JP2007091852A - Manufacturing process of polyoxyethylene polyhydric alcohol fatty acid ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing process of polyoxyethylene polyhydric alcohol fatty acid ester which is less bitter and smelly than conventional ones. <P>SOLUTION: The manufacturing process comprises treating an esterified product of a polyhydric alcohol and a fatty acid with 0.1-10 wt.% of a synthetic adsorbent containing a mixed metal oxide consisting of 50-90 wt.% of a magnesium oxide component and 10-50 wt.% of an aluminum oxide component and having a drying loss of ≤1.5 wt.% in the presence of 1-300 wt.% of water, adding ethylene oxide to the refined esterified product of the polyhydric alcohol and the fatty acid by an addition reaction to obtain its ethylene oxide derivative and treating the ethylene oxide derivative obtained with 0.1-10 wt.% of a synthetic adsorbent containing a mixed metal oxide consisting of 50-90 wt.% of a magnesium oxide component and 10-50 wt.% of an aluminum oxide component and having a drying loss of ≤1.5 wt.% in the presence of 1-300 wt.% of water. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polyoxyethylene polyhydric alcohol fatty acid ester.

Derivatives obtained by adding ethylene oxide to esterified products of polyhydric alcohols and fatty acids are used as surfactants in various applications. Among them, polyoxyethylene sorbitan fatty acid ester obtained by adding ethylene oxide to sorbitan fatty acid ester, which is a partial ester of sorbitol or sorbitan and fatty acid, is a nonionic surfactant as an emulsifying agent, dispersibility, wettability, foaming. It is known to have excellent properties such as anti-foaming properties and antifoaming properties, and is used as an emulsifier, solubilizer, dispersant, additive, etc. in a wide range of applications such as cosmetics, lubricants, synthetic resins, and detergents. Yes.
Among polyoxyethylene sorbitan fatty acid esters, polysorbate 80 is a substance described in the Japanese Pharmacopoeia and polysorbate 20, 40, 60, 65 is a substance described in a pharmaceutical additive standard, and is generally widely used as a pharmaceutical additive. in use. Furthermore, these polysorbates have been approved and used as food additives in Europe and the United States, and preparations for approval as food additives are in progress soon in Japan. Thus, the polyoxyethylene sorbitan fatty acid ester is used in a very wide field.
However, as the physical properties of polyoxyethylene sorbitan fatty acid ester, for example, the properties of polysorbate 40, 60, 65 in the Japanese Pharmaceutical Additives Standard and polysorbate 80 in the Japanese Pharmacopoeia are “taste is slightly bitter and has a slightly unique smell. It is a substance that can feel bitterness, oxidative odor, and deteriorated odor, as described in "Yes".
This bitterness and odor is used when used as a food additive in Europe, the United States, etc., and when used as a food additive in Japan, where approval of the food additive is planned soon, or for toothpaste, washing and washing. In applications such as oral cosmetics such as mouth preparations, lip cosmetics such as lipsticks and lip balms, addition of this may be very disadvantageous.
As a production method for improving the bitterness and odor of polyoxyethylene sorbitan fatty acid ester, a method of performing steam treatment or distillation treatment or a method of treatment with an adsorbent has been reported, but pharmaceuticals, quasi drugs, cosmetics, In applications that are intended to be included in the mouth of food or the like, the actual situation is that bitterness and odor are not sufficiently satisfactory, and further development has been awaited. (Patent Document 1, Patent Document 2, Patent Document 3)

JP 2002-194074 A JP 2003-96182 A JP 2005-23227 A

  The subject of this invention is providing the manufacturing method of the polyoxyethylene polyhydric-alcohol fatty acid ester which suppressed bitterness and smell.

That is, the present invention is as follows.
(1) Oxidation product of polyhydric alcohol and fatty acid in the presence of 1 to 300% by weight of water, composite metal oxidation comprising 50 to 90% by weight of magnesium oxide component and 10 to 50% by weight of aluminum oxide component An ethylene oxide derivative obtained by adding an ethylene oxide to an esterified product of a polyhydric alcohol and a fatty acid treated with a synthetic adsorbent having a weight loss of 1.5% by weight or less. After getting
In the presence of 1 to 300% by weight of water, the obtained ethylene oxide derivative contains a composite metal oxide comprising a magnesium oxide component of 50 to 90% by weight and an aluminum oxide component of 10 to 50% by weight. A process for producing a polyoxyethylene polyhydric alcohol fatty acid ester, characterized by treatment with 0.1 to 10% by weight of a synthetic adsorbent that is 1.5% by weight or less.
(2) The production method as described above, wherein the polyoxyethylene polyhydric alcohol fatty acid ester is a polyoxyethylene sorbitan fatty acid ester.

