WO2013058080A1

WO2013058080A1 - Oily gel composition

Info

Publication number: WO2013058080A1
Application number: PCT/JP2012/075091
Authority: WO
Inventors: 坂西裕一; 橋崎要; 齋藤好廣; 田口博之
Original assignee: 株式会社ダイセル; 学校法人日本大学
Priority date: 2011-10-21
Filing date: 2012-09-28
Publication date: 2013-04-25
Also published as: JP2013087113A

Abstract

Provided is a gel-forming agent which is easily prepared and which combines high biological and environmental safety, favorable gel formation ability, excellent ease of use, and favorable ease of handling. Provided is a gel-forming agent characterized in that 1 to Y parts by weight of polyglycerin of a polymerization degree X is blended per 100 parts by weight of lecithin. (X and Y are numbers satisfying 3 ≤ X ≤ 20 and Y = 8.2Ln(X)-3.5). Also provided is an oily gel composition comprising 1-30 wt% of the gel-forming agent and 70-99 wt% of an oil-phase component, the oily gel composition being characterized in that the oily component is primarily composed of a non-polar oil.

Description

Oily gel composition

The present invention relates to a gel-forming agent and an oily gel-like composition containing the gel-forming agent and an oil phase component.

Gel-forming agents that thicken or gel-form various oil phase components such as animal and vegetable oils, mineral oils and hydrocarbons are used in various fields such as cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils. Widely used in The performance generally required for a gel-forming agent includes that a desired oil phase component can be gel-formed with a small amount of addition, and the obtained gel is stable over a long period of time. Furthermore, depending on the application, it is required to have high safety to the human body and the environment, to generate a gel having thixotropy, and to have a good tactile sensation of the obtained gel.

Conventional gel formers include low-molecular gel formers (1,2,3,4-dibenzylidene-D-sorbitol, 12-hydroxystearic acid, amino acid derivatives, etc.), polymer gel formers (polyacrylic acid derivatives) , Dextrin derivatives, etc.) are known. Low-molecular gel formers self-assemble in the oil phase components and form a huge network structure to make the oil phase components non-fluidized to form gels, while polymer gel formers make them complex. By forming an entangled network structure, gel formation of the oil phase component is caused.

On the other hand, gel formation of oil phase components by reverse string micelles has also been reported (Non-patent Documents 1-6). The reverse string micelle is a kind of self-assembly formed by a surfactant and is known to cause gel formation in order to form a network structure in the oil phase component. Since the reverse string micelle has a hydrophilic environment inside, it can contain a water-soluble drug, enzyme, etc., and has a feature not found in the above-mentioned gel forming agent.

A three-component mixed system of lecithin / water / various oil phase components has been reported as a typical system for forming the reverse string micelle (Non-patent Document 1). Examples of water substitutes include ethylene glycol, formamide, glycerin, bile salts (Non-patent Document 3), urea (Non-patent Document 4), sucrose (Non-patent Document 5), D-ribose and D-deoxy. Ribose (Non-patent Document 6) has been reported. Normally, lecithin forms reverse spherical micelles or reverse elliptical micelles in the oil phase component, but when a small amount of water or the like is added thereto, this hydrogen bonds to the phosphate group of lecithin, and the interface curvature of the molecular assembly is reduced. It is believed that reverse string micelle growth occurs to decrease.

Furthermore, gel formation of an oil phase component by an emulsion has been reported as a method for forming an oil phase component in a gel other than the above (Patent Document 1). That is, it is a gel emulsion in which one or more surfactants such as lecithin and sucrose are combined and a higher alcohol, glycerin and an oil phase component are added thereto.

Japanese Patent Laid-Open No. 5-4911

1,2,3,4-Dibenzylidene-D-sorbitol, which is a low molecular gel forming agent, is an excellent compound capable of gel-forming various types of oil phase components, but it decomposes to produce benzaldehyde. However, there is a problem with safety and it has not been put into practical use. 12-hydroxystearic acid is commercially available as a gel-forming agent for waste tempura oil, but lacks thixotropic properties. Moreover, since the gel forming agent of an amino acid derivative is hardly soluble in the oil phase component, complicated operations such as heating at a high temperature and long-time stirring are required to dissolve it. Moreover, such an operation has a problem in that it may cause a change in the quality of other components blended in the gel. On the other hand, a dextrin derivative of a polymer gel-forming agent needs to be added at a high concentration for gel formation, and also causes a “stickiness” peculiar to a polymer and is not good in use. Polyacrylic acid derivatives show good thickening gel formation when added in a small amount, but when used on the skin, a “stickiness” peculiar to polymers is produced, and the feeling of use is not good.

