通常、その反応直後では、下記一般式（４）で表される中間体化合物が生成し、α―スルホ脂肪酸エステル（２）はほとんど生成しない。そのため、その反応混合物を７０〜１００℃で約０．５〜２時間熟成することによって、中間体化合物（４）からＳＯ3を脱離させるのと同時に、残存している脂肪酸エステル（３）のスルホン化反応を進行させることにより、α−スルホ脂肪酸エステル（２）を生成させる。 When the sulfonation reaction is carried out using a thin film reactor, an intermediate compound represented by the following general formula (4) is usually produced immediately after the reaction, and α-sulfo fatty acid ester (2) is hardly produced. Therefore, by aging the reaction mixture at 70 to 100 ° C. for about 0.5 to 2 hours, SO 3 is eliminated from the intermediate compound (4), and at the same time, the remaining fatty acid ester (3) The α-sulfo fatty acid ester (2) is produced by allowing the sulfonation reaction to proceed.
上記一般式（４）において、Ｒ1、Ｒ2及びＭは、前記と同じである。
得られる混合物には中間体化合物（４）が残存するが、中間体化合物（４）を中和すると、洗浄効果に寄与しないα−スルホ脂肪酸塩となるため、洗浄剤用途においては中間体（４）の含有量をできるだけ低下させることが好ましい。
そこで、熟成工程後に、下記式で示されるように、低級アルコールを添加して中間体化合物（４）をα−スルホ脂肪酸エステル（２）とすることができる。
In the general formula (4), R 1 , R 2 and M are the same as described above.
Although the intermediate compound (4) remains in the resulting mixture, neutralization of the intermediate compound (4) results in an α-sulfo fatty acid salt that does not contribute to the cleaning effect. ) Is preferably reduced as much as possible.
Therefore, after the aging step, as shown by the following formula, a lower alcohol can be added to turn the intermediate compound (4) into an α-sulfo fatty acid ester (2).
上記式において、Ｒ1、Ｒ2及びＭは、前記と同じである。
得られたα―スルホ脂肪酸エステル（２）は、水酸化ナトリウム、水酸化カリウム等のアルカリ金属化合物でｐＨ６〜７になるように中和することにより、本発明のα―スルホ脂肪酸エステル塩（１）を得ることができる。
α―スルホ脂肪酸エステル（２）の中和に使用するアルカリ金属化合物の濃度は特に限定されないが、中和後のα―スルホ脂肪酸エステル塩（１）を含む組成物が十分な流動性を有するようにする為には、アルカリ金属化合物の濃度は、通常１０〜５０質量％の範囲で使用されることが好ましい。
In the above formula, R 1 , R 2 and M are the same as described above.
The obtained α-sulfo fatty acid ester (2) is neutralized with an alkali metal compound such as sodium hydroxide or potassium hydroxide so as to have a pH of 6 to 7, whereby the α-sulfo fatty acid ester salt (1) of the present invention (1) is obtained. ) Can be obtained.
The concentration of the alkali metal compound used for neutralization of the α-sulfo fatty acid ester (2) is not particularly limited, but the composition containing the α-sulfo fatty acid ester salt (1) after neutralization has sufficient fluidity. In order to make it, it is preferable that the concentration of the alkali metal compound is usually used in the range of 10 to 50% by mass.
本発明においては、α―スルホ脂肪酸エステル塩（１）を含む組成物の濃度増加に伴う粘度変化を抑制するため、α―スルホ脂肪酸エステル塩に対して無機塩化物塩を含有することに特徴がある。ここで、α−スルホ脂肪酸エステル塩の含有量は、該組成物中４０質量％以上、特に５０質量％以上、中でも特に６０質量％以上の界面活性剤組成物において、本発明の効果を奏するものである。また、その含有量は、該組成物中における〔α−スルホ脂肪酸エステル塩：無機塩化物塩〕の質量比が９９：１〜９０：１０であり、好ましくは９８：２〜９２：８であり、より好ましくは９７：３〜９３：７である量とする。 The present invention is characterized by containing an inorganic chloride salt with respect to the α-sulfo fatty acid ester salt in order to suppress a change in viscosity accompanying an increase in the concentration of the composition containing the α-sulfo fatty acid ester salt (1). is there. Here, the surfactant composition having an α-sulfo fatty acid ester salt content of 40% by mass or more, particularly 50% by mass or more, particularly 60% by mass or more in the composition exhibits the effects of the present invention. It is. In addition, the mass ratio of [α-sulfo fatty acid ester salt: inorganic chloride salt] in the composition is 99: 1 to 90:10, preferably 98: 2 to 92: 8. More preferably, the amount is 97: 3 to 93: 7.