  The polyoxyethylene polyhydric alcohol fatty acid ester obtained by the production method of the present invention has extremely low bitterness and odor, and can be optimally used in the fields of pharmaceuticals, quasi drugs, cosmetics, foods and the like.

The esterified product of a polyhydric alcohol and a fatty acid in the present invention is a product obtained by esterifying a hydroxyl group of a polyhydric alcohol with a fatty acid, and preferably one obtained by esterifying one hydroxyl group of a polyhydric alcohol.
Specific examples of the polyhydric alcohol that is a raw material of the esterified product include ethylene glycol, diethylene glycol, polyethylene glycol (molecular weight 200 to 11000), propylene glycol, dipropylene glycol, polypropylene glycol (molecular weight 250 to 4000), and 1,3. -Butylene glycol, glycerin, polyglycerin (degree of polymerization 2-30), erythritol, xylitol, sorbitol, mannitol, inositol, sorbitan, sorbide, sucrose, trehalose, erulose, lactosucrose, cyclodextrin, maltitol, lactitol, palatinit , Panitol, reduced starch syrup and the like. Preferred are polyethylene glycol, glycerin, erythritol, sorbitol, sorbitan, sorbide, and sucrose, and particularly preferred are sorbitol, sorbitan, and sorbide.

  Examples of the fatty acid used in the present invention include saturated or unsaturated fatty acids having 6 to 22 carbon atoms, mixed fatty acids containing these as main components, and branched chain fatty acids having 8 to 36 carbon atoms. Specifically, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, cis-9-octadecenoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid , 2-ethylhexylic acid, isostearic acid, and the like, and coconut oil fatty acid and beef tallow fatty acid which are naturally derived mixed fatty acids may be used, preferably fatty acids having 8 to 18 carbon atoms, particularly preferably dodecanoic acid, octadecane. Acid, cis-9-octadecenoic acid.

  The esterified product of a polyhydric alcohol and a fatty acid in the present invention uses a polyhydric alcohol and a fatty acid as raw materials, and a basic catalyst and phosphoric acid or an alkali salt thereof are added. To react under nitrogen flow. Specific examples of the basic catalyst include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium carbonate, and the like, preferably sodium carbonate. Specific examples of phosphoric acid or alkali salts thereof include phosphorous acid, hypophosphorous acid, and alkali salts thereof, and phosphorous acid is preferred.

  In the present invention, a synthetic adsorbent containing a composite metal oxide in the presence of 1 to 300% by weight of water based on the weight of the esterified product of a polyhydric alcohol and a fatty acid. Process.

In the present invention, the adsorbent treatment for the esterified product of polyhydric alcohol and fatty acid is performed with 0.1 to 10% by weight of a synthetic adsorbent containing a composite metal oxide in the presence of 1 to 300% by weight of water.
The amount of the synthetic adsorbent used is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. If the amount is less than 0.1% by weight, the ability to treat with the adsorbent is not sufficient, and the effect of reducing bitterness and odor is not sufficient. If it exceeds 10% by weight, it will be difficult to remove the adsorbent in a later step, and no effect will be obtained even if an amount exceeding this is used.
The treatment temperature of the synthetic adsorbent is 30 to 100 ° C, preferably 50 to 90 ° C. If the temperature is lower than 30 ° C, it takes too much processing time, and if the temperature is higher than 100 ° C, coloring, bitterness and odor are deteriorated. Usually, the processing time is 30 minutes to 3 hours.
When processing with a synthetic adsorbent, it is performed in the presence of water. The amount of water used is 1 to 300% by weight, preferably 1 to 5% by weight. If it exceeds 300% by weight, the production efficiency is lowered, which is not preferable.
After the treatment with the synthetic adsorbent, the synthetic adsorbent can also be removed by filtration and centrifugation.

