JPH08173787A - Surfactant composition - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] Surfactant composition comprising fatty acid ester of sorbitol dehydration condensation product, which can be preferably used as an oil-in-water emulsifier, and oil-in-water emulsion using the surfactant The present invention also provides a method for producing a detergent containing the same as a detergent and a surfactant composition thereof. [Structure] Monocaprylic acid ester and / or monocapric acid ester of at least one polyhydric alcohol selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, and 1,5-sorbitan, 1,4 −
A mixture of at least one polyhydric alcohol selected from sorbitan and isosorbide with dicaprylic acid and / or dicapric acid ester, and substantially free of tricaprylic acid ester and / or tricapric acid ester of polyhydric alcohol, or A surfactant composition having a content of 5% by weight or less and a weight ratio of monoester to diester in the range of 3/7 to 9/1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel surfactant composition, an oil-in-water emulsion containing the same as an emulsifier, a detergent containing the same as a cleaning base, and a method for producing the surfactant composition. It is a thing.

[0002]

2. Description of the Related Art Conventionally, it is known to use a fatty acid ester of a sorbitol dehydration condensation product obtained by reacting a dehydration condensation product of sorbitol with a higher fatty acid or a lower alcohol ester thereof as a surfactant. Conventionally, higher fatty acid esters of sorbitol dehydration condensates, which are generally used as surfactants, contain sorbitan fatty acid ester as a main component, and include sorbitan lauric acid ester, palmitic acid ester, stearic acid ester, and olein. It was an ester of higher fatty acid having 12 or more carbon atoms such as acid ester. Moreover, the higher fatty acid ester of such a sorbitol dehydration condensate contains a large amount of 10% by weight or more of a triester in addition to a monoester and a diester. The higher fatty acid ester of such sorbitol dehydration condensate serves as a highly lipophilic surfactant and is used as a water-in-oil emulsifier in the fields of food and cosmetics. On the other hand, in the fields of foods, cosmetics and perfumes, there is also a strong demand for highly safe oil-in-water emulsifiers. However, higher fatty acid esters of sorbitol dehydration condensation products as described above are
As such an oil-in-water emulsifier, it has not shown a satisfactory effect. Therefore, in order to improve this point, there is an attempt to dissolve additives such as lysophosphatide to improve emulsifying power, dispersing power, penetrating power and the like (JP-A-63-51929). Such additives are expensive and not a practical proposal.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to a surfactant composition comprising a fatty acid ester of a sorbitol dehydration condensation product which can be preferably used as an oil-in-water type emulsifier, and an oil-in-water emulsion containing the surfactant. It is an object of the present invention to provide a method for producing a detergent containing the same as a detergent base and a surfactant composition thereof.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that among fatty acid esters of sorbitol dehydration condensation products, monocaprylic acid ester and / or monocapric acid ester are used. It was found that an oil-in-water type emulsion can be easily prepared by using a mixture of dicaprylic acid ester and / or dicaprylic acid ester, and completed the present invention.

That is, according to the present invention, a monocaprylic acid ester and / or a monocapric acid ester of at least one polyhydric alcohol selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, and 1 ，
A mixture of at least one polyhydric alcohol selected from 5-sorbitan, 1,4-sorbitan, and isosorbide with dicaprylic acid and / or dicapric acid ester, wherein the tricaprylic acid ester and / or tricapric acid of the polyhydric alcohol is used. The ester is substantially not contained or the content thereof is 5% by weight or less, and the weight ratio of the monoester and the diester is 3/7 to 9/1.
There is provided a surfactant composition characterized in that

Further, according to the present invention, there is provided an oil-in-water emulsion of an oil component obtained by emulsifying an oil component in water in the presence of the surfactant composition.

Further, according to the present invention, there is provided a detergent comprising the surfactant composition as a washing base.

Furthermore, according to the present invention, at least one polyhydric alcohol selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, and caprylic acid, capric acid, caprylic acid lower alkyl ester and caprin. At least one fatty acid selected from the group consisting of acid lower alkyl esters and / or lower alkyl esters thereof is reacted in an organic solvent using a neutral thermostable lipase to produce the above surfactant composition. A method is provided.

The polyhydric alcohol used as a raw material for synthesizing the surfactant composition of the present invention is 1,5-sorbitan,
It is selected from 4-sorbitan and isosorbide. These polyhydric alcohols can be used alone or as a mixture thereof. 50% by weight of 1,4-sorbitan as polyhydric alcohol
It is preferable to use those containing the above. The structural formulas of 1,5-sorbitan, 1,4-sorbitan and isosorbide described above are as follows.

