WO2013176243A1

WO2013176243A1 - Lecithin organogel formation agent

Info

Publication number: WO2013176243A1
Application number: PCT/JP2013/064442
Authority: WO
Inventors: 要橋崎; 好廣齋藤; 博之田口; 美湖今井
Original assignee: 学校法人日本大学
Priority date: 2012-05-25
Filing date: 2013-05-24
Publication date: 2013-11-28
Also published as: JPWO2013176243A1; JP6241852B2

Abstract

Provided as an organogel formation agent for forming reverse wormlike micelles, and a thickening gel composition, are: an organogel formation agent that offers high safety for the body and environment, an agreeable usability, and favorable gelation ability; and a thickening gel composition using said organogel formation agent. Lecithin and an aliphatic carboxylic acid having 1 to 3 carboxyl groups or 0 to 2 hydroxy groups act as an organogel formation agent for forming reverse wormlike micelles of a variety of oils; using a three-component mixed system of the lecithin, the carboxylic acid, and a variety of oils, it is possible to obtain a thickening gel composition having a reverse wormlike micelle structure.

Description

Lecithin organogel former

The present invention relates to a lecithin organogel forming agent that thickens or gels oils such as animal and vegetable oils, mineral oils, hydrocarbons, and fatty acid esters.

Organogel forming agents that thicken or gelate oils such as animal and vegetable oils, mineral oils, hydrocarbons, fatty acid esters, etc. are used in various fields such as cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils. Widely used in The performance generally required for the organogel forming 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 organogel forming agents, low molecular 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. , It is prone to dripping and poor handling, and there is a problem that if either higher alcohol or glycerin is lacking, the effect cannot be obtained, high safety to the living body and environment, good gelation ability, and feeling of use. An organogel forming agent that is excellent in handling properties and has good handling properties has not been obtained.

On the other hand, there are a few reports of gelation of oil by reverse string micelles (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 cord-like micelle, it can contain water-soluble drugs, enzymes and the like, and has characteristics not found in the above-mentioned organogel forming agent.

A three-component mixed system of lecithin / water / various oils has been reported as a typical system for forming this reverse string micelle (Non-patent Document 1). Examples of water substitutes include glycerin (Non-patent document 2), ethylene glycol (Non-patent document 2), formamide (Non-patent document 2), bile salts (Non-patent document 3), and inorganic salts (Non-patent document). 4) has been reported. 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 that these conventional reverse-like micelles have, in reverse-like micelles composed of typical lecithin / water / various oils, since water is contained in the ingredients, drugs that are susceptible to hydrolysis are blended. It is not possible. Those using glycerin as a substitute for water increase the viscosity but do not cause sufficient gelation. 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 skin, eyes, etc., and those using inorganic salts are used at high temperatures to dissolve gelling agents in oil. Heating is necessary and it is not easy to adjust to thickening or gelation.

The present inventors include lecithin / sucrose fatty acid ester (Patent Document 2), lecithin / saccharide (Patent Document 3), lecithin / urea (Patent Document 4), lecithin / polyglycerin (Patent Document 5), lecithin / ascorbic acid. Or as an organogelator that forms reverse string-like micelles of its derivative (Non-patent Document 5), it has high safety to the living body and environment, good gelation ability, excellent usability, and good handling properties. An organogel former was proposed. However, those using sucrose fatty acid esters and saccharides have the problem that odors peculiar to carbohydrates occur, and those using urea are not suitable for the food field. There is a problem that there is a limit.

Japanese Patent Laid-Open No. 5-4911 International Publication No. 2010/082487 Pamphlet International Publication No. 2010/122694 Pamphlet JP 2010-270299 A JP 2012-20979 A

The present invention, as an organogel-forming agent and thickening gel-like composition that forms reverse string micelles, is required to have high safety to the living body and the environment, excellent usability, and good gelling ability. It is an object of the present invention to provide an organogel-forming agent that has both, and a thickened gel-like composition using the organogel-forming agent.