Next, as a problem with conventional reverse-like micelles, in reverse-like micelles composed of typical lecithin / water / various oil phase components, water is contained in the components, so that the drug is susceptible to hydrolysis. Etc. cannot be blended. In addition, when glycerin liquid at room temperature is used as a substitute for water, gel-forming ability is insufficient. Similarly, when ethylene glycol or formamide liquid at room temperature is used, it is strong against the skin, eyes, mucous membranes, etc. There is a problem that it cannot be applied to the human body because of its irritation. Further, when bile salts, urea, sucrose, D-ribose, etc., which are solid at normal temperature, are used, there is a problem that the preparation method becomes complicated as compared with the case where liquid is used. Therefore, a gel-forming agent that is easy to prepare and that has all of high safety to living bodies and the environment, good gel-forming ability, excellent usability, good handleability, etc. has not been obtained so far.

Patent Document 1 is a gel emulsion in which one or more surfactants such as lecithin and sucrose are combined and a higher alcohol, glycerin and oil phase components are added thereto. This gel has low elasticity compared to the gels composed of the gel formers and reverse string micelles described above, so it is easy to spill and poor handling, and it is effective if either higher alcohol or glycerin is missing. There is a problem that it cannot be obtained.

Accordingly, an object of the present invention is to provide a gel-forming agent that is easy to prepare and has all of high safety against living bodies and the environment, good gel-forming ability, excellent usability, and good handling properties.
Another object of the present invention is to provide an oily gel-like composition having excellent gel stability, which comprises the gel-forming agent having the above-mentioned excellent properties and an oil phase component.

As described above, when the gel forming agent and thickening gel composition are used in various fields such as cosmetics, pharmaceuticals, foods, paints, inks, lubricating oils, etc., the desired oil phase component is added with a small amount. It is required that a gel can be formed and that the obtained gel is stable over a long period of time. Furthermore, depending on the application, it is required that the gel is extremely safe for the human body, generate a gel having thixotropy, and have a good tactile sensation. However, in the prior art, it was not possible to obtain a sufficient gel forming agent having all of them.

Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have used a three-component mixed system of lecithin / polyglycerin / oil phase component, and formed a gel-forming agent composed of reverse string micelles and a thickened gel. Succeeded in obtaining the composition.

The lecithin used in the present invention is an amphoteric phospholipid having two alkyl chains, and is widely used as a food emulsifier for emulsification of dairy products, viscosity reduction of chocolate, and pharmaceutical preparations. High safety against On the other hand, polyglycerin is used as a moisturizer for cosmetics and as an emulsifier for food because of its strong hydrogen bonding ability and high safety.

In the present invention, a three-component mixed system of lecithin / polyglycerin / oil phase component was used for the preparation of a gel-forming agent capable of forming reverse cord-like micelles. It has been found that there is a blending range.

That is, the present invention
An oily gel composition comprising 1 to 30% by weight of a gel forming agent and 70 to 99% by weight of an oil phase component,
The gel forming agent is a gel forming agent in which 1 to Y parts by weight of polyglycerin having a polymerization degree X is blended with 100 parts by weight of lecithin.
Provided is an oily gel composition characterized in that the oily component is mainly composed of a nonpolar oil.
(X and Y are numbers satisfying 3 ≦ X ≦ 20 and Y = 8.2Ln (X) −3.5.)

The nonpolar oil is preferably liquid paraffin, and the liquid paraffin preferably has an average molecular weight of 250 to 500.

The present invention also provides
Provided is a gel forming agent characterized in that 1 to Y parts by weight of polyglycerin having a polymerization degree X is blended with 100 parts by weight of lecithin.
(X and Y are numbers satisfying 3 ≦ X ≦ 20 and Y = 8.2Ln (X) −3.5.)