The polyhydric alcohol used in the present invention can be obtained by intramolecular dehydration condensation of sorbitol. The sorbitol dehydration condensation product thus obtained contains the above-mentioned 1,5-sorbitan, 1,4-sorbitan, isosorbide and unreacted sorbitol. In the case of the present invention, 1,5-sorbitan, 1,4-sorbitan, and isosorbide can be separated from the sorbitol dehydration condensate, and the single product or the mixed product can be used as a surfactant raw material. Further, in the case of the present invention, the sorbitol dehydration condensate can be advantageously used as it is as a raw material for the surfactant composition.

The component composition of the sorbitol dehydration condensation product preferably used in the present invention is as follows: sorbitol: 0 to 1
0% by weight, preferably 0-5% by weight, sorbitan (1,
Total amount of 5-sorbitan and 1,4-sorbitan): 1
0 to 100% by weight, preferably 10 to 97% by weight, particularly preferably 50 to 80% by weight, isosorbide: 0 to 9
It is 0% by weight, preferably 3 to 50% by weight. The component composition of the sorbitol dehydration condensate can be changed according to the dehydration reaction conditions of sorbitol, the reaction method, the catalyst, and the like. It can also be prepared by mixing the individual products. The smaller the amount of sorbitol in the sorbitol dehydration condensate, the more preferable. However, when the content of sorbitol is 10% by weight or less, the performance of the obtained surfactant composition is not particularly adversely affected.

As the other raw material of the surfactant composition of the present invention, caprylic acid [CH ₃ (CH ₂ ) ₆ COOH] or capric acid [CH ₃ (CH ₂ ) ₈ COOH] or their lower alcohol ester is used. Used. The lower alcohol ester has 1 to 1 carbon atoms such as methyl ester, ethyl ester, propyl ester and butyl ester.
The alcohol ester of 4 can be mentioned.

In order to produce the surfactant composition of the present invention, first, the above-mentioned polyhydric alcohol or a mixture thereof (including sorbitol dehydration condensation product itself), caprylic acid or a lower alkyl ester thereof or capric acid or The lower alkyl ester is esterified by a conventionally known method. The esterification reaction in this case is
It can be carried out in the presence of a base catalyst such as sodium hydroxide or potassium hydroxide, or an acid catalyst such as sulfuric acid or paratoluenesulfonic acid.

When a polyhydric alcohol or a mixture thereof is reacted with caprylic acid or its lower alkyl ester, the proportion of caprylic acid or its lower alkyl ester used is
0.1 to 1 mol of polyhydric alcohol or a mixture thereof
The amount is 20 mol, preferably 1 to 10 mol. As the catalyst, it is preferable to use sodium hydroxide, potassium hydroxide, calcium hydroxide or the like. The reaction temperature is 100 to 300 ° C, preferably 150 to 250 ° C. The reaction is carried out under reduced pressure or under the flow of an inert gas so that water or lower alcohol by-produced in the reaction can be easily distilled out of the system. In the esterification reaction, a tricaprylic acid ester is produced in addition to the monocaprylic acid ester and the dicaprylic acid ester. In the present invention, the triester removes the tricaprylic acid ester from the reaction product, and the content thereof is substantially reduced. Is specified to be 0% or 5% by weight or less. The composition of the caprylic acid ester of polyhydric alcohol which is preferable as the surfactant composition of the present invention is shown as follows: monoester: 30 to
90% by weight, preferably 60-80% by weight, diester: 10-70% by weight, preferably 20-40% by weight,
Triester: 0-5% by weight, preferably 0-3% by weight
Is. The weight ratio of monoester and diester is 3 /
It is 7 to 9/1, preferably 5/5 to 8/2. The weight ratio of this monoester and diester can be adjusted by the reaction conditions in the esterification reaction,
Further, it can be adjusted by mixing the monoester and diester separated and collected from the reaction product by a column or the like in a predetermined ratio.

When the polyhydric alcohol or a mixture thereof is reacted with capric acid or its lower alkyl ester, the proportion of capric acid or its lower alkyl ester used is
0.1 to 1 mol of polyhydric alcohol or a mixture thereof
The amount is 20 mol, preferably 1 to 10 mol. Further, as the catalyst, it is preferable to use a basic catalyst such as sodium hydroxide. The reaction temperature is 100 to 300 ° C, preferably 150 to 250 ° C. The reaction is carried out under reduced pressure or under the flow of an inert gas so that water or lower alcohol by-produced in the reaction can be easily distilled out of the system. In the esterification reaction, a tricapric acid ester is produced in addition to the monocapric acid ester and the dicapric acid ester. In the present invention, the triester removes the tricapric acid ester from the reaction product, and the content thereof is substantially reduced. 0% or 5% by weight
It is specified below. The composition of capric acid ester of polyhydric alcohol which is preferable as the surfactant composition of the present invention is shown as follows: monoester: 30 to 90% by weight, preferably 60
-80% by weight, diester: 10-70% by weight, preferably 20-40% by weight, triester: 0-5% by weight,
It is preferably 0 to 3% by weight. The weight ratio of monoester to diester is 3/7 to 9/1, preferably 5/5.
~ 8/2. The weight ratio of the monoester and diester can be adjusted by the reaction conditions in the esterification reaction, and the monoester and diester separated and recovered from the reaction product by a column or the like are mixed at a predetermined ratio. It can be adjusted by
Further, in the present invention, the caprylic acid and / or the lower alkyl ester thereof and the capric acid and / or the lower alkyl ester can be subjected to the reaction in the form of a mixture of both.