前記反応式により得られたα−スルホ脂肪酸エステル塩（１）を含む組成物は、特に、濃度４０質量％以上で急激に粘度が上昇し、ハンドリング性が極めて悪い。
しかしながら、このα−スルホ脂肪酸エステル塩組成物に無機塩化物塩を、〔α−スルホ脂肪酸エステル塩：無機塩化物塩〕の質量比が９９：１〜９０：１０の割合の範囲内とすることにより、α−スルホ脂肪酸エステル塩組成物の濃度が４０質量％以上の場合であっても、濃度増加に伴う粘度変化を極めて緩慢に抑えることができる。より具体的には、α−スルホ脂肪酸エステル塩組成物に無機塩化物塩を前記の割合で配合すれば、濃度４０質量％以上での粘度の上昇は抑制され、流動性が極めて優れた組成物となる。また、希釈性、溶解性も良好であるので、ハンドリング性が優れている。
In particular, the composition containing the α-sulfo fatty acid ester salt (1) obtained by the above reaction formula has a sharply increased viscosity at a concentration of 40% by mass or more, and the handling property is extremely poor.
However, the inorganic chloride salt is added to the α-sulfo fatty acid ester salt composition so that the mass ratio of [α-sulfo fatty acid ester salt: inorganic chloride salt] is in the range of 99: 1 to 90:10. Thus, even when the concentration of the α-sulfo fatty acid ester salt composition is 40% by mass or more, a change in viscosity accompanying an increase in concentration can be suppressed very slowly. More specifically, when an inorganic chloride salt is added to the α-sulfo fatty acid ester salt composition in the above proportion, an increase in viscosity at a concentration of 40% by mass or more is suppressed, and the composition has excellent fluidity. It becomes. In addition, since the dilutability and solubility are also good, handling properties are excellent.
本発明で使用する無機塩化物塩としては、塩化ナトリウム、塩化カリウム、塩化リチウム等のアルカリ金属塩化物が好ましく、特に塩化ナトリウムが好ましい。
α−スルホ脂肪酸エステル塩組成物に添加するときの無機塩化物塩の形態は、粉末、フレーク等の固体、水等の溶媒に溶解させた溶液のいずれでもよい。
本発明の界面活性剤組成物の調製方法に特に制限はなく、目的の組成物が得られる方法であれば、いかなる方法も採用することができる。α−スルホ脂肪酸エステル塩と無機塩化物塩の混合割合は、〔α−スルホ脂肪酸エステル塩：無機塩化物塩〕の質量比が９９：１〜９０：１０になるように、適宜選定される。
α−スルホ脂肪酸エステル塩を製造する際に無機塩化物塩が副生する場合には、α−スルホ脂肪酸エステル塩と無機塩化物塩の混合割合は、副生する無機塩化物塩の量を考慮にいれて調整される。
As the inorganic chloride salt used in the present invention, alkali metal chlorides such as sodium chloride, potassium chloride and lithium chloride are preferable, and sodium chloride is particularly preferable.
The form of the inorganic chloride salt when added to the α-sulfo fatty acid ester salt composition may be a powder, a solid such as flake, or a solution dissolved in a solvent such as water.
There is no restriction | limiting in particular in the preparation method of surfactant composition of this invention, What kind of method can be employ | adopted if it is a method by which the target composition is obtained. The mixing ratio of the α-sulfo fatty acid ester salt and the inorganic chloride salt is appropriately selected so that the mass ratio of [α-sulfo fatty acid ester salt: inorganic chloride salt] is 99: 1 to 90:10.
When an inorganic chloride salt is by-produced when producing an α-sulfo fatty acid ester salt, the mixing ratio of the α-sulfo fatty acid ester salt and the inorganic chloride salt takes into account the amount of the inorganic chloride salt by-produced. To adjust.
