JP3487881B2 - Surfactant - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant having a high ability to reduce surface tension, and it is used as a food additive or cosmetic for the purposes of emulsification, solubilization, dispersion, washing, anticorrosion, lubrication, antistatic and wetting. It can be used as a commercial, pharmaceutical and industrial surfactant.

[0002]

2. Description of the Related Art Conventionally, various compounds such as polyoxyethylene alkyl ethers have been used as emulsifying or solubilizing agents.
Polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene alkylphenyl ether and other non-ionic surfactants of ethylene oxide type, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, polyglycerin condensed ricinoleic acid Known food-grade surfactants such as esters. Among them, polyglycerin fatty acid ester and polyglycerin condensed ricinoleic acid ester are the most useful surfactants because they are safe to humans and the environment and have high versatility because a variety of compositions can be obtained.

[0003]

Polyglycerin used as a raw material for polyglycerin fatty acid ester or polyglycerin condensed ricinoleic acid ester is generally dehydrated and condensed by heating glycerin as a raw material in the presence of a catalyst such as sodium hydroxide, and if necessary. It is obtained by purification by distillation, decolorization, deodorization, ion exchange resin treatment, etc. The end point of dehydration condensation is usually determined by the result of measuring the hydroxyl value. The polyglycerols on the market are called tetramer polyglycerin hexamer polyglycerin and decamer polyglycerin according to the average degree of polymerization calculated from the hydroxyl value. However, it is actually a mixture of various glycerin polymers having a degree of polymerization of 1 to 10 or more. Generally, in the case of synthesizing an ester by esterification reaction of these polyglycerin and fatty acid, the reactivity is different depending on the degree of polymerization of glycerin, and polyglycerin having a low degree of polymerization is selectively esterified. As a result, the obtained ester is a mixture of a low polymerization degree polyglycerol ester having an ester bond with more fatty acids than the target and an unreacted high polymerization degree polyglycerol having no ester bond. Therefore, the emulsifying and solubilizing power originally possessed cannot be exhibited. For example, when producing useful substances such as fat-soluble vitamins such as vitamin E and carotene as beverages, it is not possible to solubilize transparently with existing food-grade surfactants, and it is possible to produce products with good storage stability. There wasn't. Further, other surfactants, for example, polyoxyethylene sorbitan ester, can be used in the production of pharmaceuticals and cosmetics, but when producing useful substances such as fat-soluble vitamins such as vitamin E and carotene as a beverage, they are not sufficient alone. Since it does not have sufficient solubilizing ability, an auxiliary agent such as ethanol is required. Therefore, when it is consumed in large quantities, it becomes drunk, which is a social problem especially for young people.
Furthermore, in the cosmetics industry, polyoxyethylene derivatives are used as hydrophilic emulsifiers, but there are problems with safety such as skin irritation and alternatives are being sought, but conventional polyglycerin esters and sucrose fatty acids have been demanded. Ester has insufficient performance and cannot be replaced.

[0004]

[Means for Solving the Problems] The present inventors have accomplished the present invention as a result of earnest research in view of the above points. That is, the present invention relates to a polyglycerin having a low degree of polymerization and having a narrow distribution of the degree of polymerization, and a surfactant comprising a polyglycerin fatty acid ester obtained by using a fatty acid as a raw material. 70% polyglycerin
The present invention relates to "a surfactant containing an ester of polyglycerin and a fatty acid containing the above". The present invention will be described in detail below. The surfactant of the present invention is a substance added for the purpose of stabilization when mixing a lipophilic substance and a hydrophilic substance,
It has a strong surface activity. These substances have both a lipophilic functional group and a hydrophilic functional group in the molecule, and reduce the surface tension of water. The polyglycerin of the present invention is a substance obtained by dehydration condensation of glycerin or the like, which has a hydroxyl group and an ether bond in the molecule and has no other functional group. Polyglycerin is usually obtained by heating glycerin under normal pressure or reduced pressure in the presence of an alkaline catalyst. Depending on the purpose of use, it removes low-boiling components through gas such as nitrogen and steam, and ion exchange resins, ion exchange membranes, etc. Depending on the boiling point by removing ionic components such as used catalysts, removing color components and odor components by using an adsorbent such as activated carbon, reducing treatment by hydrogenation, or by molecular distillation or rectification. It is purified by fractionation.