In the esterification reaction in the presence of the above-mentioned chemical catalyst such as acid or base, the obtained reaction product contains
Since a large amount of triester is produced, it is necessary to separate and remove the triester from the reaction product in order to obtain the surfactant composition of the present invention. Is still unsatisfactory in terms of. According to the study of the present inventors, when the esterification reaction is carried out in an organic solvent using a neutral thermostable lipase without using a chemical catalyst, by-production of triester is prevented and the monoester is prevented. It has been found that a mixture of and diester can be obtained efficiently.

When the esterification reaction is carried out in the presence of neutral thermostable lipase, the reaction temperature is 40 to 95 ° C, preferably 60 to 90 ° C. As the neutral thermostable lipase, 50 mg of the lipase powder is dissolved in 0.4 ml of phosphate buffer (0.1 M, pH 7) and the residual activity after heating at 70 ° C. for 30 minutes is 40% or more, preferably 80%.
% Or more, more preferably 95% or more,
Any one can be used as long as it has the maximum hydrolysis activity in the range of pH 5.0 to 10.0, more preferably pH 5.5 to 9.5. Examples of such neutral thermostable lipase include porcine pancreatic lipase, yeast lipase derived from yeast of the genus Candida, mold lipases such as those of the genus Alpengillus and genus Mucor, and bacterial lipases such as the genus Cydomonas. Further, those obtained by modifying the above lipase by genetic engineering etc. are also included. As the preferable neutral thermostable lipase used in the present invention, a neutral thermostable lipase derived from Candida antarctica (sp-382, sp-435, manufactured by NOVO Co., maximum activity pH 7.5), Mucormiehe
i) Neutral thermostable lipase derived from Lipozyme, N
OVO Co., Ltd., maximum active pH 6.0) and the like can be used, but the invention is not limited thereto.

The lipase may be a purified enzyme or a crude enzyme, but is preferably immobilized. The immobilization method may be any of the carrier binding method, the cross-linking method and the entrapping method, but the carrier binding method is particularly preferable from the viewpoint of activity expression and the like. As the immobilization carrier, activated carbon, porous glass,
Acid clay, bleaching clay, kaolinite, alumina, silica gel, bentonite, hydroxyapatite, calcium phosphate, inorganic substances such as metal oxides, starch, natural polymers such as gluten, polyethylene, polypropylene, phenolformaldehyde resin, acrylic resin, anion Examples thereof include synthetic polymers such as exchange resins and cation exchange resins. In the present invention, it is preferable to use a porous polymer, for example, porous polyethylene, porous polypropylene, porous phenol formaldehyde resin or the like. The amount of lipase used during the reaction can be appropriately selected and is not limited, but it may be 0.1% to 100 parts by weight of the polyhydric alcohol.
It may be in the range of 1 to 10000 parts by weight, preferably 1 to 2000 parts by weight.

Examples of the organic solvent include aliphatic hydrocarbons such as n-heptane, n-hexane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclobutane; benzene, toluene, xylene and phenol. Aromatic hydrocarbons such as; ketones such as acetone and methyl isobutyl ketone; acetonitrile, morpholine, N-methylmorpholine, N
-Ethylmorpholine, 2-nitropropane, pyridine, 2-ethylpyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 2,4. 6-trimethylpyridine, pyrrole, N-methylpyrrole, piperidine, N-methylpiperidine, N-ethylpiperidine, piperazine, N-methylpiperazine, 1,4-dimethylpiperazine, pyrrolidine, 1-methylpyrrolidine,
Quinoline, butylamine, tributylamine, N, N,
N ', N'-tetramethyl-1,6-hexanediamine, N, N, N', N'-pentamethyl-diethylene-
Nitrogen-containing solvents such as triamine and dimethylformamide; ethers such as dimethyl ether, diethyl ether and dioxane; γ-butyrolactone, α-
Esters such as acetyl-γ-butyrolactone, diethyl carbonate, ethylene carbonate, propylene carbonate; halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride; sulfoxide solvents such as dimethyl sulfoxide; 2,4-dimethyl- 3-pentanol 1,6
-Secondary alcohols such as dimethyl 4-heptanol; tertiary-butyl alcohol, tertiary-amyl alcohol, diacetone alcohol, 2,4-dimethyl-3-
Pentanol, 2,6-dimethyl-4-heptanol,
Tertiary alcohols such as 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 3-propyl-3-pentanol, 2-methyl-2-hexanol, 2-ethyl-2-hexanol. And the like.

