JP5679215B2 - Oil gel consisting of reverse string micelles - Google Patents

Description

  The present invention relates to an oil gelling agent for thickening or gelling oil such as animal and vegetable oils, mineral oils, hydrocarbons, fatty acid esters, and the like, and a thickening gel-like composition containing the oil and oil gelling agent Related to things.

  Oil gelling agents that thicken or gelate oils such as animal and vegetable oils, mineral oils, hydrocarbons, and fatty acid esters are used in various fields such as cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils. Widely used in The performance generally required for the oil gelling agent includes that the target oil can be gelled with a small amount of addition, and that the obtained gel is stable over a long period of time. Furthermore, depending on the application, it is required to have high safety for the human body, to produce a gel having thixotropy, and to have a good tactile feel of the obtained gel.

  Conventionally, as oil gelling agents, low molecular weight gelling agents (1,2,3,4-dibenzylidene-D-sorbitol, 12-hydroxystearic acid, amino acid derivatives, etc.), polymer gelling agents (polyacrylic acid derivatives) , Dextrin derivatives, etc.) are known. Low-molecular gelling agents self-assemble in oil and form a huge network structure, and the oil becomes non-fluidized to form a gel. On the other hand, high-molecular gelling agents are intertwined in a complex network structure. Forming oil causes gelation of the oil.

  1,2,3,4-Dibenzylidene-D-sorbitol, a low molecular gelling agent, is an excellent compound that can gel various types of oils, but is safe in that it decomposes to produce benzaldehyde. Has not been put to practical use. 12-hydroxystearic acid is commercially available as a gelling agent for waste tempura oil, but lacks thixotropic properties. Moreover, since the gelling agent of an amino acid derivative is hardly soluble in oil, complicated operations such as heating at a high temperature and stirring for a long time 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 gelling agent needs to be added at a high concentration for gelation, and also causes a “sticky feeling” peculiar to polymers and is not good in use. Polyacrylic acid derivatives show good thickening gelation 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.

  In order to solve these problems, a gel emulsion (Patent Document 1) containing 1 or 2 kinds of natural surfactants such as lecithin and sucrose fatty acid ester, higher alcohol, glycerin and oil has been proposed. Therefore, there is a problem that dripping or the like is liable to occur and handling property is poor, and if either higher alcohol or glycerin is missing, the effect cannot be obtained. In addition, as an oil gelling agent that is safe for the human body, an agent containing an α-aminolactam derivative as an active ingredient has been proposed (Patent Document 2). However, heating and dissolution are required, and high safety to living bodies and the environment is proposed. In addition, an oil gelling agent having excellent gelling ability, excellent usability, and good handling properties has not been obtained.

  On the other hand, oil gelation by reverse string micelles has also been reported in a small number (Non-Patent Documents 1-3). The reverse string micelle is a kind of self-assembly formed by a surfactant, and is known to cause gelation in order to form a network structure in oil. Since it has a hydrophilic environment inside the reverse string micelle, it is possible to encapsulate water-soluble drugs, enzymes, etc., and it has a feature not found in the oil gelling agent described above.

  As a typical system for forming the reverse string micelle, a three-component mixed system of lecithin / water / various oils has been reported (Non-patent Document 1). Moreover, ethylene glycol, formamide, and bile salts (Non-patent Document 3) have only been reported as substitutes for water. Normally, lecithin forms reverse spherical micelles or reverse elliptical micelles in oil, but when a small amount of water is added to this, hydrogen bonds to the phosphate groups of lecithin and the interface curvature of the molecular assembly decreases. It is believed that reverse string micelle growth occurs.

  As a problem with conventional reverse-like micelles, in reverse-like micelles consisting of typical lecithin / water / various oils, since water is contained in the ingredients, drugs that are susceptible to hydrolysis are blended. I can't. In addition, ethylene glycol and formamide, which are substitutes for water, cannot be applied to the human body because they have strong irritation to the skin, eyes, mucous membranes and the like. In addition, bile salts are surfactants derived from living organisms, but they may cause inflammation when attached to the skin, eyes, etc., and are highly safe for the living body and the environment, good gelation ability, excellent use feeling, No oil gelling agent that has all the good handling properties has been obtained.