As a result of intensive studies to solve the above problems, the present inventors have found that any one carboxylic acid having a lecithin / carboxyl group of 1 to 3 and a hydroxy group of 0 to 2 is a reverse string of various oils. It acts as an organogel forming agent that forms micelles, and using a ternary mixed system of carboxylic acid / various oils of any one of these lecithin / carboxyl groups 1 to 3 and hydroxy groups 0 to 2, It has been found that a thickened gel-like composition having a string-like micelle structure can be obtained and the above-mentioned problems can be solved.

That is, the present invention
[1] An organogel-forming agent that forms reverse string-like micelles composed of (a) lecithin, (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups.
[2] The organogel forming agent as described in [1] above, wherein the carboxylic acid has a molecular weight of 250 or less.
[3] As a mixing ratio of (a) lecithin and (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups, (a) lecithin and (b) The organogel-forming agent as described in [1] or [2] above, wherein (b) the carboxylic acid is contained in an amount of 0.1 to 35% by mass relative to the total mass of the carboxylic acid.
[4] A thickened gel-like composition comprising at least the organogel-forming agent according to any one of [1] to [3] above and (c) an oil component to form reverse string micelles.
[5] The thickened gel-like composition as described in [4] above, wherein the thickened gel-like composition is at least one of cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils object.
[6] The above-mentioned [4], wherein the organogel former is contained in an amount of 1 to 70% by mass with respect to the thickened gel composition as a mixing ratio of the organogel former and (c) oil component. Or the thickening gel-like composition as described in [5].
[7] A method for producing an organogel forming agent for forming reverse string micelles, wherein (a) lecithin, (b) one of aliphatic carboxyls having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups A method for producing an organogel forming agent, comprising dissolving an acid in an organic solvent and then evaporating the organic solvent.
[8] A method for producing a thickened gel-like composition in which reverse string micelles are formed, wherein (a) lecithin, (b) any one of carboxyl groups 1 to 3, and hydroxy groups 0 to 2 After the aliphatic carboxylic acid is dissolved in an organic solvent, the organic solvent is evaporated to obtain an organogel forming agent, and (c) an oil component is added to and mixed with the organogel forming agent. A method for producing a viscous gel composition.

The organogel forming agent for forming reverse string micelles of the present invention not only has 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. Can be The resulting thickened gel-like composition has thixotropic properties, is difficult to drip, has good handling properties, has long-term stability over several months, and has a maximum gelled viscosity (zero shear viscosity) of 100 Pa · s. As described above, there is an effect that a material of 10,000 Pa · s or more can be obtained. The transparency of the thickened gel-like composition can also be adjusted according to the organogel former used, the preparation conditions for the thickened gel-like composition, and the like, from transparent to translucent, white turbid, and the application used. 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

Hereinafter, the present invention will be described in detail. The organogel forming agent of the present invention is a material that can thicken or gel various oil components to form reverse string micelles. The organogel forming agent of the present invention comprises (a) lecithin, (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups, and various (c) oil components are added. When mixed, it becomes thickened or gelled to form a thickened gel-like composition having a reverse string-like micelle structure.

Reverse string-like micelles are 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 viscoelastic gel. In addition, since it has a hydrophilic environment inside, it is possible to enclose water-soluble components, drugs, enzymes, and the like.

The inventors of the present invention have conducted extensive research on reverse string micelles, and as a result, 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. In addition, paying attention to aliphatic carboxylic acids having a hydroxy group of 0 to 2, it was found that reverse string micelles can be formed from lecithin, the carboxylic acid and various oils.

The present inventors observed the structure of the obtained thickened or gel-like preparation, specifically, the thickened gel-like preparation formed by mixing lecithin, the carboxylic acid 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 a Nano-STAR manufactured by Bruker AXS, with an X-ray source of CuKα rays and an output of 45 kV / 120 mA. The SAXS measurement was performed at 25 ° C.

FIG. 2 shows a scattering curve (scattering intensity I (q) of a small-angle X-ray scattering measurement of a thickened gel composition in which 2% by mass of lecithin, 0.35% by mass of citric acid and 97.65% by mass of n-decane are mixed. ) And the scattering vector q). Here, q = (4π / λ) sin θ, θ is the scattering angle, and λ is the wavelength of the X-ray. According to this, since the scattering curve did not show a clear diffraction peak, it can be seen that no regular structure was formed. In this scattering curve, 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. Further, the cross-section radius (r) of the reverse cord-like micelle was determined to be 1.9 nm by the Cross-section plot based on the equations (1) and (2).