Of these, the nitrogen-containing solvents, which are particularly preferably used alone, are pyridine, 2-ethylpyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine and 2,4-dimethyl. Pyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, N
-Methylpyrrole, N-methylpiperidine, N-ethylpiperidine, 1,4-dimethylpiperazine, 1-methylpyrrolidine, and isooctane, γ-butyrolactone, α-acetyl-γ-butyrolactone, diacetone alcohol and the like can also be used. , But not limited to these. Other organic solvents may be used alone, but are preferably used in combination, for example, N-methylmorpholine and N-methylpiperidine;
It is possible to use a mixture of two or more kinds of organic solvents such as tertiary butyl alcohol and N, N'-dimethylformamide; tertiary amyl alcohol and N, N'-dimethylformamide, among them, tertiary alcohol And a polyhydric alcohol-soluble solvent are preferable, and the solvent mixing ratio in such a case can be appropriately selected.
It can range from 9 to 99: 1. The amount of the organic solvent used is preferably such that the polyhydric alcohol or lipase moves in the reaction vessel to promote the reaction, and is not particularly limited, but for example, 1 to 99% (W of the reaction system). /
W), preferably about 10 to 95% (W / W), may be added and reacted. Further, these organic solvents may be gradually added as the reaction progresses.

Regarding the water content in the reaction system, the water content does not necessarily have to be 0%, but the lower the water content, the better in view of the stability of the enzyme and the prevention of re-decomposition of the ester. A system in which water is not added is preferable.

The reaction mode for producing caprylic acid or capric acid ester of polyhydric alcohol is, for example, a packed column system in which immobilized lipase is packed in a column and a substrate solution is supplied to the column for reaction, and the enzyme is mixed with an enzyme in a stirring tank. There are a batch system in which a substrate is reacted and a continuous stirring tank system in which the reaction is continued in the stirring tank, but the reaction can be carried out by adopting any system. Further, water or lower alcohol is produced as a by-product in this enzymatic reaction, but it is necessary to remove this by-product in order to proceed the reaction efficiently. As a method of removing these by-products, for example, a method of adsorbing and removing with zeolite, molecular sieves, sodium sulfate, etc., a method of aeration with dry air or an inert gas in the reaction tank, and a method of evaporating and removing into the gas, or a reaction Although there is a method of reducing the pressure in the system to evaporate it and discharging it from the reaction system, any method can be used in combination with the enzyme reaction of the present invention. After completion of the reaction, the desired ester can be separated and collected from the reaction product by a known method. In the method for producing a surfactant composition using the neutral thermostable lipase, those containing a monoester and a diester can be obtained, which is adjusted by the ratio of the polyhydric alcohol and the fatty acid component, the reaction temperature, the reaction rate, etc. can do.

The surfactant composition of the present invention is excellent in the action of emulsifying an oil component in water. By adding the surfactant composition of the present invention together with the oil component to water or an aqueous solution, and stirring and mixing them. An oil-in-water type emulsion can be obtained. As the oil, animal and vegetable fats and oils, fat-soluble vitamins, waxes, fatty acid esters,
There are mineral oils, paraffins, higher alcohols, aromatic carboxylic acid esters, chlorinated hydrocarbons, polyolefins, silicones and the like, and these can be used alone or as a mixture of two or more kinds. Examples of the animal fats and oils include beef tallow, lard, fish fat, milk fat and the like,
Examples of vegetable oils and fats include, but are not limited to, coconut oil, palm oil, palm kernel oil, corn oil, cottonseed oil, rapeseed oil, soybean oil, and the like.

The surfactant composition of the present invention is used in an amount of 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of oil in order to obtain a stable emulsion. Is good. If the amount is too small, the stability of the emulsion is not sufficient, and if the amount is too large, the effect is not significantly improved, which is economically disadvantageous. The weight ratio of emulsifier / water phase is preferably 0.005 or more, more preferably 0.01-0.10.

In the formation of an emulsion (oil-in-water type) using the surfactant composition of the present invention, other polymeric emulsion stabilizers and the like may be used in combination, if necessary. Agents, thickeners, rust preventives, pH adjusters and the like can also be used in combination. As a polymeric emulsion stabilizer,
Examples thereof include methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, and starch.

Since the surfactant composition of the present invention has the following features, it can be advantageously used as a base for detergents. Excellent cleaning power compared to existing sorbitan ester. In particular, it has excellent cleaning power for food oil that remains on the plate. A foaming detergent is obtained as compared with existing sorbitan esters. Detergents that often come into contact with the body of the surfactant composition of the present invention, such as dishwashing agents, working detergents, skin /
Needless to say, when used as a hair cleaning agent (body shampoo, hair shampoo, etc.), clothes cleaning agent, etc., a highly safe cleaning agent can be obtained. It has the effect of having very little tightness on the skin. Furthermore, the detergent containing the surfactant composition of the present invention, which is composed of only food additives, has extremely high safety, and is a detergent for food, a food manufacturing machine, a food container, a baby bottle, etc. It can be advantageously used as an agent.