JP-A-5-4911 Japanese Patent Application Laid-Open No. 10-256571

P. L. Luisi et al. Colloid & Polymer Science, vol.268, p.356 (1990) Yu. A. Shchipunov, Colloids and Surfaces A, vol.183-185, p.541 (2001) S. H. Tung et al. Journal of the American Chemical Society, vol.128, p.5751 (2006)

  The present invention requires an oil gelling agent and a thickened gel-like composition for forming reverse string micelles, which are required to have high safety against living bodies and the environment, excellent usability, and good gelling ability. It is an object of the present invention to provide an oil gelling agent and a thickened gel-like composition using the oil gelling agent.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used lecithin / saccharide as an oil gelling agent for various oils, and also used a three-component mixed system of these lecithin / saccharide / various oils. Thus, it is possible to obtain a thickened gel-like composition having a reverse cord-like micelle structure, and the thickened gel-like composition is extremely safe for the human body and the environment, has a good gelling performance, and has a long-term It has been found that the above problems can be solved.

  And, the present inventors include an oil gelling agent containing lecithin and saccharides to form reverse string micelles, and a thickened gel-like composition containing the oil gelling agent and various oil components to form reverse string micelles. It came to invent.

That is, the present invention
[1] An oil gelling agent which contains (a) lecithin and (b) saccharides to form reverse string micelles.
[2] The oil gelling agent according to [1] above, wherein the (a) lecithin is either soybean lecithin or egg yolk lecithin.
[3] The oil gelling agent according to the above [1] or [2], wherein the (b) saccharide comprises at least one of a monosaccharide, an oligosaccharide, a polysaccharide, and a deoxy form thereof. .
[4] As a mixing ratio of (a) lecithin and (b) saccharide, 0.1 to 50% by mass of (b) saccharide is contained with respect to the total mass of (a) lecithin and (b) saccharide. The oil gelling agent according to any one of the above [1] to [3], wherein
[5] A thickened gel-like composition comprising at least the oil gelling agent according to any one of [1] to [4] above and (c) an oil component to form reverse string micelles.
[6] The thickened gel-like composition as described in [5] above, wherein the thickened gel-like composition is at least one of cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils object.
[7] The above-mentioned [5], wherein the oil gelling agent is contained in an amount of 1% by mass to 70% by mass with respect to the thickened gel-like composition as a mixing ratio of the oil gelling agent and (c) the oil component. Or the thickening gel-like composition as described in [6].

  The oil gelling agent that forms the reverse string micelle of the present invention has not only the advantage and effect of being environmentally friendly with high safety to living bodies and the environment, but also gels the target oil with a small amount of addition. It can be widely used as an oil gelling agent for various cosmetics, pharmaceuticals, foods, paints, inks, lubricating oils and the like. The resulting thickened gel-like composition has thixotropic properties, is difficult to drip, has good handling properties, and has long-term stability over one year. The transparency of the thickened gel-like composition can be adjusted depending on the oil gelling agent to be used, the preparation conditions of the thickened gel-like composition, and the like, from transparent to translucent, white turbidity and the intended use. In addition, it has a hydrophilic environment inside the reverse cord-like micelle structure, and has characteristics not found in conventional thickening gel-like compositions that can contain water-soluble components, drugs, enzymes, and the like.

Reverse micelle structure diagram Scatter curve diagram of small angle X-ray scattering measurement

  The present invention is described in detail below. The oil gelling agent of the present invention is a material that can thicken or gel various oil components to form reverse string micelles. The oil gelling agent of the present invention contains (a) lecithin, (b) saccharide, and thickened or gelled when various (c) oil components are added and mixed to form a reverse string-like micelle structure. Become a composition.

  A reverse worm-like micelle is a kind of self-assembly formed by a surfactant. The surfactant is an amphiphilic substance having a hydrophilic group and a hydrophobic group in the molecule, and forms a self-assembly in water or oil according to the balance of the groups. As shown in FIG. The reverse string-like micelle in which the micelle has grown into a cylindrical shape forms a temporary network structure and forms a highly elastic gel. In addition, since it has a hydrophilic environment inside, it is possible to enclose water-soluble components, drugs, enzymes, and the like.

  As a result of intensive studies on the reverse string micelles, the present inventors have found that a substance that causes reverse string micelle growth requires two conditions. One is that it has two or more functional groups capable of hydrogen bonding with the phosphate group of lecithin, and the second is that it has a slight hydrophobicity. It has been found that reverse string-like micelles can be formed with sugars and various oils.