Here, Rc is the radius of rotation of the cross section. In addition, the exact length of the reverse-like micelles could not be calculated due to the limitation of the measurement range, but the simulation using the theoretical scattering function assuming rod-like particles using equation (3) (Calculated curve in the figure) ) Shows that the length (t) of the reverse string micelle is longer than 50 nm.

Here, J ₁ is a linear Bessel function. In addition, the thickened gel-like composition obtained by thickening or gelling the oil component using the organogel-forming agent of the present invention can be said to have reverse cord-like micelles formed from the gelation state and physical properties. .

(A) Lecithin as the organogel-forming agent of the present invention is a lipid product mainly composed of phosphatidylcholine and widely distributed in living organisms such as natural animals, plants, and microorganisms, and is used in liver, egg yolk, soybean, yeast, etc. Many are known to be included. Representative lecithin includes egg yolk lecithin, soybean lecithin and the like, and it is preferable to use them. Lecithin can be used alone or in admixture of two or more, and the lecithin preferably has a phosphatidylcholine content of about 55 to 99% by weight. 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, the proton of which is substituted with choline as the amine function. 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.

いない Unhydrogenated phosphatidylcholine (PC) that is 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 commonly used as fatty acids esterifying glycerol, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and possibly C20- Contains C22 fatty acids.

As the component (b) as the organogel forming agent of the present invention, any one carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups is used. A radix in this range is suitable for thickening and gelling the oil that forms reverse string micelles. Any carboxylic acid may be used as long as it is soluble in the organic solvent used in preparing the thickened gel composition. Among these, it is more preferable that these are selected from among those that are widely used in medical products, foods, supplements, cosmetics and the like, have no toxicity to the human body, and have high safety. Furthermore, the carboxylic acid has a molecular weight of 350 or less, preferably 300 or less, more preferably 250 or less from the viewpoint of thickening gelation.

Examples of the carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids. Of these, aliphatic carboxylic acids are preferred. Specifically, monocarboxylic acids such as acetic acid (molecular weight: 60.05, the same applies hereinafter), propionic acid (74.08), pyruvic acid (88.06), benzoic acid (122.12), oxalic acid (126 .07), malonic acid (104.1), succinic acid (118.09), fumaric acid (116.07), maleic acid (116.1), dicarboxylic acids such as phthalic acid (166.14), aconitic acid (174.11), 1,2,3-propanetricarboxylic acid (176.12), trimellitic acid (210.14), trimesic acid (210.14) and the like, glycolic acid (76.05), lactic acid Hydroxy monocarboxylic acids such as (90.08), glyceric acid (106.08), salicylic acid (138.12), 3,4-dihydroxybenzoic acid (154.12), L (+)-sake Hydroxydicarboxylic acids such as acid (150.09), L (−)-malic acid (134.09), citramalic acid (148.11), hydroxyphthalic acid (182.13), citric acid (192.12), Examples thereof include hydroxytricarboxylic acid such as isocitric acid (192.12). Preferably, pyruvic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aconitic acid, 1,2,3-propanetricarboxylic acid, glycolic acid, lactic acid, glyceric acid, L (+)-tartaric acid, L (−)-Malic acid, citric acid, and isocitric acid can be used.

The mixing ratio of (a) lecithin (b) the carboxyl group of 1 to 3 and the hydroxy group of 0 to 2 constituting the organogel-forming agent of the present invention is such that reverse micelles are Any mixing ratio can be used as long as it can be formed. (A) 1 to 70% by mass of lecithin, preferably 1.5 to 45% by mass, more preferably 2 to 30% by mass, and (b) 0.1 to 20% by mass, preferably 0.15% of the carboxylic acid. It can be ˜15% by mass, more preferably 0.2˜10% by mass. The mass ratio of (b) the carboxylic acid to the total amount of the organogel former varies depending on the (c) oil component, but when expressed as 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 7% by mass or more, and the upper limit is experimentally 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass. % Or less.

