JPH0420037B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) This invention relates to unsaturated oils and fats for cosmetics, and its purpose is to maintain the temperature at 50±2°C immediately after refining as well as at least after refining.
The purpose of the present invention is to provide unsaturated oils and fats for cosmetics that maintain a peroxide value of 20 or less even after 30 days have passed. In general, there are many types of cosmetic products such as lipsticks and vanishing creams, and each type is formulated with a combination of different raw materials, and the types of antioxidants added to cosmetic products vary. Selected to best suit multiple raw material types. Furthermore, since it is used directly on the skin, the amount of antioxidant added is as small as the formulation allows. However, since it is not known what other raw materials will be mixed with general-purpose raw materials immediately after purification, it is not possible to predict the future combination and add an appropriate antioxidant in advance for storage. The raw material immediately after its purification should be stored without or with a trace amount of antioxidant added. This invention was made based on this idea, and aims to provide general-purpose unsaturated oils and fats for cosmetics that can be preserved without adding antioxidants even after at least 30 days have elapsed from purification to formulation. . (Background of the Invention) In general, unsaturated oils and fats exist widely in nature with the structure of unsaturated triglyceride oil or unsaturated wax-type ester oil, and although they have a relatively large number of carbon atoms, they are liquid due to the degree of unsaturation. Alternatively, it is soft and has many uses, and unsaturated synthetic oils (unsaturated wax-type ester oils) such as oleyl oleate are also widely used as raw materials for cosmetics. However, many unsaturated fats and oils are extremely unstable, and as mentioned above, unsaturated fats and oils include triglycerides and wax-type esters.
The latter is more easily oxidized than the former, and the smell is likely to return. Furthermore, in recent years, it has been said that oils and fats that have changed over time can cause skin damage, and that POV (peroxide value) of 20 or more is not desirable. Therefore, stabilization of unsaturated wax-type esters as raw materials for cosmetics has been a major issue in the industry. (Prior art) These unsaturated oils and fats can be purified from natural oil and fat raw materials or synthetic crude oils by oxidative bleaching using a batch method, or by adding activated clay and/or activated carbon, heating and stirring, and then filtering them out. Or, if necessary, it is commonly carried out industrially to add means such as wintering or molecular distillation to these processes, and edible oils and fats are commercialized by such refining and used in various foods. Addition of antioxidants for refined oils and fats is considered an effective means for improving stability. In fact, such conventional technology is called "oil chemistry".
(edited by Japan Oil and Fat Manufacturers Association) magazine discloses hydrogenation treatment as a technology for refining raw material oils and fats, and also includes alkali purification and activated clay adsorption treatment (Volume 19) to remove catalyst poisons before hydrogenation treatment. No. 8, p. 26). Furthermore, pages 36 to 39 of the issue of the "Oil Chemistry" magazine
Page discloses a technique for performing the activated clay adsorption treatment before and after hydrogenation treatment, and in fact, refined unsaturated oils and fats such as edible unsaturated oils and fats (unsaturated triglyceride oils) are manufactured by such refining methods. has been done. However, these conventional refining methods take advantage of the characteristics of unsaturated oils and fats, while highly improving their unique odor and color, especially their stability against oxidative deterioration over time, to produce unsaturated oils and fats for cosmetics. I can't. In particular, unsaturated wax-type ester oils are generally indigestible by humans and can cause diarrhea or seborrhea if eaten. Due to its stability, no known technology has yet found a solution. The reason for this is that the activated clay treatment that is performed before the hydrogenation treatment is performed simply to remove catalyst poisons, so its purpose is different. This is because clay treatment is usually an additive mixing method that requires a filtration process. Therefore, an example of an attempt to overcome these drawbacks is proposed in Japanese Patent Publication No. 42-23589 as ``Advanced Purification and Deodorization Method for Edible Hydrogenated Oil (Saturated Triglyceride Oil)''. Indeed, this method is not a conventional method of simply mixing activated clay and hydrogenated fats and oils and then filtering it, but a technology in which the hydrogenated fats and oils are passed through a layer of activated silicic acid. Because of this, the degree of purification is improved over that of the prior art. In fact, this publication describes a refined oil with a yield rate of 90% and sufficient quality as an edible fat (saturated triglyceride oil). However, even though the refined unsaturated oils and fats produced by this proposed method have sufficient stability as edible oils and fats, they do not change color immediately after purification or even after 30 days at 50°C without adding any antioxidants. This could not be said to be sufficient as an unsaturated oil or fat for cosmetics, which needs to be stored without returning to its odor. In particular, the stability of unsaturated wax-type ester oil cannot be achieved using only the above-mentioned known techniques. In other words, the unsaturated oils and fats that have undergone the refining process may still retain the odor characteristic of crude oil, and over time, due to further oxidative deterioration, the so-called "odor return" occurs.