The present inventors have observed the structure of the obtained thickened or gel-like preparation, specifically the thickened gel-like preparation formed by mixing lecithin, D-ribose and n-decane. . The thickened gel-like preparation is transparent, has no crystal structure, is optically isotropic, and does not show a characteristic pattern as a polarized image. From the scattering curve measured by small angle X-ray scattering (SAXS), since a clear diffraction peak was not obtained, no regular structure was formed, and the thickened gel-like composition of the present invention was an inverted string micelle. It can be said that it forms.
In addition, the thickened gel composition of the present invention forms a reverse string-like micelle, and thus depends on the oil to be thickened or gelled, but is transparent if the oil itself is transparent. .

  SAXS measurement was performed using Nano-STAR manufactured by Bruker AXS, Inc., the X-ray source was CuKα ray, and the output was 45 kV / 120 mA. All SAXS measurements were performed at 25 ° C.

FIG. 2 shows a thickened gel composition 1 (sample 1) in which 2% by mass of lecithin, 0.2% by mass of D-ribose, and 97.8% by mass of n-decane, 10% by mass of lecithin, D- Thickening gel composition 2 (sample 2) mixed with 1% by weight ribose and 89% by weight n-decane, thickened by mixing 20% by weight lecithin, 2% by weight D-ribose and 78% by weight n-decane. The scattering curve (relationship of scattering intensity I (q) and scattering vector q) of the small-angle X-ray scattering measurement with the gel-like composition 3 (sample 3) is shown. Here, q = (4π / λ) sin θ, θ is the scattering angle, and λ is the wavelength of the X-ray. According to this, since no scattering curve showed a clear diffraction peak, it can be seen that no regular structure was formed.
In the scattering curve of Sample 1 having the lowest oil gelling agent concentration among these three samples, the slope on the low q side of the log-log plot is -1. This suggests the presence of long rod-like particles, ie reverse string micelles. Moreover, the cross-sectional radius (r) of the reverse string-like micelle was determined to be 1.9 nm by the Cross-section plot based on the formulas (1) and (2).
Here, Rc is the radius of rotation of the cross section. In addition, the exact length of the reverse string micelle could not be calculated due to the limitation of the measurement range, but the length (t) of the reverse string micelle is about 500 mm or more from the simulation using the equation (3). It was shown that.
Here, J ₁ is a first-order Bessel function. In Samples 2 and 3, the low q-side scattering intensity decreased and the inclination tended to be gentle. This result shows that in Sample 2 and Sample 3, the amount of reverse string micelle per unit volume in the sample is increased. That is, it can be considered that the contribution of the structure factor is increased due to the proximity of the reverse string micelles, and the scattering intensity on the low q side is reduced.
Further, the thickened gel-like composition obtained by thickening or gelling the oil component using the oil gelling agent of the present invention is similarly formed with reverse string-like micelles in view of the gelation state and physical properties. It can be said.

  (A) Lecithin as an oil gelling agent of the present invention is a mixture of naturally occurring phospholipids, such as soybean-derived soybean lecithin, egg yolk-derived egg yolk lecithin, purified lecithin with increased purity, enzyme-treated lysolecithin, etc. Modified lecithin can be used. Lecithin is an amphoteric phospholipid having two alkyl chains, and is widely used as a food emulsifier in emulsification of dairy products, reduction in viscosity of chocolate, and in pharmaceutical preparations. Moreover, it is a hydrophobic amphoteric surfactant and has high safety to living bodies and the environment. In the present invention, it is preferable to use soybean lecithin and egg yolk lecithin among lecithins.

  (B) Saccharides as oil gelling agents of the present invention are synonymous with saccharides, are widely distributed in nature, and are the most important among human nutrients, and extremely safe for living bodies and the environment. There are monosaccharides, oligosaccharides, polysaccharides and the like. Examples of monosaccharides include glyceraldehyde, erythrose, xylitol, D-xylose, D-ribose, D-galactose, D-glucose, D-sorbitol, fructose and the like. Examples of oligosaccharides include maltose, cellobiose, lactose, and sucrose. Examples of polysaccharides include amylose, amylopectin, glycogen, and dextran. Moreover, the deoxy sugar by which the alcoholic hydroxyl group of these saccharides of monosaccharide, oligosaccharide, and polysaccharide was substituted by hydrogen can be illustrated. Among these, constituent sugars of ribonucleic acid, food additives, D-ribose as a sweetener, D-glucose as a glucose, galactose, and these deoxy sugars can be exemplified as preferable examples. Since these are widely distributed in nature and are also human nutrients or biological components, they are not toxic to the human body, are highly safe, are industrially inexpensive and easy to obtain.