The synthetic adsorbent containing the composite metal oxide used in the present invention includes a composite metal oxide composed of 10 to 90% by weight of the magnesium oxide component and 10 to 50% by weight of the aluminum oxide component. The content of the product is 50 to 95% by weight, the loss on drying is 1.5% by weight or less, preferably 50 to 90% by weight of the magnesium oxide component, and 10 to 50% by weight of the aluminum oxide component, The loss on drying is 1.5% by weight or less.
The loss on drying is represented by the weight reduction rate of the synthetic adsorbent after 2 hours at 110 ° C., and indicates the amount of water contained in the molecule of the synthetic adsorbent.
Use of a synthetic adsorbent containing a fired activated composite metal oxide is effective in improving bitterness and odor, and the firing activation temperature is generally 200 to 1000 ° C. for 2 to 6 hours. Is.
The synthetic adsorbent containing the fired activated composite metal oxide has almost no moisture in the molecule and can be used as a dehydrating agent. The weight loss on drying of the synthetic adsorbent containing the fired activated composite metal oxide is 1.5% by weight or less, preferably 1.0% by weight or less.
Examples of such commercial activated activated adsorbents include Kyoward 300, Kyoward 500, Kyoward 1000, Kyoward 2000, and Tomita Pharmaceutical Co., Ltd. manufactured by Kyowa Chemical Industry Co., Ltd. Tomix AD300 and the like.

As the catalyst used for the ethylene oxide addition reaction to the esterified product of a polyhydric alcohol and a fatty acid, one or more of known alkali metal or alkaline earth metal oxides, hydroxides, alcoholates, etc. may be used. it can. Specific examples include potassium hydroxide, sodium hydroxide, calcium hydroxide, calcium oxide, sodium methoxide and the like. The amount of the catalyst used is not particularly limited, but is generally 0.01 to 5.0% by weight based on the final weight of the ethylene oxide addition reaction product.
In the present invention, an ethylene oxide addition reaction is performed on an esterified product of a polyhydric alcohol and a fatty acid in the presence of a catalyst. At this time, ethylene oxide is directly injected into a slurry of the esterified product of a polyhydric alcohol and a fatty acid and the catalyst. Alternatively, ethylene oxide may be injected after dissolving and suspending in a water-soluble solvent such as water or alcohol or a water-insoluble solvent such as hexane or toluene. The solvent may be removed during the reaction or after completion of the reaction by a reduced pressure treatment or the like, or may be mixed in the addition reaction product without being removed depending on the application.

The polyoxyethylene polyhydric alcohol fatty acid ester of the present invention can be usually obtained by adding 1 to 100 moles of ethylene oxide to an esterified product of a polyhydric alcohol and a fatty acid. When used as a food application, those added with 5 to 40 mol are preferable.
The polyoxyethylene polyhydric alcohol fatty acid ester is preferably a polyoxyethylene sorbitan fatty acid ester. The number of fatty acid esters is preferably a monoester of 1 to 3, more preferably 1. Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, and polyoxyethylene sorbitan monooleate are particularly preferred. Commercially available products include polyoxyethylene (20) sorbitan monolaurate (polysorbate 20), polyoxyethylene (20) sorbitan monostearate (polysorbate 60), polyoxyethylene (20) sorbitan tristearate (polysorbate 65), Polyoxyethylene (20) sorbitan monooleate (polysorbate 80) can be mentioned. These compounds are suitable for pharmaceuticals, quasi drugs and food applications.
The reaction temperature of the ethylene oxide addition reaction in the present invention can be generally carried out at about 50 to 180 ° C, preferably 80 to 150 ° C. When the reaction temperature is lower than 50 ° C., the reaction may be difficult to proceed. When the reaction temperature is higher than 180 ° C., exposure to a high temperature may cause coloring and deterioration odor. The reaction pressure is preferably 0.1 to 0.8 MPa, and more preferably 0.1 to 0.4 MPa.