The phenomenon is remarkable, and the increase in peroxide value is usually difficult to improve, making refined oils and fats extremely unsatisfactory as unsaturated oils and fats for cosmetics. This tendency is particularly noticeable in orange roughy oil and fragrant whale oil, which are mainly oils and fats with an unsaturated wax type ester structure. Research on the stability of unsaturated oils and fats has been conducted for a long time, and the cause of their instability is a complex process triggered by the denaturation of the unsaturated bonds themselves, that is, the initial oxidation reaction in the presence of air, heat, light, and trace heavy metals. This is said to be based on the chain induction of oxidative decomposition and polymerization reactions. However, due to the degree of unsaturation of unsaturated fats and oils, hydrogenation treatment cannot be performed until they lose their liquid or soft characteristics. Therefore, even though unsaturated oils and fats are referred to as unsaturated fats and oils, it is natural that their stability varies greatly depending on the degree of unsaturation, the position of the unsaturated bond, geometric isomer, etc. Addition of an inhibitor can stabilize it for practical purposes, but linoleic acid, linolenic acid, etc. are difficult to put into practical use. Therefore, one method for stabilizing unsaturated fatty acids is to selectively remove trace or small amounts of polyene components with two or more unsaturated bonds, whether conjugated or non-conjugated, that exist in refined unsaturated fats and oils. There is a method of selectively hydrogenating the polyene component of unsaturated oils and fats in order to dramatically improve the sequestration and stability over time. However, in cases where particularly high quality is required, such as cosmetic raw materials, selectively hydrogenated oil is still insufficient due to the problem of residual odor, and more thorough decolorization, deodorization, and stability improvement are required. It was hot. For example, hardened beef tallow (saturated triglyceride oil) or purified stearic acid obtained from it still has a unique odor and is unavoidably used, but there is a strong demand in the industry for potentially improving its quality. Furthermore, the problem with this selective hydrogenation treatment method is that the problem of oxidation deterioration over time still remains, and the problem is that it cannot withstand long-term storage and quality deteriorates due to return of odor and coloring due to oxidation deterioration over time. It was hot. In fact, in the example of the draft example "Advanced purification and deodorization method for edible hydrogenated oil" in the above-mentioned Japanese Patent Publication No. 42-23589, hydrogenated edible hydrogenated oil is purified by passing through an activated silicic acid layer, and then further It is disclosed in Example (2) that the oil obtained by selectively hydrogenating and passing this fat and oil through the activated silicic acid layer again is even better in quality than the refined fat and oil produced by this draft example method even when used for human consumption. As mentioned above, this proposed method is a method for refining unsaturated fats and oils, in particular, the adsorption treatment is performed by dissolving fats and oils in n-hexane. In the process of treating fats and oils by passing them through an activated silicic acid layer, similar to the technology disclosed in Japanese Patent Application No. 53-102910, which is a conventional example, in which degummed vegetable oil is passed through an activated carbon layer at least once, adsorption is performed. It was an excellent treatment method. However, the method disclosed in Japanese Patent Publication No. 42-23589, in which the refined oil is selectively hydrogenated again and then subjected to adsorption treatment, also had the following drawbacks. In other words, the conditions for selective hydrogenation are insufficient,
Even though the sample iodine value is 81.6, the iodine value after hydrogenation is 75.8. Even if the oil is obtained through a treatment such that the iodine value after hydrogenation is 75.8, it is difficult to avoid an increase in peroxide value over time and it is sufficient as an edible oil. However, it is not suitable as unsaturated oils and fats for cosmetics, which need to be stored without changing color or returning odor even after 30 days at 50°C without adding antioxidants. Furthermore, since activated silicic acid, an adsorbent with excellent adsorption properties, is used, components other than the impurities that need to be removed may be adsorbed and removed, resulting in an extremely low yield of the final purified product at around 70%. However, it had the disadvantage that it was not suitable for industrial purification methods. In addition, all of these known techniques relate to methods for refining edible fats and oils (unsaturated triglyceride oil), and regarding unsaturated wax-type ester oil, which is more unstable than unsaturated triglyceride oil,
There is no specific description of oils and fats that maintain a peroxide value of 20 or less not only immediately after purification, but also at least 30 days after purification at 50°C, and the conditions for refining such oils and fats. However, it was not possible to solve the above-mentioned problems unique to cosmetic raw materials. (Solution) Therefore, the present inventors solved the problem without losing the liquid or soft properties characteristic of unsaturated oils and fats.
In addition, we have conducted extensive research into unsaturated oils and fats for cosmetics that can be preserved without adding antioxidants even after 30 days at 50°C. As a result, the present inventors found that an unsaturated ester oil of a higher alcohol and a higher fatty acid contains two or more double bonds in the hydrocarbon moiety of either or both of the higher alcohol and the higher fatty acid. By using an unsaturated ester oil which has been processed and also contains some peroxide as a raw material oil and fat, and refining this raw material oil and fat by a combination of a selective hydrogenation process and a column chromatographic purification process. obtained, not only immediately after purification, but also at least after purification.