  The mixing ratio with the (a) lecithin (b) saccharide constituting the oil gelling agent of the present invention may be in any range as long as it is a mixing ratio capable of forming reverse string micelles. (A) 1-70% by mass of lecithin, preferably 1.5-45% by mass, more preferably 2-25% by mass, (b) 0.1-30% by mass of saccharide, preferably 0.15-15 It can be made into the mass%, More preferably, it is 0.2-5.2 mass%. The mass ratio of (b) saccharides to the total amount of the oil gelling agent varies depending on (c) oil component, but when expressed in mass% of (b) component / ((a) component + (b) component), The lower limit is 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is experimentally 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less. It is.

  The oil component (c) that can be gelled in the present invention is not particularly limited, and is oil such as animal and vegetable oils, mineral oils, hydrocarbons, and fatty acid esters. Only polar oil, nonpolar oil, or a mixture of polar oil and nonpolar oil may be used. Specifically, fish oil such as fish oil, liver oil, whale oil, head, lard, horse oil, sheep oil, animal oil, vegetable oil such as animal oil, palm oil, palm oil, cacao butter, olive oil, rapeseed oil, linseed oil, etc .; Hydrocarbons such as liquid paraffin, isoparaffin, kerosene, heavy oil, isooctane, n-heptane, n-decane and cyclohexane; higher fatty acids such as lauric acid, palmitic acid, stearic acid, oleic acid and behenic acid, isopropyl myristate And fatty acid esters such as 2-octyldodecyl myristate and isopropyl palmitate. These oils can be used singly or as a mixture of two or more.

  The oil to be gelled may be dissolved, dispersed, emulsified, suspended or mixed at a concentration that does not hinder thickening or gelling of the added component. Examples of such additive components include surfactants, ultraviolet absorbers, moisturizers, preservatives, preservatives, bactericides, depending on the application such as cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils. There are antioxidants, fluidity improvers, fragrances, pigments, enzymes, physiologically active substances, and the like, and examples include organic compounds or inorganic compounds such as titanium oxide, talc, mica, and water.

  When the oil component (c) is gelled with the oil gelling agent containing (a) lecithin (b) saccharide of the present invention, the oil gelling agent is thickened or gelled with respect to the oil component, and the reverse string-like micelle is formed. Any amount can be mixed as long as it can be formed. As a mixing ratio of the oil component, (a) lecithin is 1 to 70% by mass, preferably 1.5 to 45% by mass, more preferably 2 to 25% by mass, and (b) saccharide is 0.1 to 30% by mass. When the content is 0.15 to 15% by mass, more preferably 0.2 to 5.2% by mass, (c) the oil component is 30 to 99% by mass, preferably 50 to 98% by mass, more preferably It can be 70-97 mass%.

  Moreover, the mixing ratio of the oil gelling agent to the thickened gel-like composition is expressed by mass% of ((a) component + (b) component) / ((a) component + (b) component + (c) component). And the lower limit is 1% by mass or more, preferably 1.5% by mass or more, more preferably 2% by mass or more, and the upper limit is 70% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass. % Or less. By adding within this range and adding and mixing the oil component, the thickened gel-like composition can be obtained. The gel strength can be adjusted by the concentration of the oil gelling agent and the mixing ratio of (a) lecithin and (b) saccharide.

  The thickening gel-like composition of the present invention contains (a) lecithin (b) saccharide, various (c) oil components are added, and other additive components are added as necessary to dissolve uniformly. By this, it can be gelled to form an inverted string micelle structure. As an example of preparation of a thickened gel composition, (a) component: an organic solvent solution of lecithin and (b) component: saccharides are each enclosed in a required amount container, stirred, and completely (b) component: saccharides. After the organic solvent is dissolved, the organic solvent is completely evaporated by drying under reduced pressure, and then (c) the required amount of the oil component is added and further stirred overnight, and the container is placed in a room temperature constant temperature bath for stabilization as needed. It can be obtained by standing for days. It can also be prepared by dissolving a mixture of (a) lecithin, (b) saccharide and various (c) oil components by heating and cooling to room temperature. The heating at this time may be any temperature as long as the mixture dissolves, but is preferably in the range of 50 ° C to 80 ° C. At this time, in order to prevent lecithin from being oxidized, it is preferably carried out in a nitrogen atmosphere or by adding an antioxidant. The thickening gel-like composition is produced immediately by adding, mixing, and stirring each component, and long-time stirring and standing for stabilizing the gel-like material is appropriately performed as necessary. It only has to be set, and in some cases it is not necessary.