本発明のアニオン界面活性剤組成物は、洗浄剤組成物の成分として好適に使用することができる。この場合、該洗浄剤組成物には、必要に応じて色素、香料、可溶化剤、ビルダー等の補助剤を適宜加えることができる。更に、洗浄力や泡立ちを調整する目的で、α−スルホ脂肪酸エステル塩以外のアニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、ノニオン界面活性剤等を添加することができる。
本発明の界面活性剤組成物は、例えば、食器用洗剤、シャンプー、衣料用洗剤等に好適に用いることができる。
The anionic surfactant composition of the present invention can be suitably used as a component of a cleaning composition. In this case, auxiliary agents such as pigments, fragrances, solubilizers, and builders can be appropriately added to the cleaning composition as necessary. Furthermore, an anionic surfactant other than an α-sulfo fatty acid ester salt, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like can be added for the purpose of adjusting detergency and foaming.
The surfactant composition of the present invention can be suitably used for, for example, tableware detergents, shampoos, clothing detergents and the like.
以下の実施例及び比較例において、目的とするα−スルホ脂肪酸エステル塩の含有量は高速液体クロマトグラフを用いて測定し、無機塩化物塩の含有量はイオンクロマトグラフによる塩化物イオン濃度の測定により算出した。高速液体クロマトグラフ及びイオンクロマトグラフの条件は下記のとおりである。
（１）高速液体クロマトグラフ
装置：ＨＬＣ−８２２０ＧＰＣ（東ソー株式会社製）
カラム：ＴＳＫｇｅｌ ＯＤＳ−８０Ｔｓ（４．６ｍｍＩ．Ｄ．×７５ｍｍ）（東ソー株式会社製）
移動相：メタノール／水（容量比）＝８０／２０、０．２５Ｍ過塩素酸ナトリウム、０．１（ｗ／ｖ％）リン酸
流速：１．０ｍｌ／分
カラム温度：４０℃
（２）イオンクロマトグラフ
装置：ＩＣＳ−９０（ＤＩＯＮＥＸ社製）
カラム：ＩｏｎＰａｃ ＡＳ１６ （ＤＩＯＮＥＸ社製）
移動相：０．０３Ｍ水酸化ナトリウム水溶液
流速：１．５ｍｌ／分
カラム温度：３５℃
In the following Examples and Comparative Examples, the target α-sulfo fatty acid ester salt content is measured using a high performance liquid chromatograph, and the inorganic chloride salt content is measured by measuring the chloride ion concentration by ion chromatography. Calculated by The conditions of the high performance liquid chromatograph and ion chromatograph are as follows.
(1) High performance liquid chromatograph apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel ODS-80Ts (4.6 mm ID × 75 mm) (manufactured by Tosoh Corporation)
Mobile phase: methanol / water (volume ratio) = 80/20, 0.25 M sodium perchlorate, 0.1 (w / v%) phosphoric acid Flow rate: 1.0 ml / min Column temperature: 40 ° C.
(2) Ion chromatograph device: ICS-90 (manufactured by DIONEX)
Column: IonPac AS16 (manufactured by DIONEX)
Mobile phase: 0.03 M aqueous sodium hydroxide flow rate: 1.5 ml / min Column temperature: 35 ° C.