In addition, the oily gel-like composition referred to in the present invention refers to a gel-like composition that does not contain water or contains a very small amount (for example, 1% by weight or less, preferably 0.2% by weight or less).

Since the gel forming agent of the present invention has the above-described configuration, it is easy to prepare, has high safety to living bodies and the environment, and has all of good gel forming ability, excellent usability, and good handling properties. Moreover, it is excellent also in transparency.
Since the oily gel-like composition of the present invention has the above-described configuration, it has high safety with respect to a living body and the environment, and has excellent usability and gel stability. Moreover, it is excellent also in transparency.

[lecithin]
Lecithin is a lipid product mainly composed of phosphatidylcholine, widely distributed in living organisms such as natural animals, plants, and microorganisms, and is known to be contained in a large amount in liver, egg yolk, soybean, yeast and the like. Representative lecithin includes egg yolk lecithin, soybean lecithin and the like. Lecithin can be used alone or in admixture of two or more. As lecithin, a phosphatidylcholine content of about 55 to 99% by weight is preferable. Those in this range tend to be creamy, have a moderate consistency, do not flow down when applied to the skin, and have a good feeling of use. Natural lecithin is only in the L-α-form, but others can be used. Since natural lecithin is easily oxidized and unstable, it may be hydrogenated by a known method before use. In the present invention, such hydrogenated lecithin is also included in “lecithin”.

Phosphatidylcholine means an ester obtained by reacting glycerol (glycerin) with at least one unsaturated fatty acid and phosphoric acid, and the proton of the phosphoric acid is substituted with choline as an amine functional group. In the present invention, phosphatidylcholine in which an unsaturated bond is hydrogenated is also included in “phosphatidylcholine”.

In the present invention, phosphatidylcholine is particularly defined according to the following general formula (I). Here, R ₁ and R ₂ , independently of each other, are (corresponding) aliphatic hydrocarbon groups derived from saturated or unsaturated fatty acids having 4 to 24 carbon atoms (that is, saturated or saturated carbon atoms having 3 to 23 carbon atoms). Unsaturated aliphatic hydrocarbon groups), which may be either linear or branched and may be substituted with one or more hydroxyl and / or amine functional groups. X represents a choline residue. The phosphatidylcholine may be one of the compounds represented by the formula (I) or a mixture of two or more.

In one embodiment of the present invention, fatty acids corresponding to R ₁ and R ₂ (R ₁ COOH, R ₂ COOH) are, for example, butyric acid, caproic acid, caprylic acid, capric acid, caproleic acid, lauric acid, laurolein. Acid, myristic acid, tyristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, isostearic acid, dihydroxtearic acid, and ricinoleic acid.

Non-hydrogenated phosphatidylcholines (PC) that are suitable for the practice of the compositions of the present invention may be of “natural” or “synthetic” origin.

“Natural” PC can be obtained by extraction from animal or plant sources such as soybeans, sunflowers, or eggs. Unhydrogenated phosphatidylcholine obtained from natural products, such as soybeans, is generally used as fatty acids esterifying glycerol as palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and possibly C _{20. Contains ~ 22} fatty acids.

[Polyglycerin]
The polyglycerin used in the present invention is produced using various methods. For example, (1) a method of addition polymerization of glycidol to glycerol, (2) an operation of addition polymerization of epichlorohydrin to glycerol, dehydrochlorination under alkaline conditions, and then ring-opening with dilute sulfuric acid to the desired degree of polymerization (3) A method in which glycidol protected with a hydroxyl group is added to glycerin, followed by deprotection, and this is repeated until the desired degree of polymerization. (4) Thermal condensation in the presence of alkali And (5) a method in which an allyl halide is added to glycerin and epoxidized, followed by ring opening with water, and this is repeated until an arbitrary degree of polymerization is achieved. Among these, the most preferable production method is the method (1), which can be suitably used as a gel forming agent for the oily gel composition.

