JPH0311809B2 - - Google Patents
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- Publication number
- JPH0311809B2 JPH0311809B2 JP59265978A JP26597884A JPH0311809B2 JP H0311809 B2 JPH0311809 B2 JP H0311809B2 JP 59265978 A JP59265978 A JP 59265978A JP 26597884 A JP26597884 A JP 26597884A JP H0311809 B2 JPH0311809 B2 JP H0311809B2
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- Japan
- Prior art keywords
- acid
- added
- product
- ethylene oxide
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔技術分野〕 本発明は、新規な乳化剤に関するものである。[Detailed description of the invention] 〔Technical field〕 The present invention relates to a novel emulsifier.
従来、医薬分野や化粧料の分野においては、一
方の液体をこれとは相溶しない他の液体中に微粒
子状で分散させるために乳化剤が使用されてい
る。これらの乳化剤のうち、特に高級脂肪酸のカ
ルボキシル基にエチレンオキサイドを付加させて
得られるポリエチレングリコール高級脂肪酸エス
テルは、低毒性で低刺激性の乳化剤として広く用
いられている。
Conventionally, in the fields of medicine and cosmetics, emulsifiers have been used to disperse one liquid in the form of fine particles in another liquid that is not compatible with the other liquid. Among these emulsifiers, polyethylene glycol higher fatty acid esters, which are obtained by adding ethylene oxide to the carboxyl group of higher fatty acids, are particularly widely used as low-toxic and non-irritating emulsifiers.
しかしながら、このような従来の高級脂肪酸系
非イオン乳化剤は、乳化剤としてすぐれている反
面、安全性の問題もあり、またその乳化系は安定
性に欠けるものであつた。 However, although such conventional higher fatty acid-based nonionic emulsifiers are excellent as emulsifiers, they also have safety problems, and their emulsification systems lack stability.
本発明は、このような従来の高級脂肪酸系非イ
オン乳化剤に見られる諸欠点の克服された乳化剤
を提供することを目的とする。
An object of the present invention is to provide an emulsifier that overcomes the various drawbacks found in conventional higher fatty acid-based nonionic emulsifiers.
本発明によれば、下記一般式（）で表わされ
る乳化剤が提供される。
According to the present invention, an emulsifier represented by the following general formula () is provided.
一般式（）
（式中、Y1及びY2はポリオキシアルキレン基、
Y3はポリオキシアルキレン基又はアルキルアミ
ノ基を表わす）
前記において示したポリオキシアルキレン基
は、エテレンオキシドやプロピレンオキシド等の
アルキレンオキシド又はアルキレンクロルヒドリ
ンや、塩化エチレンを単独又は複数組合せて付加
重合させて得られるもので、その付加モル数は、
通常１〜50、好ましくは10〜30である。アルキル
アミノ基は、通常、炭素数１〜22の直鎖又は分枝
鎖状アルキル基を１個又は２個有するアミノ基で
ある。 General formula () (In the formula, Y 1 and Y 2 are polyoxyalkylene groups,
( Y3 represents a polyoxyalkylene group or an alkylamino group) The polyoxyalkylene group shown above can be added with alkylene oxide such as ethylene oxide or propylene oxide, alkylene chlorohydrin, or ethylene chloride alone or in combination. It is obtained by polymerization, and the number of moles added is:
Usually 1-50, preferably 10-30. The alkylamino group is usually an amino group having one or two straight or branched alkyl groups having 1 to 22 carbon atoms.