  Examples of the organic solvent used for preparing the thickened gel composition include lower alcohols such as methanol, ethanol, propanol and butyl alcohol; polyhydric alcohols such as ethylene glycol and propylene glycol; acetone, 2-butanone and cyclohequinone. Ketones such as tetrahydrofuran, ethers such as 1,4-dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; chloroform and carbon tetrachloride Halogenated hydrocarbons such as dichloromethane, dichloroethane, isopropyl bromide, ethyl bromide, dichlorobenzene, tetrachloroethane, trichloroethane, trichloroethylene, ethylene tetrachloride; water, etc. Among them, lower alcohols are preferred. . These organic solvents may be used alone or in combination.

  The thickening gel-like composition of the present invention can be used as various products exhibiting a gel state at room temperature as a cleaning agent, cosmetics, medicine, food, deodorant, bath agent, fragrance, deodorant and the like. Especially suitable for use in detergents, cosmetics and pharmaceuticals. Examples of the detergent include food detergents, dish detergents, kitchen detergents, facial cleansers, body soaps, shampoos, rinses and the like. 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 cosmetics, 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 Vitamins, amino acids, placenta extract, and the like, which can be used alone or in combination.

  The thickened gel-like composition formed by adding and mixing various oils to the oil gelling agent of the present invention has a reverse string-like micelle structure, so it has a hydrophilic environment inside and is a water-soluble component・ It is possible to enclose drugs and enzymes. These reverse string micelles are nanometer-scale extremely fine molecular aggregates, and these reverse string micelles have a lecithin-saccharide molecule polar group facing inward and a hydrophobic group facing outward. Since many are gathered, a hydrophilic environment, that is, a small water pool (water phase) is formed inside. Examples of water-soluble substances that can be encapsulated include moisturizers, whitening agents, anti-inflammatory agents, antibacterial agents, hormone agents, vitamins, various amino acids and their derivatives, enzymes, antioxidants, hair restorers, etc. Ingredients.

  In the thickened gel-like composition formed by adding and mixing various oils to the oil gelling agent of the present invention, a water-soluble substance, a water-soluble drug, and an enzyme that are hardly soluble or insoluble in oil are directly or When the aqueous solution is contacted, mixed and stirred, the water-soluble substance is taken into the reverse string micelle and can be dissolved in the thickening gel. The transparency of the formed thickened gel-like composition can be adjusted according to the oil gelling agent used, the preparation conditions of the thickened gel-like composition, and the like, from transparent to translucent, white turbid, and the application used.

The oil gelling agent of the present invention is excellent in gelation ability for various oils, can form a stable gel for a long time even when added at a low concentration, and particularly a gel of higher hydrocarbons has excellent thixotropic properties, and There is no shortcoming such as “stickiness”. Moreover, the oil gelling agent of the present invention is made of material components such as lecithin and saccharide that are highly safe and biodegradable for living bodies and the environment, and is an environmentally harmonious type.
The oil gelling agent of the present invention is further used in fields other than the above, such as quasi-drugs, inks, paints, lubricating oils, plastics, rubbers, metals, etc., as well as agriculture, fisheries, waste oil treatment, etc. be able to.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, unless otherwise specified, a compounding quantity is shown by the mass%.

[Evaluation of thickening gel composition]
Viscosity measurement was performed at a constant temperature of 25 ° C. using a cone plate (diameter 60, 35 mm, cone angle 1 ° and 4 °) and a rotational rheometer (RheoStress 600, manufactured by HAAKE) equipped with a Peltier temperature controller. In addition, in order to prevent evaporation of a solvent, it measured using the solvent trap. Specifically, the sample was sandwiched between the cone plate and the sample stage, and the cone plate was rotated in a fixed direction to apply a shear rate stepwise to the sample. The shear stress was calculated for each shear rate, and the viscosity was calculated from the relationship of viscosity = shear stress / shear rate.
Moreover, based on this, the state of thickening gelation was evaluated as follows.
◎ Gelation (100 Pa · s or more): ○ Thickening (10 Pa · s or more and less than 100 Pa · s): x Insufficient thickening gelation (less than 10 Pa · s)