The concentration of the surfactant composition of the present invention in the detergent depends on the desired detergent and is 0.01% to 100%.
The range is selected. Generally, in consideration of usability and the like, it is preferably 1 to 80% by weight, more preferably 1 to 50% by weight, and particularly preferably 3 to 40% by weight. By further adding and blending a surfactant component having an anion group to the detergent composition of the present invention, a more practical product can be obtained. The addition of the surfactant component having an anionic group contributes to the increase in foaming power. This is kitchen detergent,
This shows that it is advantageous for body shampoo and hair shampoo. As the surfactant component having an anion group, specifically, an anionic surfactant and / or an amphoteric surfactant is used.

Examples of the anionic surfactant include the following. (1) Fatty acid salt (soap), ether carboxylate, N
-Carboxylate type surfactants such as acyl acidic (or neutral) amino acid salts. (2) Higher alcohol sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, olefin sulfate ester salt, fatty acid ethylene glycolide sulfate ester salt, fatty acid monoglyceride sulfate ester salt, fatty acid monoalkanolamide A sulfate ester type anionic surfactant such as a sulfate salt. (3) Alkylbenzenesulfonate, alkylnaphthalenesulfonate, paraffinsulfonate, α-sulfofatty acid ester salt, α-olefinsulfonate, alkylsulfonate, monoalkylsulfosuccinate,
Sulfonate type anionic surfactants such as acyl isethionate and fatty acid amide sulfonate. (4) A phosphate ester salt-type anionic surfactant of a higher alcohol phosphate ester salt.

The surfactant is blended by appropriately selecting the chain length of the alkyl group or alkenyl group depending on the purpose of various detergents. Preferred anionic surfactants for the purpose of cleaning hard surfaces such as dishwashing detergents are polyoxyethylene alkyl ether sulfate ester salts, alkylbenzene sulfonates, and α-olefin sulfonates. Anionic surfactants that are advantageously added to skin and hair cleansing agents such as body shampoo and hair shampoo are
Soap, ether carboxylate, N-acyl acidic aminosulfate (N-acylglutamate, etc.), N-acyl neutral amino acid salt (N-methyl-β-alanine triethanolamine salt, etc.), polyoxyethylene alkyl ether sulfate Examples thereof include ester salts, α-olefin sulfonates, monoalkyl sulfosuccinates, polyoxyethylene alkyl sulfosuccinates, acyl isethionates, and higher alcohol phosphate ester salts.

Examples of the amphoteric surfactant which can be added to the detergent of the present invention in the same manner as the anionic surfactant include the following. (1) Carboxylate-type amphoteric surfactant such as betaine-type amphoteric surfactant and amino acid-type amphoteric surfactant (2) Sulfate ester-type amphoteric surfactant (3) Sulfone such as sulfobetaine-type amphoteric surfactant (4) Phosphobetaine-type amphoteric surfactants and other phosphoric acid ester-type amphoteric surfactants These are highly safe surfactants and are particularly used for detergents for skin and hair. It is a thing. For dishwashing detergents, betaine-type amphoteric surfactants such as amidopropyl betaine are advantageously blended in the present invention.

The amount of the anionic group-containing surfactant component usable in the present invention is usually 0.1 to 50% by weight, more preferably 1 to 20% by weight.

Various additives may be added to the detergent composition of the present invention as long as the effects of the surfactant composition of the present invention are not impaired. For example, polyoxyethylene alkyl ether, alkyl saccharide-based surfactant, nonionic surfactant such as fatty acid diethanolamide, semipolar surfactant such as alkylamine oxide, zeolite, builder such as sodium carbonate and sodium silicate, propylene Moisturizers such as glycol, glycerin and sorbitol, methyl cellulose, polyoxyethylene glycol distearate, viscosity modifiers such as ethanol, methyl paraben,
Preservatives such as butylparaben, potassium glycyrrhizinate, anti-inflammatory agents such as tocopherol acetate, and other fungicides, pearlizing agents, antioxidants, fragrances, dyes, UV absorbers, etc. can be added as necessary. .

[0033]

Since the surfactant composition of the present invention is a fatty acid ester of a polyhydric alcohol obtained by dehydration condensation of sorbitol, it has a high level of safety like existing sorbitan esters. Moreover, the surfactant composition of the present invention, unlike conventional sorbitan esters, has excellent oil-in-water emulsification performance, and therefore contributes significantly to the development of new foods, cosmetics, cosmetics and the like. Expected to be very large.