In general, when polyglycerin is produced from glycerin as a raw material, intramolecular condensation or 6
Polyglycerin obtained by synthesizing and purifying glycidol, epichlorohydrin, monochlorohydrin or the like as a raw material is preferable so that undesired by-products such as a member ring and an 8-membered ring are often generated. Furthermore, when reacting polyglycerin and fatty acids,
In general, low molecular weight polyglycerin has a higher reactivity with fatty acids than high molecular weight polyglycerin, and therefore uniform ester cannot be produced when polyglycerin having a wide molecular weight distribution is used as a raw material. Therefore, polyglycerin having a molecular weight distribution as narrow as possible is preferable, and for example, it can be obtained by a dehalogenation alkali metal salt reaction using glycerin or a partial alcoholate of a polymer thereof and a halogenated hydrocarbon or an oxyhalogenated hydrocarbon as raw materials. As an example of the production method, in the first step, as 1 mol of diglycerin, 1 mol of sodium hydroxide is added and dehydrated by heating to produce diglycerin monoalcolate, and 2 mol of diglycerin monoalcolate obtained in the second step is added. When 1 mol of dichlorohydrin is added and heated, polyglycerin 1 with a degree of polymerization of 5 easily
A mole is obtained.

Similarly, if polyglycerin having a degree of polymerization of 3 is used instead of diglycerin, polyglycerin having a degree of polymerization of 5 can be obtained, and if polyglycerin having a degree of polymerization of 5 is used instead of diglycerin, polyglycerin having a degree of polymerization of 11 can be obtained. it can.
Further, since the viscosity becomes high during these steps, coexistence of various solvents is advantageous in industrialization. When selecting these solvents, it is necessary that they do not interfere with the reaction or that side reactions do not occur, but in reality, the glycerol or its polymer used as the starting material for the reaction is charged in excess and dehalogenated. It is convenient to remove free glycerin or its polymer after the alkali metal salt reaction, and it is not necessary to give special consideration to the residual solvent. For example, in producing polyglycerin having a degree of polymerization of 5, diglycerin may be reacted in excess and finally distilled at 0.5 Torr or lower and 190 ° C. or higher. At this time, it is preferable that the amount of remaining diglycerin is small, but if it is 30% or less, it is practically sufficient. Alternatively, alternatively, 2 mol of monochlorohydrin can be used instead of 1 mol of dichlorohydrin to proceed with the same reaction. In this case, the obtained polyglycerin is larger than the starting glycerin or its polymer by one degree of polymerization. With respect to the degree of polymerization of the polyglycerin of the present invention, if the degree of polymerization is low, a sufficient surface-active effect cannot be obtained. Therefore, polyglycerin containing 70% or more of polyglycerin having a degree of polymerization of 4 or more is preferable. If the degree of polymerization is too high, the viscosity will be so high that handling problems will occur.
Polyglycerin containing 60% or more of 11 or more polyglycerin is more preferable. Further, as described above, the narrower the molecular weight distribution is, the more preferable is polyglycerin containing 40% or more of polyglycerin having a polymerization degree of 5, 7 or 11.

[0007] Conventionally, the degree of polymerization of polyglycerin means that when glycerin is dehydrated and condensed, 2 moles of hydroxyl groups in the molecule are converted into 1 mole of ether bond, and the hydroxyl value is measured by the standard oil and fat test method to determine the average value. It has been understood as a calculation of the degree of polymerization. This is because polyglycerin that has been supplied to the market in the past has a wide molecular weight distribution from low to high molecular weights, and has a complicated composition such as cyclic compounds that are dehydrated and condensed intramolecularly, so it is possible to quantify each component. Because it was virtually impossible. However, using such a method for measuring the degree of polymerization is inappropriate in considering the properties of polyglycerin esters obtained from these polyglycerins. Therefore, the degree of polymerization of polyglycerin in the present invention was determined by forming a polyglycerin derivative and then performing separation and quantification by the GC method (gas chromatography). Analysis by the GC method is performed at 100 ° C using a fused silica capillary tube in which a low-polarity liquid phase such as methyl silicon is chemically bonded.
It can be easily carried out by conducting a temperature increase analysis of 10 ° C./min up to 250 ° C. Further, the identification of the degree of polymerization of the peak on the gas chromatogram is carried out by, for example, introducing a gas chromatograph into a double-focusing mass spectrograph, ionizing and measuring by a method such as chemical ionization, and then measuring the molecular weight of its parent ion. This can be easily carried out by obtaining the molecular weight of the peak on the gas chromatogram and then obtaining the degree of polymerization of glycerin from the chemical formula.