本発明の乳化剤は、スピクリスポール酸（Ｓ−
酸）（４，５−ジカルボキシ−４−ペンタデカノ
リド）のラクトン環の開環によるオープンリング
酸（Ｏ−酸）（３−ヒドロキシ−１，３，４−テ
トラデカントリカルボン酸、前記一般式におい
て、Y1，Y2及びY3はいずれもOHである）又は
そのＮ−アルキルカルバモイル誘導体（１−Ｎ−
アルキルカルバモイル−３−ヒドロキシ−３，４
−テトラデカンジカルボン酸、前記一般式におい
て、Y1及びY2はOHであり、Y3はアルキルアミ
ノ基である）の中から選ばれる少なくとも１種を
原料とし、これにアルキレンオキシドやアルキレ
ンクロルヒドリン等のポリオキシアルキレン基導
入剤を付加重合させることによつて、あるいはア
ルキレングリコールやポリアルキレングリコール
等のポリオキシアルキレン基導入剤を反応させる
ことによつて得ることができる。 The emulsifier of the present invention is spicrisporic acid (S-
acid) (4,5-dicarboxy-4-pentadecanolide) by opening the lactone ring of the ring acid (O-acid) (3-hydroxy-1,3,4-tetradecanetricarboxylic acid, in the general formula, Y 1 , Y 2 and Y 3 are all OH) or its N-alkylcarbamoyl derivative (1-N-
Alkylcarbamoyl-3-hydroxy-3,4
-tetradecanedicarboxylic acid, in the above general formula, Y 1 and Y 2 are OH and Y 3 is an alkylamino group) is used as a raw material, and alkylene oxide or alkylene chlorohydrin is added to this as a raw material. It can be obtained by addition polymerization of a polyoxyalkylene group-introducing agent such as, or by reacting a polyoxyalkylene group-introducing agent such as alkylene glycol or polyalkylene glycol.
本発明で原料として用いられるオープンリング
酸はスピクリスポール酸から誘導される。このス
ピクリスポール酸は、ブドウ糖を原料として、微
生物工業プロセスにより、Penicillum
spiculisporumの代謝産物として高収率で大量に
生産されるもので、安全性が高く、生分解性の高
いものである。このものは、通常、培養法によれ
ば、100％の構造選択率で得られ、このものは、
C10のアルキル基、ラクトン環及び二つのカルボ
キシル基をもつとともに、光学活性を有し、水に
不溶の結晶である。はじめ、培養液中では三塩基
酸であるそのオープンリング酸であるが、このも
のは、加熱によりカルボキシル基の一個が内部エ
ステルを形成してγ−ラクトン環もをつ二塩基酸
（Ｓ−酸）に変換される。このＳ−酸に過剰の水
酸化ナトリウム水溶液を加えて加熱した後、塩酸
にて中和し、エチルエーテル可溶物を抽出するこ
とによりオープンリング酸（Ｏ−酸）が得られ
る。 The open ring acid used as a raw material in the present invention is derived from spicrysporic acid. This spicrysporic acid is produced from Penicillum by microbial industrial process using glucose as raw material.
It is produced in large quantities at high yields as a metabolite of spiculisporum, and is highly safe and highly biodegradable. This product is usually obtained with 100% structural selectivity by culture method, and this product is
It has a C10 alkyl group, a lactone ring, and two carboxyl groups, has optical activity, and is a water-insoluble crystal. Initially, the open ring acid is a tribasic acid in the culture solution, but when heated, one of the carboxyl groups forms an internal ester, resulting in a dibasic acid (S-acid) that also has a γ-lactone ring. ) is converted to An open ring acid (O-acid) is obtained by adding an excess aqueous sodium hydroxide solution to this S-acid, heating it, neutralizing it with hydrochloric acid, and extracting the ethyl ether-soluble material.
本発明の乳化剤は、一方の液体にこれを相溶し
ない他方の液体を微粒子状に分散させてエマルジ
ヨンを形成させる乳化能にすぐれるとともに、本
発明の乳化剤は、生体に係わる製品（医薬、香粧
品等）に好適に用いられる。
The emulsifying agent of the present invention has an excellent emulsifying ability to form an emulsion by dispersing one liquid in the form of fine particles of another liquid that is not compatible with the other liquid. (cosmetics, etc.).
本発明の乳化剤は、水溶液、含水有機溶剤溶液
及び有機溶剤溶液の形で使用され、その使用濃度
は、通常、0.01〜3.0重量％であり、好ましくは
0.1〜1.5重量％である。 The emulsifier of the present invention is used in the form of an aqueous solution, a water-containing organic solvent solution, and an organic solvent solution, and the concentration used is usually 0.01 to 3.0% by weight, preferably
It is 0.1-1.5% by weight.
本発明の乳化剤の特微は次の通りである。 The features of the emulsifier of the present invention are as follows.
(1) 乳化効果がすぐれている。(1) Excellent emulsifying effect.
(2) 乳化系の安定性がよい（数週間〜数ケ月間以
上安定性が持続）。(2) The stability of the emulsion system is good (stability lasts for several weeks to several months).
(3) 水、油及び含水有機溶剤のいずれに対しても
相溶性がよいものが得られるので使用範囲が極
めて広い。(3) It can be used in a very wide range of applications because it has good compatibility with water, oil, and water-containing organic solvents.