Selected unsaturated oils and fats for cosmetics that maintain a peroxide value of 20 or less even after 30 days at 50±2℃, and the hydrocarbon moiety of a polyenoic fatty acid or/and polyenoic fatty acid alcohol that has two or more unsaturated bonds. This is a completed unsaturated oil and fat for cosmetics, which is characterized by being denatured into a monoene form, and by reducing some of the peroxide contained therein. This is due to the surprising discovery made by the inventors, namely, that unsaturated refined oils and fats can be produced by selective hydrogen treatment, and column chromatographic purification (refined by cyclic purification and batch purification). Compared to oils and fats that are obtained by refining alone (including both types of oils and fats), unsaturated oils and fats obtained by the combined refining of both under complex specific conditions according to the present invention can dramatically prevent oxidative deterioration over time. It is based on this knowledge. Specifically, there is no relationship between the selective hydrogenation treatment and the column chromatographic purification treatment;
This was obtained through a combination process under specific conditions. (Structure of the Invention) Examples of the unsaturated ester oil of higher alcohol and higher fatty acid used as starting materials in this invention include orange roughy oil, matcha whale oil,
Furthermore, oleyl oleate etc. are preferably used,
An unsaturated ester oil containing two or more double bonds in the hydrocarbon moiety of one or both of the higher alcohol and higher fatty acid and also contains some peroxide is used. The selective hydrogenation step carried out in this invention is:
It refers to a process in which a polyene fatty acid or/and a polyene aliphatic alcohol moiety having two or more unsaturated bonds is selectively modified into a monoene form, and at the same time, a certain amount of peroxide contained therein can be reduced. Preferred specific examples thereof are as follows. The pressurization conditions are 3 atm gauge pressure or less, heating temperature 100 to 200℃, and processing time 1 to 4 hours.
Any selective hydrogenation method in the presence of a catalyst may be sufficient, and as a specific example, it is desirable to use a nickel-based catalyst or a copper-chromium based catalyst, and the most desirable specific example is
An example is NIKKIN103B (manufactured by JGC Corporation). In addition, in this invention, it is desirable to add a small amount of catalyst, and the specific amount is about 2 to 3% by weight or less based on the unsaturated ester oil that requires reduction, and It may be determined by appropriately considering the degree of purification, type, hydrogenation conditions, etc. Further, in this invention, suitable adsorbents for use in the chromatographic purification step performed as a pre-treatment or post-treatment of the selective hydrogenation step are silica gel, alumina gel, activated alumina, aluminum silicate, and magnesium silicate. , activated clay, acid clay, zeolite, and mixtures thereof, and are appropriately selected depending on the type and quality of the raw material oil. Further, in the present invention, aliphatic hydrocarbons such as petroleum ether, n-hexane, and n-pentane, and halogenated hydrocarbons such as carbon tetrachloride are preferably used as the nonpolar solvent. Here, the column chromatographic purification process is
A method in which polar impurities are removed by passing unsaturated oils and fats dissolved in the non-polar solvent through an adsorption tower filled with the adsorbent at least once. The number of times of liquid passage may be determined depending on the type of unsaturated oil and fat, the required degree of purification, the type and characteristics of the nonpolar solvent, and the type and characteristics of the adsorbent. Finally, the solvent is distilled off from the recovered solution. As mentioned above, this column chromatographic purification step is carried out as a pre-treatment or post-treatment of the selective hydrogenation step. (Effects of the Invention) The present invention provides an unsaturated ester oil of a higher alcohol and a higher fatty acid, in which the hydrocarbon moiety of one or both of the higher alcohol and the higher fatty acid-protecting acid has two double bonds. The unsaturated ester oil containing the above-mentioned substances and some peroxides is used as a raw material oil and fat, and this raw material oil and fat is purified by a combination of a selective hydrogenation step and a column chromatographic purification step. obtained by
Unsaturated oils and fats for cosmetics that maintain a peroxide value of 20 or less immediately after purification as well as at least 30 days after purification at 50±2°C, and which have two or more unsaturated bonds and/or polyene fatty acids and/or polyene fats. These unsaturated oils and fats for cosmetics are characterized by selectively modifying the hydrocarbon moiety of group alcohols into monoenes and reducing some of the peroxides contained in them. play. That is, at least 50
Even after 30 days at °C, it can be stored without adding antioxidants, and even if it is combined with any other raw materials in the future, the most compatible antioxidant can be added to the minimum required amount at the time of compounding. It can be prepared by adding only a small amount, and can effectively prevent odor return and discoloration for a long period of time. It can be used directly on the skin and is extremely effective as a raw material for cosmetics in which color and fragrance are the most important factors. In addition, as shown in the examples below, in terms of resistance to oxidative deterioration over time, the stability over time of refined unsaturated oils and fats obtained by the selective hydrogenation step and the column chromatographic refining step alone is higher. Dramatic stability can be ensured. Hereinafter, the effects of this invention will be made clearer by showing examples. Examples 1 and 2 Orange roughy oil, which is an unsaturated wax-type ester oil that is transparent and orange in color and has a strong fish oil odor, was used as a raw material. This orange roughy oil had an acid value of 0.19, a saponification value of 102.8, and an iodine value of 89.5. This orange roughy oil was subjected to selective hydrogenation treatment under the conditions shown in Table 1 below.