Since the surfactant composition of the present invention has high safety, it is advantageously used in the food field, for example, for emulsifying coffee whitener, whipped cream, ice cream, shortening, etc. , Solubilizing dairy products, juices, flavors, oils, etc., and further, anti-aging agents such as bread, cakes, cookies, foaming agents such as ice cream, sponge cakes, chocolate,
It can be used as a dispersant for cocoa, chewing gum and the like. Further, the surfactant composition of the present invention can be advantageously applied to cosmetics and cosmetics because of its high safety. For example, it can be applied to basic cosmetics such as creams, emulsions, lotions, foundations, hair products such as hair tonics, hair liquids and rinses, and perfumes, fragrances such as colognes. The field of application of the surfactant composition of the present invention as an emulsifier is not limited to the above-mentioned fields, and the surfactant of the present invention is a solubilizer of fat-soluble vitamins and antibiotics, a pharmaceutical field such as a dispersant, Further, in the field of agrochemicals, it can be applied to emulsification and dispersion of drugs and fertilizers.

The surfactant composition of the present invention was added to water to
%, And observed under a polarizing microscope, it was found that the composition of the present invention had a strong optical anisotropy, whereas the conventional commercial product did not have optical anisotropy.

The detergent containing the surfactant composition of the present invention is very excellent in detergency, foaming power, no feeling of tightness on the skin and safety as compared with the existing sorbitan ester. . Therefore, the detergent using the surfactant composition of the present invention is a detergent having an opportunity to come into contact with the human body, for example, a detergent for dishware, a detergent for a wall or floor of a house or a bathtub, a body shampoo, a hair shampoo. It is suitable as a cleansing agent, a detergent for tableware, a detergent for food manufacturing machines, a detergent for clothes and the like. The detergent composition of the present invention can be in the form of solid, granular, liquid, paste, aerosol and the like.

[0037]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention.

Example 1 Mixture of 1,4-sorbitan fatty acid monoester and diester in a weight ratio of 1: 1 (triester content: 0%)
Was prepared, and the emulsification performance of the mixture was evaluated as follows. The results are shown in Table 1 in relation to the carbon number of fatty acids.

(Evaluation of Emulsifying Performance) Food Color (Blue No. 1)
50 ml of distilled water added with was added to a 100 ml beaker, and 1 g of a mixture of 1,4-sorbitan fatty acid monoester and diester in a weight ratio of 1: 1 was added to the beaker.
Dissolve by heating at ℃. While maintaining this at 60 ° C. and stirring with a homomixer at 8,000 rpm, 50 ml of soybean oil was added dropwise thereto at a rate of about 30 g / min, and stirring was further continued for 5 minutes to prepare an emulsion. The obtained emulsified liquid was transferred to a 100 ml cylinder and allowed to stand at room temperature for 24 hours, after which the amount of water separated into the lower part of the cylinder (water separation ratio) was determined.

To confirm the type of the emulsion, one drop of the emulsion is dropped into distilled water which is a continuous phase, and it is checked whether or not the droplet diffuses into the water to determine whether it is the o / w type. The decision was made. In this case, when the droplets of the emulsified liquid diffused in water, it was determined that the emulsified liquid was an oil-in-water type (o / w type) emulsified liquid. The water separation rate was calculated according to the following formula. For reference, the water separation rate of commercially available sucrose ester was also examined in the same manner.

From the results shown in Table 1, the surfactants No1 and No2 of the present invention are other surfactants No3 to No7.
Compared with, the water separation is remarkably small and it has excellent oil-in-water emulsification performance.

[0042]

[Table 1]

Example 2 Mixtures containing 1,4-sorbitan caprylic acid monoester and diester in various proportions were prepared, and the emulsification performance thereof was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0044]

[Table 2]

Example 3 Mixtures containing 1,4-sorbitan capric acid monoester and diester in various proportions were prepared, and the emulsification performance thereof was evaluated in the same manner as in Example 1. Table 3 shows the results.

[0046]

[Table 3]

Example 4 Monoester A containing 1,4-sorbitan caprylic acid ester and capric acid ester in a weight ratio of 1: 1.
And a mixture containing 1,4-sorbitan caprylic acid diester and capric acid diester in a weight ratio of 1: 1 at various ratios were prepared, and the emulsification performance thereof was evaluated in the same manner as in Example 1. did. The results are shown in Table 4.

[0048]

[Table 4]

Example 5 Candida antarctic
a) Neutral thermostable immobilized lipase sp-435 (N)
OVO company) 100 mg, sorbitol dehydration condensate A2.
0 g (12.6 mmol), methyl caprylate 4.0 g
(25.2 mmol) and 6 g of Molecular Sieves 5A (manufactured by Junsei Kagaku Co., Ltd.) were placed in a 100 ml Erlenmeyer flask with a ground stopper, and 20 ml of an organic solvent (3-methylpyridine) was added thereto, and the mixture was heated at 60 ° C for 5 hours. The reaction was carried out at a reaction rate of 98% under shaking conditions of 200 rpm. The reaction solution thus obtained was filtered, and after separating the molecular sieve and the immobilized lipase, the organic solvent and fatty acid methyl ester in the filtrate were removed under reduced pressure to obtain a caprylic acid esterified product of a sorbitol dehydration condensation product. . The ratio of the monoester of monocaprylic acid to the diester in the esterified product obtained as described above was 82:18, and no triester was contained in the esterified product. The composition of the sorbitol dehydration condensate A is shown in the following table.