[Storage stability of thickened gel composition]
Storage stability was confirmed by enclosing the thickened gel composition prepared in Examples and Comparative Examples in a sample bottle with a diameter of 27.5 mm and a height of 70 mm and storing it in a thermostatic bath set at 25 ° C. for 6 months. Then, the separated state of the thickened gel composition was visually observed, and the storage stability was evaluated according to the following criteria.
◎ Good: ○ Slightly separated: × Poor

[Examples 1 to 8]
(Formulation of thickening gel composition)
As a component lecithin (a), soybean lecithin (trade name “L-α-Phosphatidylcholine (Soy-95%)” manufactured by Avanti Polar Lipids, Inc.), as a saccharide of component (b), D-ribose (Kanto Chemical ( Co., Ltd.), and (c) component, n-decane (manufactured by Kanto Chemical Co., Ltd. 0.774 mPa · s (25 ° C.)) was used as a blending composition shown in Table 1 to prepare a thickened gel composition. . It was set as Examples 1-8 according to each compounding composition.

(Preparation of thickened gel composition)
Preparation of the thickened gel-like composition was carried out by encapsulating (a) component: methanol solution of lecithin and (b) component: D-ribose in bottles, respectively, and stirring with a magnetic stirrer. Component (b): D-ribose is completely dissolved, and then methanol is completely evaporated by drying under reduced pressure. (C) The required amount of oil component was added, and the mixture was further stirred overnight, and prepared by allowing the bottle to stand for several days in a thermostatic bath at 25 ° C. for stabilization. In addition, also in the following Examples 9-27 and Comparative Examples 1-5, preparation of a thickening gel-like composition was based on the same preparation means.

  In Examples 1 to 8, (a) component: a thickened gel-like composition was prepared with lecithin in an amount of 2 to 25% by mass. The ratio of D-ribose in these oil gelling agents, that is, (b) component / ((a) component + (b) component) is 9% by mass to 17% by mass, and the oil gelation in the thickened gel-like composition The ratio of the agent, that is, ((a) component + (b) component) / ((a) component + (b) component + (c) component) is 2% by mass to 30% by mass. The state of the thickening gel was transparent, both were gelation ◎ to ○, and the storage stability was also ◎ good. The state of the gel of Example 1 was a thickening ◯, but there was no problem in use. The evaluation results are shown in Table 1.

[Examples 9 to 12]
(Formulation of thickening gel composition)
(A) As component lecithin, soybean lecithin (trade name “L-α-Phosphatidylcholine (Soy-95%)” manufactured by Avanti Polar Lipids, Inc.), component (b) D-ribose (manufactured by Kanto Chemical Co., Inc.) ), (C) As a component, cyclohexane (0.828 mPa · s (25 ° C.) manufactured by Kanto Chemical Co., Inc.) was used to prepare a thickened gel composition, which was used in Example 9.
Next, the component (c) was changed to isopropyl myristate (4.74 mPa · s (25 ° C.) manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a thickened gel-like composition. By changing to isopropyl palmitate (6.09 mPa · s (25 ° C.) manufactured by Wako Pure Chemical Industries, Ltd.), a thickened gel-like composition was prepared, and Example 11 was further mixed with liquid paraffin (Kanto Chemical ( 146 mPa · s (25 ° C.)), a thickened gel composition was prepared and used as Example 12. The composition is shown in Table 1.

  The ratio of D-ribose in the oil gelling agents of Examples 9 to 12, that is, (b) component / ((a) component + (b) component) is 3% to 29% by mass, in the thickened gel-like composition The ratio of the oil gelling agent ((a) component + (b) component) / ((a) component + (b) component + (c) component) is 10 mass% to 14 mass%. The state of the thickening gel was transparent, both gelled, and the storage stability was good or good. In Example 12, the storage stability was ○, but it was translucent and stable in the usual standard of 3 months, and it was in a state where there was no problem in use. The evaluation results are shown in Table 1.

[Examples 13 to 22]
(Formulation of thickening gel composition)
(A) As a component lecithin, soybean lecithin (trade name “L-α-hosphatidylcholine (Soy-95%)” manufactured by Avanti Polar Lipids, Inc.), (b) component as 2-deoxy-D-ribose (Kanto Chemical) A thickening gel-like composition was prepared using n-decane (manufactured by Kanto Chemical Co., Ltd.) as the component (c) and a blending composition shown in Table 1. It was set as Examples 13-17 according to each compounding composition.
Next, (b) component was changed to 2-deoxy-D-glucose (manufactured by Kanto Chemical Co., Inc.), and a thickening gel composition was prepared as a blending composition shown in Table 2. It was set as Examples 18-22 according to each compounding composition.