[Table] Table 2 shows the properties of unsaturated oils and fats obtained by this selective hydrogenation treatment, and Table 2-1 shows the storage characteristics at 50±2℃.
Each is shown in the table.

【table】

[Table] As is clear from this Table 2-1, it was found that orange roughy oil treated only with selective hydrogenation deteriorated in a short period of time. Two samples each of 50 g of orange roughy treated oil obtained in Examples 1 and 2 (Example 1;
a, c, Example 2; b, d) were prepared and subjected to the following column chromatographic purification treatment. That is, N-hexane is used as a nonpolar organic solvent.
The solution was dissolved in 150 ml and passed through a column packed with 100 g of adsorbent, and then 200 ml of N-hexane was passed through the column. This eluate was passed several times to elute the refined oil, and then N-hexane was passed through the column.
- Hexane was distilled off to obtain a refined oil. The adsorbent used in this test, the yield, and the properties of the purified unsaturated oil and fat obtained are shown in Tables 3 and 4. Furthermore, the storage characteristics at 50±2°C are shown in Table 4-1.

【table】

【table】

[Table] Even after 30 days at 50°C, the unsaturated fats according to the present invention, which have been subjected to column chromatographic purification after selective hydrogenation, have a low peroxide value.
It was below 20. Three samples each (Example 1; e, g,
i, Example 2; f, h, j) were prepared and subjected to batch column chromatographic purification. Table 5 shows the type and yield of the adsorbent, and Table 6 shows its properties.

【table】

[Table] From the above results, the column chromatographic purification method (multiple passes) according to the present invention is superior to the column chromatographic purification method (single pass) according to the present invention. I understand. Examples 3 and 4 Unsaturated oils and fats are yellowish brown in color and have a strong characteristic odor.
Matcha whale oil, which is an unsaturated wax-type ester oil, was mainly used. Its properties are shown in Table 8, and its storage characteristics are shown in Table 8-1. Selective hydrogenation of this Macaron whale oil was carried out under the conditions shown in Table 7.