[0050]

[Table 5]

Example 6 The reaction was performed in the same manner as in Example 5 except that 25.2 mmol of methyl caprylate was used instead of 25.2 mmol of methyl caprylate, and the reaction rate was 98%. The weight ratio of the monoester and the diester of capric acid in the esterified product was 81:19, and no triester was contained in the esterified product.

Comparative Example 1 The reaction was carried out in the same manner as in Example 5 except that 25.2 mmol of methyl laurate was used instead of 25.2 mmol of methyl caprylate, and the reaction rate was 98%. The weight ratio of lauric acid monoester to diester in the esterified product was 75:25, and no triester was contained in the esterified product.

Comparative Example 2 The reaction was carried out in the same manner as in Example 5 except that 25.2 mmol of methyl stearate was used instead of 25.2 mmol of methyl caprylate, and the reaction rate was 91%. The weight ratio of stearic acid monoester and diester in the esterified product was 69:31, and no triester was contained in the esterified product.

Comparative Example 3 The sorbitol dehydration condensate A shown in Example 5 was reacted with methyl caprylate at a reaction rate of 95% by a conventional method using sodium hydroxide as a catalyst. The weight ratio of the monoester, diester and triester of caprylic acid in the esterified product was 50:38:12.

Comparative Example 4 The sorbitol dehydration condensate A shown in Example 5 was reacted with methyl caprate at a reaction rate of 94% by a conventional method using sodium hydroxide as a catalyst. The weight ratio of the monoester, diester and triester of caprylic acid in the esterified product was 44:42:14.

The emulsification performance of the products obtained in Examples 5 to 6 and Comparative Examples 1 to 4 was evaluated in the same manner as in Example 1. Table 6 shows the results.

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[Table 6] * Phase change and become w / o.

Example 7 Sample No. 3 in Example 3 was used. A coffee beverage was compounded using samples 3-7. The compounding composition is shown in Table 7. As a result, a stable emulsion was obtained in the coffee beverage composition.

[0059]

[Table 7]

Example 8 Sample No. 3 in Example 3 was used. A coffee whitener was compounded using samples 3-7. The compounding composition is shown in Table 8. As a result, a stable emulsion was obtained in the coffee whitener composition.

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[Table 8]

Example 9 Sample No. 3 in Example 3 was used. A milk drink was compounded using samples 3-7. The compounding composition is shown in Table 9. As a result, a stable emulsion was obtained in the milk beverage composition.

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[Table 9]

Example 10 An example of a composition using oil-soluble vitamin E as a chemical emulsifier is shown below. (Component) (wt%) Tocopherol acetate 4 sorbitan ester (Sample No. 3-10) 2 Propylene glycol 10 D-sorbitol liquid 3 Sodium citrate 0.2 Citric acid 0.1 Deionized water 80.7 Vitamin of the above composition When the E emulsion was prepared, this emulsion also had good stability.

Example 11 A composition using manneb (manganese ethylene bis dithiocarbamate) as an agricultural biocidal active substance as an agrochemical emulsifier is shown below. (Component) (% by weight) Manneb 41 propylene glycol 5 sorbitan ester (Sample No. 3-10) 4 deionized water 50 To the above composition, glass beads of 2 mmφ were added in an equal amount, and wet-ground, and then glass beads were added. After removal, a stable emulsion of Manneb was obtained.

Example 11 (Detergent Example) 1,4-sorbitan having a caprylic acid monoester / diester weight ratio of 70/30 and 1,4-sorbitan having a capric acid monoester / diester weight ratio of 80/20, Moreover, the ratio of caprylic acid ester / capric acid ester is 50/50 and the triester content is 3% by weight.
Sorbitan ester samples prepared below, sorbitan myristic ester sample for comparison (mono / di = 5
/ 5) and sucrose ester sample (C ₁₂ / C ₁₆ = 1/1,
Mono / di / tri = 4/3/3) was used to prepare and evaluate a household dishwashing detergent having the component composition (% by weight) shown in Table 9. The results are shown below. It has been found that the composition containing the above sample has no feeling of tightness on the hand skin after washing, is mild to the hand, and has the washing power and the washing power required as a base wash.