In order to produce the organogel forming agent of the present invention, an organic solvent capable of dissolving both (a) lecithin and (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups After being dissolved in the organic solvent, the organogel forming agent can be produced by evaporating the organic solvent. A thickened gel-like composition in which reverse string-like micelles are formed can be obtained by adding and mixing (c) an oil component and, if necessary, an additional component to the produced organogel forming agent.

(C) Oil components that can be gelled in the present invention are not particularly limited, and are oils 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 oil, 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, n-decane, isooctane, n-octane, n-heptane, n-hexane, cyclohexane; lauric acid, palmitic acid, stearic acid, oleic acid, behenic acid, etc. Higher fatty acids, fatty acid esters such as isopropyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, medium chain fatty acids such as caprylic acid triglyceride, caprylic acid / capric acid triglyceride, caprylic acid / capric acid / lauric acid triglyceride And triglycerides. These oils can be used singly or as a mixture of two or more.

In the oil to be organogelated, the additive component may be dissolved, dispersed, emulsified, suspended or mixed at a concentration that does not hinder thickening or gelation. 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.

(C) When the oil component is gelled by an organogel forming agent comprising (a) lecithin (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups. Can be mixed with the oil component in any amount as long as it can thicken or gel and form reverse string micelles. The mixing ratio of the oil component is (a) 1 to 70% by mass of lecithin, preferably 1.5 to 45% by mass, more preferably 2 to 30% by mass, and (b) 0.1 to 20% of the carboxylic acid. (C) The oil component is 30 to 99% by mass, preferably 50 to 98% by mass, more preferably 0.1% to 15% by mass, and more preferably 0.2 to 10% by mass. The amount can be 60 to 97% by mass.

Further, the mixing ratio of the organogel forming 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 36% 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 (zero shear viscosity) can be adjusted by the type and concentration of the organogel forming agent and the mixing ratio of (a) lecithin and (b) the carboxylic acid.

The thickening gel-like composition of the present invention contains (a) lecithin (b) the carboxylic acid, various (c) oil components are added, and other additive components are added as necessary to dissolve uniformly. By doing so, it can be gelled to form an inverted string micelle structure. As an example of preparing a thickened gel-like composition, (a) lecithin and (b) each of the above carboxylic acids are enclosed in a required amount container, an organic solvent is added and stirred, and components (a) and (b) are completely produced. 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 heating and dissolving a mixture of (a) lecithin, (b) the carboxylic acid and various (c) oil components 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 oxidation of lecithin and carboxylic acid, it is preferably performed in an inert gas atmosphere such as nitrogen. 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.

The method for producing the thickened gel composition of the present invention includes (a) lecithin and (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups in an organic solvent. After dissolution, the organic solvent is evaporated to obtain an organogel-forming agent, and (c) an oil component is added to and mixed with the formed organogel-forming agent to produce a thickened gel-like composition in which reverse string micelles are formed. Is preferred.

Examples of the organic solvent used in preparing the organogel forming agent and 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- Ketones such as butanone and cyclohequinone; ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; chloroform Halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, dichloroethane, isopropyl bromide, ethyl bromide, dichlorobenzene, tetrachloroethane, trichloroethane, trichloroethylene, and ethylene tetrachloride; Preferably used Lumpur. These organic solvents may be used alone or in combination.

The thickened gel-like composition of the present invention can be used as various products that exhibit gel-like properties at room temperature as detergents, cosmetics, medicines, foods, deodorants, bath agents, fragrances, deodorizers, and the like. Particularly suitable for use in detergents, cosmetics, pharmaceuticals, and foods. 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 the cosmetics, ingredients 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 thickened gel-like composition formed by adding and mixing various oils to the organogel-forming agent of the present invention forms a reverse string-like micelle structure, so that 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. These reverse string micelles have lecithin and carboxylic acid molecule polar groups facing inward and hydrophobic groups facing outward. In the interior, a hydrophilic environment, that is, a small water pool (water phase) is formed. Examples of water-soluble substances that can be encapsulated include whitening agents, anti-inflammatory agents, antibacterial agents, hormone agents, vitamins, various amino acids and their derivatives, enzymes, antioxidants, hair restorers, and other pharmaceutical ingredients. It is done.