(4) 分散質や被乳化油及び被可溶化油が数種混合
されていても安定効果を発揮できる。(4) A stabilizing effect can be achieved even when several kinds of dispersoids, emulsified oils, and solubilized oils are mixed.
(5) 低濃度で効果を示すので経済的である。(5) It is economical because it is effective at low concentrations.
(6) 低毒性かつ低刺激性であり、広範囲に使用可
能である。(6) It has low toxicity and low irritation, and can be used over a wide range of areas.
次に本発明を実施例によりさらに詳細に説明す
る。
Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
３−ヒドロキシ−１，３，４−テトラデカント
リカルボン酸（オープンリング酸）5.0gをジメチ
ルスルホキシド（DMSO）を含むキシレン100ml
中に溶解し、ガラス製の目盛付反応管に入れ、予
じめ重量を秤量した。次に、この反応管に水酸化
カリウム0.1gを加え、反応管をオイルバスに浸漬
し、温度120〜130℃に加熱し、水酸化カリウムを
溶解させた。反応管下部に挿入したガラス管より
窒素ガスを通じながら、乾燥したエチレンオキシ
ドガスを反応管の下部に挿入したガラス管より導
入して、常圧下でエチレンオキシドの付加反応を
行つた。反応終了後、反応管の重量を測定して、
エチレンオキシドの吹込みよる重量増加を確認し
た。Example 1 5.0 g of 3-hydroxy-1,3,4-tetradecanetricarboxylic acid (open ring acid) was added to 100 ml of xylene containing dimethyl sulfoxide (DMSO).
The mixture was dissolved in a glass tube, placed in a graduated glass reaction tube, and weighed in advance. Next, 0.1 g of potassium hydroxide was added to this reaction tube, and the reaction tube was immersed in an oil bath and heated to a temperature of 120 to 130°C to dissolve the potassium hydroxide. Dry ethylene oxide gas was introduced through the glass tube inserted at the bottom of the reaction tube while nitrogen gas was passed through the glass tube inserted at the bottom of the reaction tube, and an addition reaction of ethylene oxide was carried out under normal pressure. After the reaction is complete, measure the weight of the reaction tube and
It was confirmed that the weight increased due to the injection of ethylene oxide.
次に、前記で得られた反応生成物に希塩酸を加
えて中和し、溶媒を蒸発して除き、減圧下、50℃
で十分乾燥し、さらに得られた乾燥物を高真空下
（0.04mmHg）120〜130℃に加熱して、副生したポ
リエチレングリコールを除去し、製品14.6gを得
た。得られた製品は、これを赤外吸収分析した。
その結果、オープンリング酸に見られたカルボキ
シル基の吸収（吸収ピークの先端が1742cm〓1と
1697cm〓1の２つに割れたカルボキシル基の強い
吸収）が消失し、それに代つてポリエチレングリ
コールとのエステル結合に基づく1725cm〓1の吸
収が現われ、オープリング酸に含まれる３個のカ
ルボキシル基はいずれもポリオキシエチレン基と
結合していることが確認された。また、エチレン
オキシド付加モル数（オープンリング酸に導入さ
れたエチレンオキシドの全付加モル数）をＨ−
NMR法により測定したところ、15.3モルである
ことが確認された。 Next, the reaction product obtained above was neutralized by adding dilute hydrochloric acid, the solvent was removed by evaporation, and the mixture was heated at 50°C under reduced pressure.
The dried product was further heated under high vacuum (0.04 mmHg) to 120 to 130°C to remove by-produced polyethylene glycol, yielding 14.6 g of a product. The obtained product was subjected to infrared absorption analysis.
As a result, the absorption of the carboxyl group observed in the open ring acid (the tip of the absorption peak was 1742 cm〓 1)
The strong absorption of the carboxyl group split into two at 1697cm〓 1 disappears, and in its place the absorption at 1725cm〓 1 based on the ester bond with polyethylene glycol appears, and the three carboxyl groups contained in the opening acid It was confirmed that both were bonded to polyoxyethylene groups. In addition, the number of moles of ethylene oxide added (the total number of moles of ethylene oxide introduced into the open ring acid) is
When measured by NMR method, it was confirmed to be 15.3 mol.