  In the present invention, for the polyoxyethylene polyhydric alcohol fatty acid ester obtained after the ethylene oxide addition reaction, the basic catalyst is deactivated, so that mineral acids such as phosphoric acid and sulfuric acid, or formic acid, acetic acid, caproic acid, and lactic acid are used. Short-chain aliphatic monocarboxylic acid, oxalic acid, succinic acid, malic acid, adipic acid, citric acid and other polyvalent carboxylic acids, benzoic acid, salicylic acid and other aromatic monocarboxylic acids, phthalic acid, terephthalic acid, isophthalic acid, etc. Neutralization with an aromatic polyvalent carboxylic acid or the like, washing with salting-out water, or treatment with an ion exchange resin. These treatments may be performed repeatedly or different operations may be repeated. When neutralization is performed, one type or a combination of two or more types may be performed.

Further, after this, a decoloring process can be performed if necessary. The decolorization treatment in the present invention is performed using a bleaching agent such as hydrogen peroxide, sodium hypophosphite, phosphorous acid, sodium phosphite, sodium chlorate, or sodium hypochlorite. The addition amount of the bleaching agent is preferably 0.1 to 10% by weight with respect to 100% by weight of the addition reaction product in the case of 35% hydrogen peroxide solution. The temperature for the decolorization treatment is preferably 60 to 100 ° C., and the treatment time is preferably 0.5 to 1.0 hour. These treatments may be performed by using one or a combination of two or more bleaching agents.
In the present invention, after adding ethylene oxide to the esterified product of polyhydric alcohol and fatty acid, magnesium oxide is added in the presence of 1 to 300% by weight of water based on the weight of the obtained polyoxyethylene polyhydric alcohol fatty acid ester. Burning activity at 0.1 to 10% by weight of a synthetic adsorbent having a loss on drying of 1.5% by weight or less, including a composite metal oxide having a component of 50 to 90% by weight and an aluminum oxide component of 10 to 50% by weight The treatment is performed with an adsorbent containing the converted composite metal oxide.
The treatment with a synthetic adsorbent containing a fired activated composite metal oxide of polyoxyethylene polyhydric alcohol fatty acid ester is synthesized by filtration, centrifugation, etc. after the treatment, in the same manner as in the fatty acid ester of polyhydric alcohol. The adsorbent can also be removed.

In the present invention, after treatment with a synthetic adsorbent of polyoxyethylene polyhydric alcohol fatty acid ester, a solvent such as water, ethanol, propylene glycol, erythorbic acid, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid to prevent deterioration over time Add one or more antioxidants such as propyl acid, isopropyl citrate, guaiac acid, nordihydroguaiaretic acid, disodium ethylenediaminetetraacetate, disodium ethylenediaminetetraacetate, dl-α-tocopherol Can do.
Since the polyoxyethylene polyhydric alcohol fatty acid ester obtained by the production method of the present invention has less bitterness and odor than conventional products, it can be suitably used for pharmaceuticals, quasi drugs, cosmetics, food applications, etc. In particular, it can be suitably used for food applications.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
About the Example and the comparative example, with respect to each compound, the sensory test of bitterness and odor was conducted for 10 adults.
[Sensory test (bitterness)]
The bitterness was evaluated by the subject directly including 0.1 g of the compound in his mouth. The comparative measurement of bitterness was evaluated in the following five stages, and the average value of the results was adopted.
1: Little bitterness 2: Some bitterness remains 3: Some bitterness remains 4: Somewhat strong bitterness remains 5: Strong bitterness remains [Sensory test (odor)]
The odor was evaluated by the subject directly smelling the specimen obtained by adding 100 cc of the composite to a 150 cc sample bottle. The comparative measurement was evaluated in the following five stages, and the average of the results was adopted.
1: There is almost no degradation odor of fatty acids 2: There is a slight degradation odor of fatty acids 3: Some degradation odor of fatty acids 4: There is a considerable degradation odor of fatty acids 5: There is a severe degradation odor of fatty acids [Evaluation criteria (bitterness ,smell)〕
The evaluation of bitterness and odor was considered to be most suitable for use in the mouth with less bitterness and odor when the average value obtained by 10-grade evaluation of a composite by 10 adult subjects was 1 or more and less than 3. When the average value was 3 or more, it was bitter and smelly and was not suitable for use in the mouth.