The thickened gel-like composition formed by adding and mixing various oils to the organogel forming agent of the present invention directly or with a water-soluble substance, water-soluble drug, or enzyme that is hardly soluble or insoluble in oil. 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 thickened gel-like composition formed can be adjusted according to the organogel-forming 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 organogel forming agent of the present invention is excellent in gelation ability with respect to various oils, can form a stable gel over a long period of 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" in touch. In addition, the organogel forming agent of the present invention is made of material components such as lecithin and carboxylic acid, which are highly safe and biodegradable, and are environmentally conscious.
The organogel-forming agent of the present invention is further used in fields other than the above, such as quasi-drugs, inks, paints, lubricants, plastics, rubbers, metals, etc., as well as agriculture, fisheries, waste oil treatment, etc. be able to.

Hereinafter, the present invention will be specifically described by way of 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 mm and 35 mm, cone angle 1 ° and 4 °) and a rotary rheometer (HAAKE MARSIII, manufactured by Thermo Fisher Scientific) equipped with a Peltier temperature controller. went. 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 determined for each shear rate, and the zero shear 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.
☆ Excellent gelation (zero shear viscosity of 10,000 Pa · s or more)
★ Good gelation (with zero shear viscosity of 1000 Pa · s or more and less than 10000 Pa · s)
◎ Gelation (zero shear viscosity of 100 Pa · s or more and less than 1000 Pa · s)
○ Thickening (zero shear viscosity of 10 Pa · s or more and less than 100 Pa · s)
× Insufficient thickening gelation (zero shear viscosity less than 10 Pa · s)

[Transparency of thickened gel composition]
The transparency of the gel was observed visually after encapsulating the prepared thickened gel-like composition in a sample bottle having a diameter of 27.5 mm and a height of 70 mm and storing it in a thermostatic bath set at 25 ° C. for one month. It is evaluated as ◎: transparent, ◯: translucent, Δ: cloudy, x: two-phase separation.

[Examples 1 to 11]
(Formulation of thickening gel composition)
(A) As a component lecithin, soybean lecithin (trade name L-α-Phosphatidylcholine (Soy-95%) “Avanti Polar Lipids, Inc.”), (b) component citric acid (manufactured by Kanto Chemical Co., Inc.), As a component (c), n-decane (0.774 mPa · s (25 ° C.) manufactured by Kanto Chemical Co., Inc.) was used, and a thickening gel-like composition was prepared with the composition shown in Table 1. Examples 1 to 11 were made according to the respective composition compositions.

(Preparation of thickened gel composition)
Preparation of the thickened gel-like composition was carried out by enclosing the necessary amount of component (a): lecithin and component (b): carboxylic acid in a bottle, adding methanol, and stirring using a magnetic stirrer. After completely dissolving lecithin and carboxylic acid, methanol is completely evaporated by drying under reduced pressure. (C) A necessary amount of the oil component was added and further stirred overnight, and the bottle was prepared by allowing it to stand for several days in a thermostatic bath at 25 ° C. for stabilization. In the following examples and comparative examples, the thickening gel composition was prepared by the same preparation means.

Examples 1 to 11 are prepared by preparing thickening gel compositions with component (a): lecithin in an amount of 5.0 to 20.0% by mass. The ratio of citric acid in these organogel forming agents, that is, (b) component / ((a) component + (b) component) is 11.1 to 18.4% by mass, and the organogel in the thickened gel composition The ratio of the agent, ie, ((a) component + (b) component) / ((a) component + (b) component + (c) component) is 5.9 mass% to 24 mass%. The state of the thickening gel was transparent, and all were excellent gelation ☆, good gelation ★, and gelation. In particular, when the citric acid was 2.25 mass% and 4 mass%, the gel was very well thickened with zero shear viscosity of 60100 Pa · s and 73420 Pa · s. The evaluation results are shown in Table 1.