The degree of polymerization of the glycerin unit of the polyglycerin used is 3 to 20, particularly preferably 3 to 10. If the degree of polymerization is less than 3, a stable gel cannot be obtained, and if it is greater than 20, an emulsified composition is obtained, and a transparent gel cannot be obtained, and the gel itself cannot be obtained. Polyglycerin can be used alone or in combination of a plurality of polymerization degrees.

In these polyglycerins, the IOB calculated from the organic conceptual diagram is not particularly limited, but is preferably 2 or more, more preferably 2 to 3. When the IOB calculated in the organic conceptual diagram is 2 or more, the gel composition can be obtained more easily. When the IOB calculated in the organic conceptual diagram is 2 to 3, it can be more reliably prevented from becoming an emulsified composition, and it becomes easier to obtain a gel composition. The IOB calculated from the organic conceptual diagram is a value obtained by the following formula (A).
IOB = Σinorganic / Σorganic × 10 (A)
(Reference: Nippon Emulsion Co., Ltd. “Emulsion formulation design based on organic concept”)

[Gel forming agent]
In the gel forming agent of the present invention, 1 to Y parts by weight of polyglycerin having a polymerization degree X is blended with 100 parts by weight of lecithin.
(X and Y are numbers satisfying 3 ≦ X ≦ 20 and Y = 8.2Ln (X) −3.5.)

Specifically, Y = 7 when 3 ≦ X <5, Y = 10 when 5 ≦ X <8, Y = 15 when 8 ≦ X <15, and Y when 15 ≦ X ≦ 20. = 20 is preferred,
When 3 ≦ X <5, Y = 1 to 10, when 5 ≦ X <8, Y = 5 to 10, when 8 ≦ X <15, Y = 5 to 15, and when 15 ≦ X ≦ 20 Preferably Y = 5-20,
Y = 5 if 3 ≦ X <5, Y = 10 if 5 ≦ X <8, Y = 15 if 8 ≦ X <15, Y = 20 if 15 ≦ X ≦ 20 Is more preferable.
X is not particularly limited as long as 3 ≦ X ≦ 20 is satisfied, more preferably 4 ≦ X ≦ 20, further preferably 5 ≦ X ≦ 20, and 10 ≦ X ≦ 20. Is particularly preferred.

The gel forming agent can be contained in an amount of 1 to 30% by weight, preferably 5 to 20% by weight, particularly preferably 10 to 15% by weight, based on the entire oily gel composition. If the content of the gel forming agent (the total amount of lecithin and the polyglycerin) relative to the entire oily gel-like composition is small, gel formation is poor and a stable oily gel-like composition cannot be obtained. Moreover, when there is much content of the gel formation agent with respect to the whole oil-based gel-like composition, since gel formation power and a moisturizing and water retention effect will reach a peak, there is no merit to use in large quantities, and it is not economical. Therefore, it is preferable to contain in the said range.

The lecithin content in the entire oily gel composition can be calculated from the above, but it is preferably in the range of 1 to 30% by weight, particularly preferably in the range of 5 to 20% by weight. When the content of lecithin is low, poor gel formation tends to occur and a stable oily gel composition cannot be obtained. On the other hand, when the content is too large, the gel forming ability and the moisturizing / water retaining effect reach a peak, so there is no merit of using a large amount and it is not economical. Therefore, it is preferable to contain in the said range. The content of phosphatidylcholine in the entire oily gel composition is, for example, 0.75 to 19% by weight, preferably 4 to 14% by weight.

The content of the polyglycerin in the entire oily gel composition can also be calculated from the above, but is preferably in the range of 0.1 to 5% by weight, particularly in the range of 3 to 5% by weight. preferable. If the polyglycerin content is low, a stable oily gel-like composition cannot be obtained, and if the content is too high, the gel forming ability and the moisturizing / water-retaining effect will reach a peak, so the advantage of using a large amount Not economical. Therefore, it is preferable to contain in the said range.

[Oil phase component]
The oil phase component used in the present invention is mainly composed of nonpolar oil. The non-polar oil is not particularly limited and may include hydrocarbons such as liquid paraffin, squalane and petrolatum, but liquid paraffin is preferable. The hydrocarbons are not particularly limited but are preferably liquid hydrocarbon oils having an average molecular weight of 250 to 500.