The fatty acid of the present invention is a general term for substances containing a carboxylic acid as a functional group, which is obtained by hydrolyzing fats and oils extracted from natural animals and plants and is obtained by separating or purifying without separation, and is particularly limited. Not a thing. Alternatively, it may be a fatty acid obtained by chemically synthesizing petroleum as a raw material. Alternatively, those obtained by reducing these fatty acids by hydrogenation or the like, condensed fatty acids obtained by condensation polymerization of fatty acids containing hydroxyl groups, and polymerized fatty acids obtained by heat polymerization of fatty acids having unsaturated bonds may also be used. Good. The selection of these fatty acids may be appropriately determined in consideration of the desired product effect. Natural fatty acids derived from animals and plants are preferable in consideration of environmental issues, and fatty acids having two or more unsaturated double bonds are preferable if stability over time is desired. The polyglycerin of the present invention and the fatty acid are esterified by a known method. For example, the esterification can be carried out under normal pressure or reduced pressure under an alkali catalyst, an acid catalyst or a non-catalyst. Further, the amounts of polyglycerin and fatty acid charged must be appropriately selected depending on the purpose of the product. For example, in order to obtain a hydrophilic surfactant, it is sufficient to calculate the weight so as to be equimolar by the calculation from the hydroxyl value of polyglycerin and the molecular weight of fatty acid, and charge it.
To obtain a lipophilic surfactant, the number of moles of fatty acid may be increased. The polyglycerin fatty acid ester obtained may be purified according to the usage requirements of the product. The purification method may be any known method and is not particularly limited. For example, adsorption treatment with activated carbon or activated clay, treatment under reduced pressure using water vapor, nitrogen, etc. as a carrier gas, washing with acid or alkali, molecular distillation, etc. It may be purified.

Other components can be added to the polyglycerin fatty acid ester of the present invention to facilitate the handling of the product. For example ethanol to reduce the viscosity of the product,
Propylene glycol, glycerin, polyglycerin,
You may melt | dissolve or emulsify by adding 1 type, or 2 or more types, such as water, liquid sugar, and fats and oils. Alternatively, a polysaccharide such as lactose or dextrin, or a protein such as caseinate may be added to obtain a powder. Depending on the purpose of use, the polyglycerin fatty acid ester of the present invention may be mixed with another surfactant to prepare a surfactant preparation. Examples of usable surfactants include nonionic surfactants such as glycerin fatty acid ester, propylene glycol fatty acid ester, and polyglycerin fatty acid ester, amphoteric surfactants, anionic surfactants, and cationic surfactants.
The polyglycerin fatty acid ester of the present invention may be added with other components constituting the final product to form an intermediate product. For example, one or more of oleic acid, isostearic acid, palmitic acid, lauric acid, capric acid, caprylic acid, condensed ricinoleic acid, condensed 12-hydroxystearic acid and an ester of equimolar amount of polyglycerin and vitamin E can be used.
And other oil-soluble vitamins, oil-soluble pigments such as beta-carotene, and oil-soluble physiologically active substances such as highly unsaturated fatty acids are mixed to produce water-soluble oil-soluble vitamins, oil-soluble pigments, and oil-soluble physiologically active substances. You can also The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[0010]

【Example】

Example 1 3300 g of diglycerin in a 5-liter four-necked flask
Then, 800 g of a 50% aqueous sodium hydroxide solution was added, and the mixture was heated to 140 ° C. while removing water under a nitrogen stream. After the water was distilled off, 640 g of dichlorohydrin was added dropwise over 2 hours. After dropping, the mixture is stirred at 120 ° C. for 2 hours. After removing excess diglycerin by molecular distillation, the mixture was diluted with water, decolorized and desalted with activated carbon and an ion exchange resin, and water was removed to obtain polyglycerin. This product is converted to TMS, and the above-mentioned GC
According to the method
%Met.

Example 2 500 g of ricinoleic acid and 0.8 g of sodium hydroxide were placed in a 1-liter four-necked flask and reacted at 210 ° C. while removing generated water under a nitrogen stream to obtain condensed ricinoleic acid. The acid value of this condensate was 95. 30 g of this condensed ricinoleic acid and the polyglycerin 2 obtained in Example 1
70 g was put into a 500 ml four-necked flask,
The reaction was carried out at 250 ° C. while removing the generated water under a nitrogen stream to obtain polyglycerin condensed ricinoleic acid ester. The acid value of this ester was 0.3.