前記で得られた本発明の乳化剤は、水、エタノ
ール、ベンジルアルコール、ヘキサン、アセトン
等の多くの溶剤によく溶解した。また、その0.1
％水溶液の比表面張力は0.58であり、さらに、常
温でケロシンや綿実油に対して優れた乳化作用と
乳化安定化作用を示した。即ち、30mlの目盛は試
験管にこの0.1％水溶液３mlとケロシン７mlを加
え、水平に振りまぜ（５分間、400回、振幅４cm）
た後、試験管立に立てた30℃に静置したが、よく
乳化し、乳化系は全く安定であり、２ケ月後も安
定であつた。これに対して、硫酸ドデシルナトリ
ウムの１％水溶液３mlとケロシン２mlによる乳化
系は24時間後に2.6mlの水相が分離し、不安定で
あつた。 The emulsifier of the present invention obtained above was well dissolved in many solvents such as water, ethanol, benzyl alcohol, hexane, and acetone. Also, that 0.1
The specific surface tension of the % aqueous solution was 0.58, and it also exhibited excellent emulsifying and emulsion stabilizing effects on kerosene and cottonseed oil at room temperature. That is, for the 30ml scale, add 3ml of this 0.1% aqueous solution and 7ml of kerosene to a test tube, and shake horizontally (5 minutes, 400 times, amplitude 4cm).
After that, the mixture was placed in a test tube stand and allowed to stand at 30°C, but it was well emulsified and the emulsion system was completely stable and remained stable even after 2 months. On the other hand, an emulsion system using 3 ml of a 1% aqueous solution of sodium dodecyl sulfate and 2 ml of kerosene was unstable, with 2.6 ml of the aqueous phase separating after 24 hours.
実施例 ２
オープンリング酸6.0g（0.01731モル）を500ml
容スリ付ナス形フラスコに入れ、脱水したテトラ
ヒドロフラン（THF）200mlを加え、マグネチツ
クスターラーで撹拌して溶解させた。フラスコに
（スリ付）滴下漏斗をつなぎ、等モルのオキザリ
ルクロリド2.2gにTHF100mlを加えた溶液を滴下
漏斗から３時間かけて室温（約25℃）で滴下し
た。滴下終了後、40℃に加熱して約１時間撹拌を
続けた。この後、一旦THFを蒸発させて除き、
残分をベンゼンとヘキサンの混液で洗い、再び
THFを加え、撹拌しながら滴下ロートよりドデ
シルアミン3.21g（0.01731モル）のTHF溶液を室
温で２時間かけてゆつくり滴下した。滴下終了
後、40℃に加温して約１時間撹拌を続けた。反応
生成物はエタノール２部とエチルエーテル１部と
の混合溶媒から再結晶した。白色粉末4.6gを得
た。赤外吸収スペクトルでは、1645と1555cm〓1
にアミドの吸収、1720と1755cm〓1の二つに割れ
たカルボキシル基の吸収、2908，1460及び1378cm
〓1に炭化水素鎖に基づく吸収が見られた。これ
らのことより、この製品は一般式において、Y3
がドデシルアミノ基、Y1及びY2がOH基である
ものと判定される。Example 2 500ml of open ring acid 6.0g (0.01731mol)
The mixture was placed in an eggplant-shaped flask with a slot, and 200 ml of dehydrated tetrahydrofuran (THF) was added thereto, and the mixture was stirred with a magnetic stirrer to dissolve. A dropping funnel (with slots) was connected to the flask, and a solution of 2.2 g of equimolar oxalyl chloride and 100 ml of THF was added dropwise from the dropping funnel over 3 hours at room temperature (approximately 25°C). After the dropwise addition was completed, the mixture was heated to 40°C and stirred for about 1 hour. After this, once THF is evaporated and removed,
Wash the residue with a mixture of benzene and hexane, and then rinse again.
THF was added, and while stirring, a THF solution of 3.21 g (0.01731 mol) of dodecylamine was slowly added dropwise from the dropping funnel at room temperature over 2 hours. After the dropwise addition was completed, the mixture was heated to 40°C and stirred for about 1 hour. The reaction product was recrystallized from a mixed solvent of 2 parts of ethanol and 1 part of ethyl ether. 4.6g of white powder was obtained. In the infrared absorption spectrum, 1645 and 1555 cm〓 1
Absorption of amide, 1720 and 1755cm〓 Absorption of carboxyl group split into two , 2908, 1460 and 1378cm
〓 Absorption based on hydrocarbon chains was observed in 1 . Based on these facts, this product has a general formula of Y 3
is determined to be a dodecylamino group, and Y 1 and Y 2 are OH groups.