The content of these oil phase components is in the range of 70 to 99% by weight based on the total amount of the oily gel composition, and is blended alone or in combination. When the content of the oil phase component is lower than 70% by weight, the amount of the gel forming agent is excessively large, and when it exceeds 99% by weight, the stability of the gel is deteriorated. . The content of the oil phase component is preferably 80 to 95% by weight, more preferably 85 to 90% by weight, based on the total amount of the oily gel composition.

[Others]
Lecithin itself is effective as a cosmetic that softens aged keratin by reaching all the corners of the skin, but in order to further enhance the effect as a cosmetic for skin, vitamin B, vitamin Components such as E and various fragrances can be added. As an additive component, ascorbic acid is particularly effective. The pH value of ascorbic acid is about 2, and when this is added, the pH value of the cosmetic is lowered, the keratolytic action is exhibited, and the old keratin is removed. In order to blend ascorbic acid more stably, an ascorbic acid derivative such as ascorbyl palmitate can be used. In addition, by adding a component having antibacterial action such as hinokitiol, fucoidan, salicylic acid, it is possible to cope with fungi and bacteria present in the keratin. Furthermore, when a plant anti-inflammatory / moisturizing component such as glutyrrhizic acid is added, a sedative / moisturizing effect can be expected in a state where the cured keratin is lacerated and inflamed. Moreover, in order to prevent stickiness, powders, such as a silica, a silicon powder, an alkyl acrylate copolymer, can also be added.

In the oily gel composition of the present invention, in addition to the above-described components, components used in ordinary general cosmetics can be blended. Examples include fragrances, pigments, preservatives, antioxidants, anti-inflammatory agents, ultraviolet absorbers, ultraviolet reflectors, pH adjusters, and various other medicinal ingredients such as hyaluronic acid, allantoin, and the like. Vitamins, amino acids, placenta extract, and the like, which can be used alone or in combination.

The content of the components other than the gel forming agent and the oil phase component in the oily gel composition of the present invention is usually 29% by weight or less (for example, 0.1 to 29% by weight), preferably 20% by weight or less ( For example, 0.1 to 20% by weight), more preferably 10% by weight or less (for example, 0.1 to 10% by weight).

The oily gel composition obtained in the present invention is stable for a long period of, for example, 3 months or more. Further, since it was confirmed that the rheology measurement has an appropriate elasticity, it is judged that the liquid is difficult to drip and the handling property is good. Furthermore, since it has thixotropic properties, it has good elongation when applied to, for example, skin.

The zero shear viscosity obtained from the viscosity curve obtained by rheological measurement of the oily gel composition of the present invention is defined as follows. That is, in a region where the shear rate is as close to zero as possible, there is a region that can be approximated to a Newtonian fluid even if it is a non-Newtonian fluid. The viscosity η at this time is defined as a zero shear viscosity obtained from a viscosity curve obtained by rheology measurement. The zero shear viscosity is not particularly limited, but is preferably 50 Pa · s or more, particularly preferably 100 Pa · s or more, from the viewpoint of gel stability, feel of the gel, feeling of use, handleability, and the like. The upper limit of the zero shear viscosity is not particularly limited and varies depending on the application, but is, for example, 2000 Pa · s, preferably 1000 Pa · s.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Examples 1 to 9, Comparative Examples 1 to 22
Lecithin, polyglycerin and liquid paraffin (Molesco White P-100: manufactured by Moresco) were mixed at a ratio shown in Tables 1 to 4 to prepare an oily gel composition. The rheology of the obtained oily gel composition was measured to evaluate the formation of a thickening gel and the transparency of each composition was evaluated. The results are shown in Tables 1 to 4. The numerical values in the table represent the blending ratio (% by weight) of each component. The reagents, preparation methods, and evaluation methods used are shown below.

<Reagent>
Soy lecithin was used as lecithin. Soy lecithin was from Avanti Polar Lipids, Inc. (phosphatidylcholine concentration 95%). As the liquid paraffin, Moresco White P-100 (manufactured by Moresco) was used as it was. Various polyglycerins used Daicel products as they were.