  In Examples 13 to 17, (a) component: lecithin is 5 to 25% by mass, (b) component: 2-deoxy-D-ribose, (c) component: n-decane is used to increase viscosity. A gel composition was prepared. The ratio of 2-deoxy-D-ribose in these oil gelling agents, that is, (b) component / ((a) component + (b) component) is 11% by mass to 16% by mass, in the thickened gel-like composition The ratio of the oil gelling agent ((a) component + (b) component) / ((a) component + (b) component + (c) component) is 6 mass% to 30 mass%. The state of the thickening gel was transparent, both of which were gelled ◎ to ◯, and the storage stability was also 良好 good. The state of the gel of Example 13 was a thickening ◯, but there was no problem in use. The evaluation results are shown in Table 1.

In Examples 18 to 22, (a) component: lecithin was 5 to 25% by mass, (b) component: 2-deoxy-D-glucose, and (c) component: n-decane were used in the required amounts. A thickened gel composition was prepared as shown in FIG.
The ratio of 2-deoxy-D-glucose in these oil gelling agents, (b) component / ((a) component + (b) component) is 11% by mass to 14% by mass, in the thickened gel-like composition The ratio of the oil gelling agent (component (a) + component (b)) / (component (a) + component (b) + component (c)) is 6 mass% to 29 mass%. The states of the thickening gel were all gelled ◎, all the storage stability was ◎ good, and all were transparent. The evaluation results are shown in Table 2.

  According to Examples 13-22, (a) lecithin was 5, 10, 15, 20, 25 mass%, (b) 2-deoxy-D-ribose, or (b) 2-deoxy-D-glucose, Even when the component (c) was n-decane, the thickened gel was in the form of a gelled な い し or ◯ and the storage stability was good for 6 months or longer.

[Examples 23 to 27]
(Formulation of thickening gel composition)
(A) Component: As lecithin, soybean lecithin (trade name “L-α-Phosphatidylcholine (Soy-95%)” manufactured by Avanti Polar Lipids, Inc.), (b) component as D-glucose (Wako Pure Chemical Industries, Ltd.) )), As component (c), n-decane (manufactured by Kanto Chemical Co., Ltd.) was used to prepare a thickened gel-like composition, which was designated as Example 23.
Next, the component (b) was 2-deoxy-D-galactose (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and Examples 24 and 25 were used according to each composition.
Furthermore, 6-deoxy-D-galactose (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (b), and Examples 26 and 27 were used according to the respective composition compositions. Table 2 shows the composition.

  In Example 23, a thickened gel-like composition was prepared using the necessary amounts of (b) component: D-glucose and (c) component: n-decane, and Examples 24 and 25 were prepared as component (b). : A thickened gel-like composition prepared using 2-deoxy-D-galactose, Examples 26 and 27, (b) component: thickened gel using 6-deoxy-D-galactose, respectively, in the required amounts A composition is prepared.

  The mixing ratio in Examples 23 to 27 is the ratio of saccharides in the oil gelling agent (b) component / ((a) component + (b) component) is 7% by mass to 12% by mass. The ratio of the oil gelling agent ((a) component + (b) component) / ((a) component + (b) component + (c) component) is from 6% by mass to 11% by mass. The gel state was transparent, and both gelation was excellent and the storage stability was good. In addition, although the state of the gel of Examples 24 and 26 is thickening (circle), it was a state which does not pose any problem on use. The evaluation results are shown in Table 2.

[Examples 28 to 32]
(Preparation of thickened gel composition)
In Examples 4, 9, 10, 11, and 12, preparation of the thickened gel-like composition was carried out using (a) component: lecithin, (b) component: D-ribose, and (c) oil component in the required amount bottles. The mixture was sealed, dissolved by heating at about 60 ° C., and cooled to room temperature. At that time, it was performed in a nitrogen atmosphere to prevent oxidation of lecithin.
As a blending composition shown in Table 3, a thickened gel composition was prepared. It was set as Examples 28-32 according to each compounding composition.