[Examples 12 to 20]
(Formulation of thickening gel composition)
As the component lecithin (a), soybean lecithin (trade name L-α-Phosphatidylcholine (Soy-95%), manufactured by Avanti Polar Lipids, Inc.), component (b) L (+)-tartaric acid (Kanto Chemical Co., Ltd.) N-decane (0.774 mPa · s (25 ° C.) manufactured by Kanto Chemical Co., Ltd.) as the component (c), and a thickened gel-like composition was prepared and formulated as shown in Table 2. Examples 12-20 were taken.

The ratio of L (+)-tartaric acid in the organogel formers of Examples 12 to 20, that is, (b) component / ((a) component + (b) component) was 7% to 12.3% by mass, thickening The ratio of the organogel-forming agent in the gel composition (component (a) + component (b)) / (component (a) + component (b) + component (c)) is 5.6 to 22.5 mass%. %. The state of the thickening gel was transparent or translucent, and all were excellent gelation ☆, good gelation ★, and gelation. In particular, when L (+)-tartaric acid was 1.25% by mass and 2.5% by mass, the gels were very well thickened with zero shear viscosity of 49210 Pa · s and 111500 Pa · s. The evaluation results are shown in Table 2.

[Examples 21 to 32]
(Preparation of thickened gel composition)
Preparation of the thickened gel-like composition was performed in Example 3, using 1,2,3-propanetricarboxylic acid (Wako Pure Chemical Industries, Ltd.) instead of the citric acid of component (b), and changing the blending amount. In Examples 21 to 25, trans-aconitic acid (manufactured by SIGMA-ALDRICH) was used as the component (b). Examples 26 to 28, L (-)-malic acid (manufactured by Kanto Chemical Co., Ltd.) as the component (b) Examples 29 and 30, using glycolic acid (manufactured by Kanto Chemical Co., Ltd.) as the component (b) and Example 31 using fumaric acid (manufactured by Kanto Chemical Co., Ltd.) as the component (b) Prepared. As a blending composition shown in Table 3, a thickened gel composition was prepared.

In Examples 21 to 32, the thickening gel-like composition was prepared by using (a) component: 10% by weight of lecithin and using various amounts of the various carboxylic acid (b) components. All were good gelation *, gelation, and thickening ○. Even if the gel was thickened, it was in a state that would not cause any problems in use. All the transparency was ◎ transparent. The evaluation results are shown in Table 3.

[Examples 33 to 34]
(Preparation of thickened gel composition)
Preparation of the thickened gel composition was the same as in Example 1 (a) component: lecithin, (b) component: citric acid, and (c) component cyclohexane (manufactured by Kanto Chemical Co., Ltd. 0.828 mPa · s (25 ° C.)) and liquid paraffin (146 mPa · s (25 ° C.) manufactured by Kanto Chemical Co., Inc.) were used to prepare Examples 33 to 34. As a blending composition shown in Table 4, a thickened gel composition was prepared. In Table 4, Example 7 using n-decane as the component (c) is also listed for comparison.

In Examples 33 to 34, thickened gel compositions were prepared using the necessary amounts of (a) component: lecithin, (b) component: citric acid, and various oil components, respectively. Both were excellent gelation ☆ and gelation. All the transparency was ◎ transparent. The evaluation results are shown in Table 4.

[Examples 35 to 39]
(Preparation of thickened gel composition)
Preparation of the thickened gel composition is the same as in Example 1 (a) component: lecithin, (b) component: citric acid, and (c) caprylic acid triglyceride (product name Coconut RK Kao Co., Ltd.) Examples 35 to 39 were prepared using 200.71 mPa · s (25 ° C.). As a blending composition shown in Table 5, a thickened gel composition was prepared.

In Examples 35 to 39, thickened gel compositions were prepared using the necessary amounts of (a) component: lecithin, (b) component: citric acid, and oil component, respectively. The gelation was also excellent gelation ☆, good gelation ★, and gelation. The transparency was ◎ transparent, ○ translucent, and Δwhite turbidity. The evaluation results are shown in Table 5.

[Examples 40 to 44]
(Preparation of thickened gel composition)
Preparation of thickening gel-like composition was carried out in Examples 35 to 39 by replacing caprylic acid triglyceride as component (c) with caprylic acid / capric acid triglyceride (product name: Coconard MT Kao Co., Ltd. 21.89 mPa · s ( Examples 40 to 44 were prepared using 25 ° C.). As a blending composition shown in Table 6, a thickened gel composition was prepared.