<Preparation method>
Necessary amounts of lecithin, polyglycerin and liquid paraffin were sealed in a bottle and stirred using a magnetic stirrer. Thereafter, the sample was allowed to stand for several days in a constant temperature bath at 25 ° C. to reach equilibrium, thereby preparing a sample.

<Evaluation>
Each composition obtained in Examples and Comparative Examples was evaluated by the following method.
(1) Rheology measurement Viscosity and viscoelasticity measuring device (RheoStress600, HAAKE) equipped with a cone plate sensor (cone angle 1 °, cone angle 1 °, cone angle 1 °, 2 °, 4 ° using diameter 35mm) and Peltier temperature controller. Made by the company). All measurements were carried out in a steady flow viscosity measurement mode at 25 ° C., and the viscosity was measured by changing the shear rate from 0.001 to 10 (s ⁻¹ ) in a logarithmic manner to obtain a viscosity curve. In addition, the values at the time when the fluctuation of the torque value of the apparatus was within the 5% range and the data was stabilized were adopted for each plot.

(2) Evaluation of viscosity-increasing gel formation Polyglycerin, lecithin and liquid paraffin are mixed in the ratios shown in Tables 1 to 4 to prepare an oily gel-like composition, and rheology measurement of the obtained oily gel-like composition is performed. The _zero shear viscosity η ₀ of each composition was determined from the viscosity curve obtained by rheological measurement. As described above, even in the region where the shear rate is as close to zero as possible, there is a region that can be approximated to a Newtonian fluid even if it is a non-Newtonian fluid, and the constant viscosity η shown in that region is defined as _zero shear viscosity η ₀ . Here, the viscosity becomes a constant value when the shear rate is 0.1 (s ⁻¹ ) or less, and the value is defined as _zero shear viscosity η ₀ .
Evaluation of thickening gel formation (thickening gelation) was determined as follows based on this _zero shear viscosity η ₀ (Pa · s). The results are shown in Tables 1 to 4.
◎: Zero shear viscosity η ₀ is 100 Pa · s or more ○: Zero shear viscosity η ₀ is 50 Pa · s or more and less than 100 Pa · s ×: Zero shear viscosity η ₀ is less than 50 Pa · s

(3) Evaluation of transparency The transparency of the oily gel compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 22 was visually determined as follows. The results are shown in Tables 1 to 4.
○: Transparent ×: Cloudy or two-phase separation

Since the gel-forming agent and thickening gel-like composition characterized by the reverse string micelle obtained in the present invention are extremely safe for the human body and the environment, cosmetics, pharmaceuticals, foods, detergents, It can be used as various products exhibiting a gel form at room temperature as odorants, bathing agents, fragrances, deodorants and the like. Especially suitable for cosmetics and pharmaceutical applications. Examples of cosmetics include creams, emulsions, lotions, cleansing agents, bath cosmetics, moisturizing cosmetics, blood circulation promoting / massaging agents, pack cosmetics, hair cosmetics, and the like. Examples of pharmaceuticals include ointments, molded cataplasms, sustained-release preparation bases, transdermal absorption preparations, drug delivery system carriers, electrophoresis gels, and the like. In addition, since it exhibits a characteristic viscoelastic behavior, it can be used for industrial oils such as thickeners and viscosity adjusters.

Claims

An oily gel composition comprising 1 to 30% by weight of a gel forming agent and 70 to 99% by weight of an oil phase component,
The gel forming agent is a gel forming agent in which 1 to Y parts by weight of polyglycerin having a polymerization degree X is blended with 100 parts by weight of lecithin.
An oily gel-like composition, wherein the oily component is mainly composed of a nonpolar oil.
(X and Y are numbers satisfying 3 ≦ X ≦ 20 and Y = 8.2Ln (X) −3.5.)
The oily gel composition according to claim 1, wherein the nonpolar oil is liquid paraffin, and the liquid paraffin has an average molecular weight of 250 to 500.
1. A gel forming agent characterized in that 1 to Y parts by weight of polyglycerin having a polymerization degree X is blended with 100 parts by weight of lecithin.
(X and Y are numbers satisfying 3 ≦ X ≦ 20 and Y = 8.2Ln (X) −3.5.)