Example 3 500 g of ricinoleic acid and 0.8 g of sodium hydroxide were placed in a 1-liter four-necked flask and reacted at 210 ° C. while removing generated water under a nitrogen stream to obtain condensed ricinoleic acid. The acid value of this condensate was 33.8. 60.5 g of the polyglycerin obtained in Example 1 was added thereto, and the reaction was carried out at 250 ° C. while removing the generated water under a nitrogen stream to obtain a polyglycerin condensed ricinoleic acid ester. The acid value of this ester was 0.2.

Example 4 210 g of the polyglycerin obtained in Example 1, 90 g of isostearic acid and 0.1 g of tripotassium phosphate were placed in a 500 ml four-necked flask and the resulting water was removed under a nitrogen stream at 250 ° C. After the reaction, 0.3 ml of phosphoric acid was added after the reaction to obtain polyglycerin isostearic acid ester. The acid value of this ester was 1.2.

Example 5 Polyglycerin stearic acid ester was obtained from 225.2 g of polyglycerin obtained in Example 1 and 74.2 g of stearic acid by the same process as in Example 4. The acid value of this ester was 1.0.

Example 6 Polyglycerin oleic acid was obtained from 225.2 g of polyglycerin obtained in Example 1 and 74.2 g of oleic acid by the same steps as in Example 4. The acid value of this ester was 1.0.

COMPARATIVE EXAMPLE 1 Instead of the polyglycerin obtained in Example 1, Taiyo Kagaku Great Oil # 500 (glycerin 8%, diglycerin 20%, polyglycerin 20% having a degree of polymerization 3 and polymerization degrees 4 to 11) was used. Polyglycerin condensed ricinoleic acid ester was obtained by the same process as in Example 2 except that polyglycerin 49% and polyglycerin 3% having a degree of polymerization of more than 11 were used.

Comparative Example 2 A polyglycerin-condensed ricinoleic acid ester was obtained by the same process as in Example 3 except that Great Oil # 500 manufactured by Taiyo Kagaku was used instead of the polyglycerin obtained in Example 1.

Comparative Example 3 Polyglycerin isostearic acid ester was obtained by the same procedure as in Example 4 except that Great Oil # 500 manufactured by Taiyo Kagaku was used in place of the polyglycerin obtained in Example 1.

Comparative Example 4 Polyglycerol stearic acid ester was obtained by the same procedure as in Example 5 except that Great Oil # 500 manufactured by Taiyo Kagaku was used instead of the polyglycerin obtained in Example 1.

Comparative Example 5 A polyglycerin oleic acid ester was obtained by the same steps as in Example 6 except that Great Oil # 500 manufactured by Taiyo Kagaku was used instead of the polyglycerin obtained in Example 1.

Test Example 1 Example 2 was added to 0.13 part by weight of commercially available 80% pure vitamin E.
0.4 parts by weight of the polyglycerin fatty acid ester obtained in (4) was added, and heated and mixed well. An aliquot of 0.063 parts by weight was taken, 100 ml of warm water was added and well stirred, and the turbidity was measured as an absorbance at a wavelength of 650 nm with a spectrophotometer. When the polyglycerin fatty acid ester obtained in Comparative Example 1 was replaced by the polyglycerin fatty acid ester obtained in Example 2, polyoxyethylene monolaurate ester (10 mol adduct) and sucrose monolaurate ester were similarly tested. The solution solubilized with the polyglycerin fatty acid ester obtained in Example 2 was completely transparent and had an absorbance of 0.007, whereas the polyglycerin fatty acid ester obtained in Comparative Example 1 had an absorbance of 0. 305 and sucrose lauric acid ester were 0.205, which were both cloudy, and polyoxyethylene monolauric acid ester was 0.083, which was semitransparent.

Test Example 2 1.2 parts by weight of the polyglycerin condensed ricinoleic acid ester obtained in Example 3 was dissolved in 280 parts by weight of soybean white squeezing oil, and 280 parts by weight of a 10% sodium chloride solution was stirred with a homomixer at 5000 rpm. And then 10,000 rp
The mixture was stirred at m for 2 minutes to obtain a W / O emulsion. Example 3 Comparative example 2 instead of polyglycerin condensed ricinoleic acid ester
The polyglycerin condensed ricinoleic acid ester obtained in 1 above was tested in the same manner to obtain a W / O emulsion. When both emulsions were stored at 60 ° C. for 3 days, the aqueous layer was separated in the polyglycerin condensed ricinoleic acid ester obtained in Comparative Example 2, while the polyglycerin obtained in Example 3 was observed. No separation of the aqueous layer was observed with the condensed ricinoleic acid ester.