Example 1 (Synthesis of polyoxyethylene (20 mol) sorbitan monooleate)
For 500 g of sorbitan monooleate, 25 g of water (corresponding to 5% by weight of the esterified product of polyhydric alcohol and fatty acid) and Kyoward 2000 (Kyowa Chemical Industry Co., Ltd., magnesium oxide 60 wt. %, Aluminum oxide 30% by weight, composite metal oxide content 90% by weight, loss on drying is 0.8% by weight) equivalent to 2% by weight of the esterified product of polyhydric alcohol and fatty acid And after stirring for 1 hour at 80 ° C. with stirring under a nitrogen stream, moisture is removed by treatment at −0.095 MPa (50 mmHg) for 1 hour at 100 ° C., and the adsorbent is removed by filtration. did. 426 g of the obtained sample, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into an autoclave. After the atmosphere in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 65 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) And 26 g of Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) (corresponding to 2% by weight based on the weight of polyoxyethylene polyhydric alcohol fatty acid ester) was added at 80 ° C. with stirring under a nitrogen stream. After the treatment for 1 hour, it was treated at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour to remove moisture and filtered to obtain the title substance.

Example 2 (Synthesis of polyoxyethylene monostearate (20 mol) sorbitan)
To 500 g of sorbitan monostearate, 25 g of water (corresponding to 5% by weight of the esterified product of polyhydric alcohol and fatty acid) and Kyoward 2000 (Kyowa Chemical Industry Co., Ltd., magnesium oxide 60 wt. %, Aluminum oxide 30% by weight, composite metal oxide content 90% by weight, drying loss 0.8% by weight) to 2% by weight with respect to the weight of the esterified product of polyhydric alcohol and fatty acid And after treatment at 80 ° C. for 1 hour with stirring under a nitrogen stream, moisture is removed by treatment at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour, and the adsorbent is removed by filtration. Removed. 426 g of the obtained sample, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into an autoclave. After the atmosphere in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 65 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) And 26 g of Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) (corresponding to 2% by weight based on the weight of polyoxyethylene polyhydric alcohol fatty acid ester) was added at 80 ° C. with stirring under a nitrogen stream. After the treatment for 1 hour, it was treated at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour to remove moisture and filtered to obtain the title substance.

Example 3 (Synthesis of polyoxyethylene monolaurate (20 mol) sorbitan)
For 500 g of sorbitan monolaurate, 25 g of water (corresponding to 5% by weight of the esterified product of polyhydric alcohol and fatty acid) and Kyoward 2000 (Kyowa Chemical Industry Co., Ltd., magnesium oxide 60% by weight) , 30% by weight of aluminum oxide, 90% by weight of composite metal oxide, 0.8% by weight loss on drying) equivalent to 2% by weight of esterified product of polyhydric alcohol and fatty acid And after stirring for 1 hour at 80 ° C. with stirring under a nitrogen stream, moisture is removed by treatment at −0.095 MPa (50 mmHg) for 1 hour at 100 ° C., and the adsorbent is removed by filtration. did. 426 g of the obtained sample, 1.4 g of potassium hydroxide and 0.28 g of sodium hypophosphite were charged into an autoclave, and the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 994 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred as it was for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 71 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) And 28 g of Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) (corresponding to 2% by weight with respect to the weight of polyoxyethylene polyhydric alcohol fatty acid ester) was added at 80 ° C. with stirring under a nitrogen stream. After the treatment for 1 hour, it was treated at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour to remove moisture and filtered to obtain the title substance.

Example 4 (Synthesis of polyoxyethylene (20 mol) sorbitan monooleate)
For 500 g of sorbitan monooleate, 25 g of water (corresponding to 5% by weight of the esterified product of polyhydric alcohol and fatty acid) and Kyoward 2000 (Kyowa Chemical Industry Co., Ltd., magnesium oxide 60 wt. %, Aluminum oxide 30% by weight, composite metal oxide content 90% by weight, drying loss 0.8% by weight) to 2% by weight with respect to the weight of the esterified product of polyhydric alcohol and fatty acid And after treatment at 80 ° C. for 1 hour with stirring under a nitrogen stream, moisture is removed by treatment at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour, and the adsorbent is removed by filtration. Removed. 426 g of the obtained sample, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into an autoclave. After the atmosphere in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 65 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) And 10 g of Kyoward 2000 (Kyowa Chemical Industry Co., Ltd.) (corresponding to 0.8% by weight based on the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) was added and stirred at 80 ° C. under a nitrogen stream. After 1 hour of treatment at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour to remove moisture and filtration, the title substance was obtained.