In Examples 40 to 44, thickened gel compositions were prepared using the required amounts of (a) component: lecithin, (b) component: citric acid, and oil component, respectively. The gelation was also excellent gelation ☆, good gelation ★, and gelation. The transparency was ○ translucent and Δ cloudy. The evaluation results are shown in Table 6.

[Examples 45 to 47]
(Preparation of thickened gel composition)
In Examples 40 to 42, the thickened gel composition was prepared by replacing caprylic acid / capric acid triglyceride as component (c) with caprylic acid / capric acid / lauric acid triglyceride (product name: Coconard ML, Kao Corporation). Examples 45 to 47 were prepared using 30.13 mPa · s (25 ° C.)). As a blending composition shown in Table 7, a thickened gel composition was prepared.

In Examples 45 to 47, thickened gel compositions were prepared using the required amounts of (a) component: lecithin, (b) component: citric acid, and oil component, respectively. The gelation was good and the gelation was. The transparency was ○ translucent and Δ cloudy. Table 7 shows the evaluation results.

[Comparative Examples 1 to 3]
(Formulation of thickening gel composition)
(A) Component: Soy lecithin (trade name “L-α-Phosphatidylcholine (Soy-95%)” manufactured by Avanti Polar Lipids, Inc.) 10% by mass as lecithin, n-decane (Kanto Chemical) as component (c) Co., Ltd.), cyclohexane (manufactured by Kanto Chemical Co., Ltd.), liquid paraffin (manufactured by Kanto Chemical Co., Ltd.) 90% by mass as a blending composition, thickening gel-like compositions were prepared as Comparative Examples 1 to 3. .

Comparative Examples 1 to 3 did not use the carboxylic acid of component (b), so a thickening gel could not be formed. Table 8 shows the composition and evaluation results. On the other hand, in the present invention, as shown in the examples, for the oil component (c) n-decane, a viscosity increase of about 144 million times was easily obtained at 25 ° C. and 0.774 mPa · s. The thickening gel could not be formed even with the carboxylic acid (b) and the oil component (c).

According to the present invention, lecithin and any one aliphatic carboxylic acid having a carboxyl group of 1 to 3 and a hydroxy group of 0 to 2 can be used to form reverse string micelles by a three-component mixed system of various oils. An organogel forming agent 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., various cosmetics, pharmaceuticals, foods It can be widely used as an organogel forming agent. Furthermore, the thickening gel composition formed by using the organogel forming agent has thixotropic properties, good handling properties, and good long-term stability.

Claims

(A) Lecithin, (b) Organogel-forming agent that forms reverse cord-like micelles composed of any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups.
2. The organogel forming agent according to claim 1, wherein the carboxylic acid has a molecular weight of 250 or less.
As a mixing ratio of (a) lecithin and (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups, (a) lecithin and (b) 3. The organogel forming agent according to claim 1, comprising 0.1 to 35% by mass of the carboxylic acid based on the total mass.
A thickened gel-like composition comprising at least the organogel-forming agent according to any one of claims 1 to 3 and (c) an oil component to form reverse string micelles.
The thickening gel-like composition according to claim 4, wherein the thickening gel-like composition is at least one of cosmetics, pharmaceuticals, foods, paints, inks, and lubricating oils.
6. The mixing ratio of the organogel-forming agent and (c) oil component contains 1 to 70% by mass of the organogel-forming agent with respect to the thickened gel composition. Thickening gel composition.
A method for producing an organogel forming agent that forms reverse string micelles, wherein (a) lecithin and (b) any one aliphatic carboxylic acid having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups are organically formed A method for producing an organogel-forming agent, comprising evaporating an organic solvent after being dissolved in a solvent.
A method for producing a thickened gel-like composition in which reverse string micelles are formed, wherein (a) lecithin, (b) any one aliphatic carboxyl having 1 to 3 carboxyl groups and 0 to 2 hydroxy groups After dissolving the acid in the organic solvent, the organic solvent is evaporated to form an organogel-forming agent, and (c) an oil component is added to and mixed with the organogel-forming agent. A method for producing the composition.