元素分析の実測値はＣ（％）67.17（計算値
67.93），Ｈ（％）11.17（10.81），Ｎ（％）2.93（2.7
3）
であつた。旋光度は［α］＝−16.8（Ｃ＝0.803g／
dl，EtOH）であつた。このものは、水に不溶で
あり、メタノールとクロロホルムに易溶でベンゼ
ンとアセトンに難溶、ヘキサンに不溶であつた。 The actual value of elemental analysis is C (%) 67.17 (calculated value
67.93), H (%) 11.17 (10.81), N (%) 2.93 (2.7
3)
It was hot. The optical rotation is [α] = -16.8 (C = 0.803g/
dl, EtOH). This product was insoluble in water, easily soluble in methanol and chloroform, sparingly soluble in benzene and acetone, and insoluble in hexane.
つぎに、前記で得た製品に対してエチレンオキ
シド付加体の合成を行つた。即ち、上記のように
して合成した二鎖アルキル型誘導体〔１−（Ｎ−
ドデシルカルバモイル）−３−ヒドロキシ−３，
４−テトラデカンジカルボン酸〕4.0gを、DMSO
を含むキシレン100mlに溶解し、金属ナトリウム
0.1gを加え、実施例１と同様にしてエチレンオキ
シドを吹き込んだ。これより、前記一般式におけ
るY1及びY2がポリオキシアルキレン基で、Y3が
アルキルアミノ基である生成物が得られた。エチ
レンオキシド付加モル数は10.6モルであつた。こ
のものは、エタノール、アセトン、ヘキサン、ベ
ンジルアルコールなどに可溶であり、水に難溶で
あつた。ベルガモツト油などの精油やラノリンな
どに対しても相溶性を示した。 Next, an ethylene oxide adduct was synthesized using the product obtained above. That is, the two-chain alkyl type derivative [1-(N-
dodecylcarbamoyl)-3-hydroxy-3,
4.0g of 4-tetradecanedicarboxylic acid in DMSO
Sodium metal dissolved in 100ml of xylene containing
0.1 g was added and ethylene oxide was blown in the same manner as in Example 1. As a result, a product was obtained in which Y 1 and Y 2 in the general formula are polyoxyalkylene groups and Y 3 is an alkylamino group. The number of moles of ethylene oxide added was 10.6 moles. This product was soluble in ethanol, acetone, hexane, benzyl alcohol, etc., and sparingly soluble in water. It also showed compatibility with essential oils such as bergamot oil and lanolin.
Claims (1)
Y3はポリオキシアルキレン基又はアルキルアミ
ノ基を示す。） で表わされる乳化剤。[Claims] 1. General formula (In the formula, Y 1 and Y 2 are polyoxyalkylene groups,
Y 3 represents a polyoxyalkylene group or an alkylamino group. ) An emulsifier represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59265978A JPS61146330A (en) | 1984-12-17 | 1984-12-17 | Polybasic acid polyoxyalkylene glycol ester type surface active agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59265978A JPS61146330A (en) | 1984-12-17 | 1984-12-17 | Polybasic acid polyoxyalkylene glycol ester type surface active agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61146330A JPS61146330A (en) | 1986-07-04 |
| JPH0311809B2 true JPH0311809B2 (en) | 1991-02-18 |
Family
ID=17424665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59265978A Granted JPS61146330A (en) | 1984-12-17 | 1984-12-17 | Polybasic acid polyoxyalkylene glycol ester type surface active agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61146330A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2753524B2 (en) * | 1987-06-11 | 1998-05-20 | セイコープレシジョン株式会社 | Video printer |
| JP2017025149A (en) * | 2015-07-17 | 2017-02-02 | 三洋化成工業株式会社 | Non-ionic surfactant and method of producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5829130A (en) * | 1981-08-15 | 1983-02-21 | Hitachi Maxell Ltd | Magnetic recording medium |
| JPS58216729A (en) * | 1982-06-11 | 1983-12-16 | Nippon Shokubai Kagaku Kogyo Co Ltd | Dispersing agent for use in coal-water slurry |
-
1984
- 1984-12-17 JP JP59265978A patent/JPS61146330A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61146330A (en) | 1986-07-04 |
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