Test Example 3 1.5 parts by weight of the polyglycerol isostearic acid ester obtained in Example 4 was dissolved in 100 parts by weight of water, and 50 parts by weight of jojoba oil was added with stirring with a homomixer at 5000 rpm, and then at 10,000 rpm. The mixture was stirred for 2 minutes to obtain an O / W emulsion. Example 4 A polyoxyethylene sorbitan monostearate (10 mol adduct) was used in place of polyglycerol isostearate to obtain an O / W emulsion in the same manner.
When added to 00 ml, the emulsion using polyglycerin isostearic acid ester was uniformly dispersed in water, whereas polyoxyethylene sorbitan monostearate ester was observed to have an oil layer separated on the surface of water.

Test Example 4 To 100 parts by weight of water, 1 part by weight of the polyglycerin stearic acid ester obtained in Example 5 was added and dissolved by heating at 60 ° C. While stirring with a homomixer at 5000 rpm, 100 parts by weight of soybean white squeezing oil heated to 60 ° C. was added,
Then, the mixture was stirred at 10,000 rpm for 2 minutes to obtain an O / W emulsion. The polyglycerin stearic acid ester obtained in Comparative Example 4 was also treated in the same manner to obtain 60 parts of the two emulsions obtained.
When left at 12 ° C. for 12 hours, separation of the oil layer was observed with the polyglycerin stearic acid ester obtained in Comparative Example 4, whereas no separation was observed with the polyglycerin stearic acid ester obtained in Example 5. It was

Test Example 5 20 parts by weight of glycerin was added to 10 parts by weight of the polyglycerin oleate obtained in Example 6 and heated to 50 ° C. While stirring with a glass rod, 80 parts by weight of silicon oil heated to 50 ° C. was gradually added to obtain an emulsified composition. When this was stored at 40 ° C. for 1 month, no change was observed. On the other hand, when the polyglycerin oleic acid ester and the polyoxyethylene sorbitan monooleic acid ester (10 mol addition product) obtained in Comparative Example 5 were operated in the same manner, separation of the oil layer occurred during the addition of the silicone oil and the emulsified composition was obtained. It could not be prepared.

[0026]

According to the present invention as proved in the above examples, the surfactant of the present invention can greatly reduce the surface tension of water, which is impossible in the fields of foods, pharmaceuticals and cosmetics until now. Obviously, it becomes possible to produce a completely solubilized product and a stable emulsion that have been produced.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI // A61K 7/00 A61K 7/00 N (56) References JP-A-6-192065 (JP, A) JP-A-60- 262827 (JP, A) JP 2-177848 (JP, A) JP 60-120800 (JP, A) JP 3-81252 (JP, A) JP 63-56585 (JP, A) JP-A-5-78279 (JP, A) JP-A-6-166658 (JP, A) JP-A-6-41007 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B01F 17/44 A23L 1/035 C09K 3/16 C10M 105/38 C11D 1/68 A61K 7/00

Claims (4)

(57) [Claims] 1. 70% of polyglycerin having a degree of polymerization of 4 or more
A surfactant containing the ester of polyglycerin containing 40% or more of polyglycerin having a degree of polymerization of 5 and fatty acid, which is the above-described polyglycerin. 2. 70% of polyglycerin having a degree of polymerization of 4 or more
A surfactant containing an ester of a polyglycerin containing 40% or more of polyglycerin having a degree of polymerization of 7 and a fatty acid, the polyglycerin containing the above. 3. 70% of polyglycerin having a degree of polymerization of 4 or more
A surfactant containing the ester of polyglycerin containing 40% or more of polyglycerin having a degree of polymerization of 11 and fatty acid, which is the above-mentioned polyglycerin. 4. The polyglycerin is a polyglycerin obtained by a dehalogenation alkali metal salt reaction using a partial alcoholate of glycerin or a polymer thereof and a halogenated hydrocarbon or an oxyhalogenated hydrocarbon as raw materials. The surfactant according to 3.