Example 5 (Synthesis of polyoxyethylene (20 mol) sorbitan monooleate)
For 500 g of sorbitan monooleate, 25 g of water (corresponding to 5% by weight of the esterified product of polyhydric alcohol and fatty acid) and Kyoward 2000 (Kyowa Chemical Industry Co., Ltd., magnesium oxide 60 wt. %, Aluminum oxide 30% by weight, composite metal oxide content 90% by weight, drying loss 0.8% by weight) to 2% by weight with respect to the weight of the esterified product of polyhydric alcohol and fatty acid And after treatment at 80 ° C. for 1 hour with stirring under a nitrogen stream, moisture is removed by treatment at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour, and the adsorbent is removed by filtration. Removed. 426 g of the obtained sample, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into an autoclave. After the atmosphere in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 65 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) And 5 g (corresponding to 0.4% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) of KYOWARD 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at 80 ° C. under a nitrogen stream After 1 hour of treatment at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour to remove moisture and filtration, the title substance was obtained.

Comparative Example 1 (Synthesis of polyoxyethylene (20 mol) sorbitan monooleate)
426 g of sorbitan monooleate, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into the autoclave, and the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 65 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd., magnesium oxide 60% by weight, aluminum oxide 30% by weight, composite metal oxide content 90% by weight, loss on drying 0.8% by weight) (Corresponding to 2% by weight based on the weight of the oxyethylene polyhydric alcohol fatty acid ester) and after stirring for 1 hour at 80 ° C. with stirring under a nitrogen stream, at −0.095 MPa (50 mmHg) at 100 ° C. It was treated for 1 hour to remove moisture and filtered to obtain the title substance.

Comparative Example 2 (Synthesis of polyoxyethylene (20 mol) sorbitan monostearate)
426 g of sorbitan monostearate, 1.3 g of potassium hydroxide and 0.26 g of sodium hypophosphite were charged into the autoclave, and the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 65 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd., magnesium oxide 60% by weight, aluminum oxide 30% by weight, composite metal oxide content 90% by weight, loss on drying 0.8% by weight) (Corresponding to 2% by weight based on the weight of the oxyethylene polyhydric alcohol fatty acid ester) and after stirring for 1 hour at 80 ° C. with stirring under a nitrogen stream, at −0.095 MPa (50 mmHg) at 100 ° C. It was treated for 1 hour to remove moisture and filtered to obtain the title substance.

Comparative Example 3 (Synthesis of polyoxyethylene monolaurate (20 mol) sorbitan)
426 g of sorbitan monolaurate, 1.4 g of potassium hydroxide, and 0.28 g of sodium hypophosphite were charged into an autoclave. After the atmosphere in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 120 ° C. with stirring. Subsequently, 994 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred as it was for 2 hours to complete the reaction.
After taking out the reaction composition from the autoclave and neutralizing with 85% phosphoric acid to adjust the pH to 6-7, 71 g of water (corresponding to 5% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) 28 g (Polyester 2000) (manufactured by Kyowa Chemical Industry Co., Ltd., magnesium oxide 60% by weight, aluminum oxide 30% by weight, composite metal oxide content 90% by weight, loss on drying 0.8% by weight) (Corresponding to 2% by weight based on the weight of the oxyethylene polyhydric alcohol fatty acid ester) and after stirring for 1 hour at 80 ° C. with stirring under a nitrogen stream, at −0.095 MPa (50 mmHg) at 100 ° C. It was treated for 1 hour to remove moisture and filtered to obtain the title substance.

Comparative Example 4 (Synthesis of polyoxyethylene (20 mol) sorbitan monooleate)
To 500 g of sorbitan monooleate, 25 g (corresponding to 5% by weight of the esterified product of polyhydric alcohol and fatty acid) of water and Kyoward 2000 (Kyowa Chemical Industry Co., Ltd., magnesium oxide 60 wt. %, Aluminum oxide 30% by weight, composite metal oxide content 90% by weight, drying loss 0.8% by weight) to 2% by weight with respect to the weight of the esterified product of polyhydric alcohol and fatty acid And after treatment at 80 ° C. for 1 hour with stirring under a nitrogen stream, moisture is removed by treatment at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour, and the adsorbent is removed by filtration. Removed. 426 g of the obtained sample, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into an autoclave. After the atmosphere in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
The reaction composition was taken out from the autoclave, neutralized with 85% phosphoric acid to adjust the pH to 6-7, then treated at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour to remove moisture and filtered. The title material was obtained.