According to Examples 28 to 32, (a) component: lecithin is 10 mass%, (b) component: D-ribose, (c) component: n-decane, cyclohexane, isopropyl myristate, isopropyl palmitate, flow Thickened gel compositions were prepared using the required amounts of paraffin, and the states of the thickened gels were both gelation ◎, ◯, and storage stability ◎. The state of the thickening gel of Example 29 was thickening ◯, but there was no problem in use. The transparency of the gel is determined by enclosing the thickened gel-like composition in a sample bottle with a diameter of 27.5 mm and a height of 70 mm and storing it in a thermostatic bath set at 25 ° C. for 6 months, and then UV-visible. The transmittance was measured at a wavelength of 550 nm using a spectrophotometer (V-530, manufactured by JASCO Corporation). The transmittance was evaluated as transparent: 1, translucent: 2, white turbidity: 3 based on transmittances of 100 to 90%, 89 to 50%, and 49% or less. The evaluation results are shown in Table 3.
The transparency is either transparent or cloudy, and can provide transparency according to the application used as the thickening gel composition.

[Comparative Examples 1-5]
(Formulation of thickening gel composition)
(A) Component: Soy lecithin (trade name “L-α-Phosphatidylcholine (Soy-95%)” Avanti Polar Lipids, Inc.) 10% by mass as lecithin, n-decane (Kanto Chemical) as component (c) A thickened gel-like composition was prepared using 90% by mass as a blending composition, and it was designated as Comparative Example 1. A thickened gel-like composition was prepared as Comparative Example 2 in the same manner as in Comparative Example 1 except that the component (c) was changed to cyclohexane (manufactured by Kanto Chemical Co., Ltd.). A thickened gel composition was prepared as Comparative Example 3 in the same manner as in Comparative Example 1 except that the component (c) was changed to isopropyl myristate (manufactured by Wako Pure Chemical Industries, Ltd.). A thickened gel composition was prepared as Comparative Example 4 in the same manner as in Comparative Example 1 except that the component (c) was changed to isopropyl palmitate (manufactured by Wako Pure Chemical Industries, Ltd.). A thickened gel composition was prepared as Comparative Example 5 in the same manner as Comparative Example 1 except that component (c) was changed to liquid paraffin (manufactured by Kanto Chemical Co., Inc.).

  Since Comparative Examples 1-5 did not use the saccharide of component (b), a thickening gel could not be formed. Table 2 shows the composition and the evaluation results. On the other hand, in the present invention, as shown in Examples, the oil component (c) n-decane has a viscosity increase of 2.5 million times at 0.774 mPa · s at 25 ° C., and the cyclohexane has a temperature of 25 ° C. At 0.828 mPa · s, 6 million times the viscosity increase, isopropyl myristate at 25, 4.74 mPa · s, 60,000 times the viscosity increase, isopropyl palmitate at 6.00 mPa · s at 25 ° C. However, a viscosity increase of 40,000 times and liquid paraffin easily obtained a viscosity increase of 7,000 times at 146 mPa · s at 25 ° C. It should be noted that the thickening gel could not be formed even with the saccharide (b) and the (c) oil component.

ADVANTAGE OF THE INVENTION According to this invention, the oil gelling agent which can form a reverse string-like micelle with the 3 component mixed system of a lecithin / sugar / various oil can be provided. The thickened gel-like composition formed with reverse string micelles has a hydrophilic environment inside the reverse string micelles, and can contain water-soluble ingredients, drugs, enzymes, etc. It can be widely used as an oil gelling agent for pharmaceuticals and foods. Further, the thickened gel composition formed by using the oil gelling agent has thixotropic properties, good handling properties, and good long-term stability.

Claims (7)

(A) An oil gelling agent that forms reverse string-like micelles composed of lecithin and (b) saccharides. The oil gelling agent according to claim 1, wherein the (a) lecithin is either soybean lecithin or egg yolk lecithin. The oil gelling agent according to claim 1 or 2, wherein the (b) saccharide comprises at least one of a monosaccharide, an oligosaccharide, a polysaccharide, and a deoxy form thereof. As a mixing ratio of the (a) lecithin and (b) saccharide, 0.1 to 50% by mass of (b) saccharide is contained with respect to the total mass of (a) lecithin and (b) saccharide. The oil gelling agent according to any one of claims 1 to 3. A thickened gel-like composition comprising at least the oil gelling agent according to any one of claims 1 to 4 and (c) an oil component to form reverse string micelles. The thickening gel-like composition according to claim 5, wherein the thickening gel-like composition is at least one of cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils. 7. The oil gelling agent is contained in an amount of 1% by mass to 70% by mass with respect to the thickened gel composition as a mixing ratio of the oil gelling agent and the oil component (c).
The thickening gel-like composition as described in 1.