実施例１〜３
薄膜式反応器を用いて、パルミチン酸メチルにＳＯ3ガスを接触させ、反応モル比（ＳＯ3／パルミチン酸メチル）＝１．２の条件でスルホン化した。得られたスルホン化物を４つ口フラスコに仕込み、８０℃で６０分間加熱熟成を行い、スルホン化物に対して５質量％のメタノールを滴下し、更に８０℃で６０分間加熱熟成を行って、α−スルホパルミチン酸メチルエステルを得た。
このα―スルホパルミチン酸メチルエステルを水酸化ナトリウム水溶液中に投入し、ｐＨ６．８になるように中和を行い、α−スルホパルミチン酸メチルエステル塩水溶液（α―スルホパルミチン酸メチルエステル塩含量：９．３質量％）を得た。
得られたα―スルホパルミチン酸メチルエステル塩水溶液に塩化ナトリウムを加え、ロータリーエバポレーターと凍結乾燥機を用いて濃縮、あるいは水で希釈し、遠心分離器（株式会社久保田製作所製、ＫＵＢＯＴＡ ２０１０）で気泡の除去処理を施し、各濃度のα−スルホパルミチン酸メチルエステル塩水溶液を得た。
ＶＡＲ−５０ビスコアナライザー（ＲＥＯＬＯＧＩＣＡ Ｉｎｓｔｒｕｍｅｎｔｓ ＡＢ製）のローターにコーン角４°、直径４０ｍｍのコーンプレートを取り付けて、５０℃で各水溶液の粘度を測定した。結果を表１に示す。
Examples 1-3
Using a thin-film reactor, SO 3 gas was brought into contact with methyl palmitate and sulfonated under the condition of a reaction molar ratio (SO 3 / methyl palmitate) = 1.2. The obtained sulfonated product was charged into a four-necked flask and subjected to heat aging at 80 ° C. for 60 minutes, 5% by mass of methanol was added dropwise to the sulfonated product, and further subjected to heat aging at 80 ° C. for 60 minutes to obtain α -Sulfopalmitic acid methyl ester was obtained.
This α-sulfopalmitic acid methyl ester is put into an aqueous sodium hydroxide solution, neutralized to pH 6.8, and an α-sulfopalmitic acid methyl ester salt aqueous solution (α-sulfopalmitic acid methyl ester salt content: 9.3 mass%) was obtained.
Sodium chloride is added to the obtained α-sulfopalmitic acid methyl ester salt aqueous solution, concentrated using a rotary evaporator and a freeze dryer, or diluted with water, and air bubbles are generated using a centrifuge (KUBOTA 2010, manufactured by Kubota Corporation). The α-sulfopalmitic acid methyl ester salt aqueous solution with each concentration was obtained.
A cone plate having a cone angle of 4 ° and a diameter of 40 mm was attached to the rotor of a VAR-50 Visco Analyzer (manufactured by REOLOGICA Instruments AB), and the viscosity of each aqueous solution was measured at 50 ° C. The results are shown in Table 1.
比較例１〜３
塩化ナトリウムを加えない他は実施例１〜３と同様に行った。結果を表１に示す。
Comparative Examples 1-3
Except not adding sodium chloride, it carried out similarly to Examples 1-3. The results are shown in Table 1.
表１から、塩化ナトリウムを含むα−スルホパルミチン酸メチルエステル塩等のα−スルホ脂肪酸エステル塩組成物は、α−スルホ脂肪酸エステル塩を４０質量％以上という高濃度に含有していても粘度が低く、流動性に優れていることが分かる。 From Table 1, α-sulfo fatty acid ester salt composition such as α-sulfo palmitic acid methyl ester salt containing sodium chloride has a viscosity even if it contains α-sulfo fatty acid ester salt at a high concentration of 40% by mass or more. It can be seen that it is low and has excellent fluidity.
実施例４
実施例１で得られたα−スルホパルミチン酸メチルエステル塩組成物を乾燥させて得た粉末（α−スルホパルミチン酸メチルエステル塩含有量：８０．０質量％、塩化ナトリウム含有量：３．０質量％、α−スルホパルミチン酸ナトリウム塩含有量：１．１質量％、硫酸ナトリウム含有量：０．６質量％）を用いて、希釈性及び溶解性を調べた。具体的には、この粉末１．２５ｇを３０ｍＬビーカーに採り、７０℃に加熱した水浴でビーカーを加熱し、ビーカー中の粉末を融解させた。
次いで、氷浴中でビーカーを冷却し、融解液を凝固させ、氷浴中で冷却した蒸留水８．７８ｇをビーカー中に加えた。氷浴中で５分間静置した後、ビーカーを５０℃水浴中に移し、マグネティックスターラー（三田村理研工業株式会社製、ＣＯＮＳＴＡＮＴ ＴＯＲＱＵＥ ＭＡＧＭＩＸ ＳＴＩＲＲＥＲ、回転子寸法：長さ１５ｍｍ、直径５ｍｍ、回転数：２００ｒｐｍ）を用いて撹拌した。撹拌開始後、２０分間で凝固物は完全に溶解した。このことから、塩化ナトリウムを含む本発明のα−スルホ脂肪酸エステル塩組成物は、希釈性、溶解性が良好で、ハンドリング性に優れていることが分かる。
Example 4
Powder obtained by drying the α-sulfopalmitic acid methyl ester salt composition obtained in Example 1 (α-sulfopalmitic acid methyl ester salt content: 80.0% by mass, sodium chloride content: 3.0 Dilutability and solubility were examined using a mass%, α-sulfopalmitic acid sodium salt content: 1.1 mass%, sodium sulfate content: 0.6 mass%). Specifically, 1.25 g of this powder was taken in a 30 mL beaker, and the beaker was heated in a water bath heated to 70 ° C. to melt the powder in the beaker.