【table】

【table】

【table】

[Table] As shown in Table 8-1, it was found that the peroxide value of Macaroma whale oil treated only with selective hydrogenation increased within a short period of time, and the oil deteriorated. Two samples of 50 g of the selectively hydrogenated whale oil obtained in Examples 3 and 4 were each prepared. (Example 3: a, c, Example 4: b, d) This sample was dissolved in 150 ml of N-hexane as a non-polar organic solvent, passed through a column packed with 100 g of adsorbent, and further 200 ml of N-hexane. This eluate is circulated and purified oil is eluted. Furthermore, N-hexane was distilled off to obtain a refined oil. Adsorbents, yields and results are shown in Tables 9 and 10. The storage characteristics are shown in Table 10-1.

【table】

【table】

[Table] Table 10-1 After selective hydrogenation treatment as described above,
After column chromatographic purification,
Even after 30 days of storage at 50℃, the peroxide value does not exceed 20. Example 5 Pale yellow color with oily odor, oxidation value of 0.2, saponification value
187.5, this olive oil is an unsaturated triglyceride oil with an iodine value of 81.3.
Dissolve g in 150 ml of non-polar organic solvent N-hexane,
The liquid was passed through a column packed with 100 g of adsorbent (Example 5; activated clay), and then N-hexane was passed through it. After circulating the eluate, the N-hexane was evaporated to form a purified oil. did. The properties of this refined oil are shown in Table 11, and the storage characteristics are shown in Table 11.
-1 Table shows each.

【table】

[Table] As shown in Table 11-1, column chromatographic purification alone increases the peroxide value and deteriorates the oil in a short period of time. This refined oil was subjected to selective hydrogenation treatment under the conditions shown in Table 12.

[Table] The properties of the obtained refined oil are shown in Table 13.
-1 respectively.

【table】

【table】

[Table] After,
In this way, when selective hydrogenation treatment is performed after column chromatographic purification treatment, the peroxide value is 50.
Even after 30 days at ℃, there is only slight deterioration. <Oxidability over time> Purified unsaturated fats and oils obtained in Examples 1, 3, and 5 (specimens A, B, C) and Examples 1 and 3 as comparative examples
Intermediately purified unsaturated fats and oils obtained in Example 5 (unsaturated fats and oils subjected to selective hydrogenation treatment) (Samples D and E) and intermediately purified unsaturated fats and oils obtained in Example 5 (unsaturated fats and oils subjected to only column chromatographic circulation purification treatment) Put 50g of unsaturated fats and oils (sample F) into a 100ml glass beaker and leave it in a thermostat at 50±2°C, and
Tests were conducted for POV value and odor. This test method is the same as the storage property test described above. The POV value was measured based on the Japan Oil Chemists' Association Standard Oil and Fat Analysis Test Method 2.4.12-1. Regarding odor, we summarized the results after 30 days and
Shown in the table. The daily changes in POV are summarized in Figure 1.

[Table] As can be seen from Examples 1 to 5 and the results of the daily oxidation test, the unsaturated oils and fats for cosmetics according to the present invention can be purified without adding antioxidants even after 30 days at 50°C. It is found that it has particularly excellent oxidation stability over time, and is extremely useful as a cosmetic raw material because there is no so-called odor return phenomenon.

[Brief explanation of drawings]

FIG. 1 is a diagram showing oxidation characteristic curves over time of oils and fats obtained in Examples and Comparative Examples of the present invention. A...Example 1, B...Example 2, C...Example 3, D...Orange roughy oil subjected to only selective hydrogenation treatment, E... Macro whale oil only subjected to selective hydrogenation treatment , F...Olive oil that has only been subjected to column chromatographic circulation purification.

Claims (1)

[Claims] 1. An unsaturated ester oil of a higher alcohol and a higher fatty acid, which contains two or more double bonds in the hydrocarbon portion of either or both of the higher alcohol and the higher fatty acid-protecting acid, and has some It is obtained by using an unsaturated ester oil that also contains peroxides as a raw material oil and refining this raw material oil and fat by a combination of a selective hydrogenation step and a column chromatographic refining step, and immediately after purification. Of course, polyene fatty acids and/or polyene aliphatic alcohols are unsaturated oils and fats for cosmetics that maintain a peroxide value of 20 or less even after 30 days at 50±2°C after purification, and have two or more unsaturated bonds. 1. An unsaturated oil and fat for cosmetic use, characterized in that the hydrocarbon moiety of is selectively modified into a monoene form, and a certain amount of peroxide contained therein is reduced.