Comparative Example 5 (Synthesis of polyoxyethylene (20 mol) sorbitan monooleate)
426 g of sorbitan monooleate, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into the autoclave, and the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
The reaction composition was taken out from the autoclave, neutralized with 85% phosphoric acid to adjust the pH to 6-7, then treated at −0.095 MPa (50 mmHg) at 100 ° C. for 1 hour to remove moisture and filtered. The title material was obtained.

Comparative Example 6 (Synthesis of polyoxyethylene (20 mol) sorbitan monooleate)
426 g of sorbitan monooleate, 1.3 g of potassium hydroxide, and 0.26 g of sodium hypophosphite were charged into the autoclave, and the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 120 ° C. with stirring. . Subsequently, 880 g of ethylene oxide was dropped and reacted at 120 ° C. with a dropping device, and the mixture was stirred for 2 hours to complete the reaction.
The reaction composition was taken out from the autoclave, neutralized with 85% phosphoric acid to adjust the pH to 6 to 7, and 274 g of water (corresponding to 21% by weight with respect to the weight of the polyoxyethylene polyhydric alcohol fatty acid ester) was added. Then, it was treated at −0.095 MPa (50 mmHg) at 100 ° C. to remove moisture and filtered to obtain the title substance.

* 1)
1: Polyoxyethylene (20 mol) sorbitan monooleate 2: Polyoxyethylene (20 mol) sorbitan monostearate 3: Polyoxyethylene (20 mol) sorbitan monolaurate * 2) Pretreatment of polyhydric alcohol and fatty acid Treat the esterified product with an adsorbent. (The amount of mixed metal oxide and water added during pre-treatment in the table is shown as a percentage of the weight of the esterified product of polyhydric alcohol and fatty acid)
* 3) Post-treatment Treatment with an adsorbent for ethylene oxide derivatives of esterified products of polyhydric alcohols and fatty acids. (The added amount of composite metal oxide and water added during post-treatment in the table is expressed as a percentage of the weight of polyoxyethylene polyhydric alcohol fatty acid ester)
* 4) Bitter evaluation result 1 or more and less than 3: ○ 3 or more and 5 or less: ×
* 5) Odor evaluation result 1 or more and less than 3: ○ 3 or more and 5 or less: ×

From the results of Table 1, it is judged that the smaller the sensory test values for bitterness and odor, the more optimal it can be used for pharmaceuticals, quasi drugs, cosmetics, and food applications.
In Comparative Examples 1 to 3, an esterification product of a polyhydric alcohol and a fatty acid that is not pretreated is subjected to an addition reaction with ethylene oxide and then treated with an adsorbent containing a composite metal oxide. In Comparative Example 4, pre-processing is performed, but post-processing is not performed. Although these are very bitter, the bitterness is considerably reduced in Examples 1 to 3 in which pretreatment and posttreatment were performed, and the effects of the present invention are clear.

Claims (2)

An esterified product of a polyhydric alcohol and a fatty acid, in the presence of 1 to 300% by weight of water, contains a composite metal oxide comprising a magnesium oxide component of 50 to 90% by weight and an aluminum oxide component of 10 to 50% by weight. The ethylene oxide derivative was obtained by the addition reaction of ethylene oxide with the esterified product of a polyhydric alcohol and a fatty acid which were treated with 0.1 to 10% by weight of a synthetic adsorbent having a loss on drying of 1.5% by weight or less. rear,
In the presence of 1 to 300% by weight of water, the obtained ethylene oxide derivative contains a composite metal oxide comprising a magnesium oxide component of 50 to 90% by weight and an aluminum oxide component of 10 to 50% by weight. A process for producing a polyoxyethylene polyhydric alcohol fatty acid ester, characterized by treatment with 0.1 to 10% by weight of a synthetic adsorbent that is 1.5% by weight or less.   The production method according to claim 1, wherein the polyoxyethylene polyhydric alcohol fatty acid ester is a polyoxyethylene sorbitan fatty acid ester.