[Evaluation Method] Evaluation Method for "Tightening" Feeling of Hand Skin After soaking the hand in a 10% by weight aqueous solution of a cleaning agent for 5 minutes, rinsing with running water and drying the hand with a towel, "tightening" feeling Was sensory-evaluated based on the following criteria. The score was the average of 5 panelists. Here, the "tightening" feeling of the hand skin means that the water content of the skin is lost and a feeling of twitching occurs.

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Detergency 2 g of a detergent was weighed on a sponge (trade name ScotchBright, manufactured by Sumitomo 3M Limited) containing 38 g of tap water in advance, put on the palm and rubbed lightly 5 times. Next, five flat plates (diameter 20 cm) coated with 0.5 g of butter were washed with the above sponge. After thoroughly rinsing by allowing tap water to flow down, the dish was erected vertically, and the water repellency up to 5 seconds later was observed and evaluated according to the following criteria. Evaluation criteria: ○ A water film is uniformly spread over one surface and gets wet △ A water repellency is observed on a part of the dish surface, and an oil film remains on a part × A water repellency is observed on the entire surface

Foaming power An aqueous solution containing 0.15% by weight of a detergent was prepared, and 3 liters thereof were placed in a vat having a diameter of 30 cm and a depth of 12 cm,
At a liquid temperature of 25 ° C., the operation of compressing an air-containing sponge in the liquid is repeated 10 times, and after bubbling, 0.5 g of butter is applied to each side of the plate 10 times and the back side 5 times each. The number of dishes that can be washed by rubbing with a sponge to a foam height of 3 mm was regarded as the foaming property.

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[Table 9]

Example 12 (Shampoo) (Components) (% by weight) Ammonium lauryl sulfate 15 Palm oil fatty acid amide propyl betaine 10 Sorbitan ester (Sample No. 3-10) 10 Palm oil fatty acid diethanolamide 4 Clodaphos SG (PO5) Mol, EO10 mol cetyl phosphate) 2 acrylate 1000 (lanolin fatty acid PEG ester) 3 deionized water 56 A shampoo having the above component composition was produced. This shampoo had no squeaky feeling during washing and had a good feel after drying.

Example 13 (Body shampoo) (Component) (wt%) Sodium α-olefin sulfonate 6 Palm oil fatty acid amide propyl betaine 3 sorbitan ester (Sample No. 3-10) 6 Potassium myristate 10 Deionized Water 75 A body shampoo having the above component composition was produced. This body shampoo had a good feel on the skin after use.

An example of a composition composed of only food additives as a food cleaning agent is shown below. (Component) (wt%) Sorbitan ester (Sample No. 3-10) 15 Sodium citrate 10 Gluconic acid 5 Propylene glycol 1 Ethanol 9 Carboxymethylcellulose (CMC) 0.15 Deionized water 59.85 For food of the above component composition A detergent was produced. Although this detergent has a slightly low foaming property, it has a high stability and a detergency as a food additive composition.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C11D 1/68 // A23L 1/035 A61K 47/14 H (72) Inventor Kenji Isobe Head office Sumida-ku, Tokyo 1-3-7 Lion Co., Ltd. (72) Inventor Ryozo Iwasaki 1-3-7 Hongo Main Office, Sumida-ku, Tokyo Lion Corporation

Claims (8)

[Claims] 1. A monocaprylic acid ester and / or monocapric acid ester of at least one polyhydric alcohol selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, and 1,5-sorbitan, 1. ，
A mixture of at least one polyhydric alcohol selected from 4-sorbitan and isosorbide with dicaprylic acid and / or dicapric acid ester, and substantially containing the tricaprylic acid ester and / or tricapric acid ester of the polyhydric alcohol. A surfactant composition characterized in that it is absent or its content is 5% by weight or less, and the weight ratio of the monoester and diester is in the range of 3/7 to 9/1. 2. A mixture of at least one polyhydric alcohol monocaprate ester and dicaprate ester selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, wherein said polyhydric alcohol tricaprin is used. The acid ester is substantially not contained or the content thereof is 5% by weight or less, and the weight ratio of the monocapric acid ester to the dicapric acid ester is 3/7.
The surfactant composition is in the range of 9/1. 3. The surfactant composition according to claim 1, wherein the polyhydric alcohol contains 50% or more of 1,4-sorbitan. 4. An oil-in-water emulsion of an oil component obtained by emulsifying an oil component in water in the presence of the surfactant composition according to claim 1. 5. The oil-in-water emulsion according to claim 4, wherein the oil is an edible oil or a cosmetic oil. 6. A detergent comprising the surfactant composition according to claim 1. 7. The cleaning agent according to claim 6, which contains an anionic active agent. 8. Among at least one polyhydric alcohol selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, and among caprylic acid, capric acid, caprylic acid lower alkyl ester and capric acid lower alkyl ester. The method for producing a surfactant composition according to claim 1, wherein at least one fatty acid selected from the above and / or its lower alkyl ester is reacted in an organic solvent using a neutral thermostable lipase.