The beaker was then cooled in an ice bath to solidify the melt and 8.78 g of distilled water cooled in an ice bath was added into the beaker. After standing for 5 minutes in an ice bath, the beaker was transferred to a 50 ° C. water bath, and a magnetic stirrer (manufactured by Mitamura Riken Kogyo Co., Ltd. CONSTANT TORQUE MAGMIX STIRERR, rotor dimensions: length 15 mm, diameter 5 mm, rotation speed: 200 rpm) ). The coagulum completely dissolved in 20 minutes after the start of stirring. From this, it can be seen that the α-sulfo fatty acid ester salt composition of the present invention containing sodium chloride has good dilutability and solubility and excellent handling properties.
比較例４
比較例１で得られたα−スルホパルミチン酸メチルエステル塩組成物を乾燥させて得た粉末（α−スルホパルミチン酸メチルエステル塩含有量：７８．５質量％、塩化ナトリウム含有量：０．０質量％、α−スルホパルミチン酸ナトリウム塩含有量：１．４質量％、硫酸ナトリウム含有量：０．７質量％）１．２７ｇを３０ｍＬビーカーに採り、７０℃に加熱した水浴でビーカーを加熱し、ビーカー中の粉末を融解させた。
次いで、氷浴中でビーカーを冷却し、融解液を凝固させ、氷浴中で冷却した蒸留水８．７４ｇをビーカー中に加えた。氷浴中で５分間静置した後、ビーカーを５０℃水浴中に移し、前記マグネティックスターラーを用いて撹拌した。撹拌開始後、２０分間で撹拌を止めたところ、液晶が器壁に付着していたことから、塩化ナトリウムを含まないα−スルホ脂肪酸エステル塩組成物（比較例４）は、希釈性・溶解性が悪く、ハンドリング性が悪いことが分った。なお、上澄みを速やかに採取し、ディスポーザブルメンブレンフィルター（ＡＤＶＡＮＴＥＣ社製、１３ＨＰ０２０ＡＮ）にてろ過したろ液のα−スルホパルミチン酸メチルエステル塩の濃度を測定し、溶解率を算出した結果、８５．４％であった。
Comparative Example 4
Powder obtained by drying the α-sulfopalmitic acid methyl ester salt composition obtained in Comparative Example 1 (α-sulfopalmitic acid methyl ester salt content: 78.5% by mass, sodium chloride content: 0.0 (Mass%, sodium α-sulfopalmitate content: 1.4 mass%, sodium sulfate content: 0.7 mass%) 1.27 g was taken in a 30 mL beaker and heated in a water bath heated to 70 ° C. The powder in the beaker was melted.
The beaker was then cooled in an ice bath to solidify the melt and 8.74 g of distilled water cooled in an ice bath was added into the beaker. After allowing to stand in an ice bath for 5 minutes, the beaker was transferred to a 50 ° C. water bath and stirred using the magnetic stirrer. When stirring was stopped for 20 minutes after the start of stirring, the liquid crystal was adhered to the vessel wall, so that the α-sulfo fatty acid ester salt composition containing no sodium chloride (Comparative Example 4) was dilutable and soluble. However, it was found that handling was poor. The supernatant was collected immediately, the concentration of α-sulfopalmitic acid methyl ester salt in the filtrate filtered through a disposable membrane filter (manufactured by ADVANTEC, 13HP020AN), and the dissolution rate was calculated. %Met.
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