JPH01288330A - Microemulsion - Google Patents

Abstract

PURPOSE:To elevate the thermal stability of a microemulsion by preparing the microemulsion by mixing a hydrophilic surfactant, a specified oil, a polyhydric alcohol, and water in specified amount resp. and by specifying the average grain size. CONSTITUTION:A microemulsion is prepared by mixing (a) a hydrophilic surfac tant, (b) at least one selected from a group consisting of an oil having an in organic property 0 in an organic conceptional figure with the number of C >=17, an oil wherein 0 < inorganic property <= 20 with the number of C >=18, an oil wherein 20 < inorganic property <= 50 with the number of C >=19, an oil wherein 50 < inorganic property <= 100 with the number of C >=20, an oil wherein 100 < inorganic property <= 150 with the number of C >=21, an oil wherein 150 < inorganic property <= 200 with the number of C >=22, and an oil wherein 200 < inorganic property <= 250 with the number of C >= 23, (c) a polyhydric alcohol and (d) water. In this case, the content of (b) is adjusted to 0.005-60% in weight, the weight ratio of (a) to (b) is made (1 : 0.5)-(1 : 10), and the average grain size is made 0.01-0.15mum.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a compound having an average particle size of 0, which allows a large amount of oil to be stably blended over a wide temperature range with a small amount of hydrophilic surfactant.
．． 01 to 0.15 μm.

[Prior Art] Conventionally known microemulsions are as follows.

That is, the first is obtained using a conventional nonionic surfactant and oil, the second is a combination of an anionic surfactant and a cosurfactant, and the third is a combination of an anionic surfactant and a nonionic surfactant. It uses a combination of a surfactant or an electrolyte.

The first is that when a hydrocarbon such as cyclohexane or n-heptane is added to an aqueous solution of a nonionic surfactant such as +so-RCHO(CH2CH2O) 9H and the temperature is raised, the nonionic surfactant becomes cloudy. In front of this point, a region appears where the amount of solubilized hydrocarbons (oil) increases rapidly (Kozo Shinoda, 209-225, Solution and Solubility, Maruzen). It is known that in the 1W region from the solubilization limit temperature to the cloud point shown in the phase diagram, the solubility of oil in the aqueous phase increases dramatically, forming a so-called microemulsion. However, microemulsions (1w region) with increased oil solubilization obtained with nonionic surfactant-hydrocarbon systems that have been studied previously have maintained the hydrophilic-lipophilic balance of the system. It is thermodynamically stable within a very narrow temperature range (from a few degrees Celsius to about 10 degrees Celsius), but if it deviates even slightly from this range, the system becomes cloudy immediately or over time, and eventually separates into water and oil. It is said to be put away. For this reason, it is extremely difficult to apply it to cosmetics or pharmaceuticals.

The second method is to balance the hydrophilic-lipophilic balance of the system by combining an anionic surfactant and co-surfactants such as pentanol, hexanol, and octatool. The aim is to utilize the region where the amount of solubilization increases rapidly. The third is
By adding an electrolyte to a combination of a lipophilic nonionic surfactant and a specific anionic surfactant, or a combination of a lipophilic nonionic surfactant and an ionic surfactant, the hydrophilic-philic It attempts to utilize the region where the amount of solubilized hydrocarbons (oil) increases rapidly within a very narrow ratio range where the oil balance is balanced (Kozo Shinoda, Hiroyuki Saijo, 808-314.35.1986 , JP-A-58-1
28311, JP-A-58-1.31127). In the second and third methods, stability against temperature has been solved, but the composition in which the microemulsion exists thermodynamically stably is very limited, and if it deviates from this range, it will be immediately Or, it was said that it would become cloudy and separate over time. For this reason, there is a concern that in actual product systems, the formulation may be considerably limited or complicated. Furthermore, the second method uses a cosurfactant such as hexanol, which poses a safety problem.

In this way, if conventionally known microemulsions are to be used practically, they must be used within a thermodynamically stable solubilization range within a narrow temperature or composition range, and if they deviate from this range. This was considered impossible from a stability standpoint.

On the other hand, ultraviolet absorbers may be added to general emulsions as additives. In particular, in recent years, skin aging caused by sunlight has become a problem, and the role of ultraviolet absorbers has been attracting attention as a means of preventing sunburn caused by ultraviolet rays from the sun.
Cosmetics containing ultraviolet absorbers are increasingly appearing on the market. However, there is currently no way to blend large amounts of this kind of oil, which has a large molecular weight, into a transparent or translucent form, so it is currently necessary to blend it into bases such as white creams and emulsions. Even though there was an idea to use a microemulsion that could make a large amount of oil transparent or translucent with a small amount of emulsifier, it was impossible to put it into practical use due to the above technical problems.

[Problems to be Solved by the Invention] As described above, although conventional microemulsions have the advantage of being transparent or translucent and can contain a large amount of oil with a small amount of surfactant, First, there is a problem with stability against temperature, and the composition has to be extremely limited or complicated in order to achieve stability, so no examples of practical use have been found.

Particularly in cosmetics and pharmaceuticals, a system in which a very small amount of oil is solubilized with a large amount of emulsifier is generally used as a base for lotion or lotion type that contains a transparent oil. Since it is necessary to use a large amount of oil, there was a safety problem when trying to incorporate a large amount of oil.

Furthermore, similar problems exist with lotions and lotions that contain UV absorbers as additives. There was a technical constraint that it had to be used for

In particular, when used in sunscreen cosmetics, medicines, etc., the following problems arise.

That is, most of the ultraviolet absorbers used on the market are liquid or solid oil-soluble with high viscosity, and many of them are highly polar. For this reason, there are problems such as severe irritation to the skin and unpleasant stickiness during use, so it is often used in a state dissolved in oil. However, oils that can dissolve ultraviolet absorbers often have to be highly polar from the viewpoint of solubility, leaving problems such as unpleasant stickiness during use. Therefore, with the exception of those for special uses such as sun care, efforts have been made to incorporate them into aqueous bases as white emulsions such as milky lotions and creams, and considerable improvements have been made.

However, these types cannot satisfy problems such as stickiness.

Therefore, it is considered most desirable to use a solubilized type such as a lotion or lotion that has a smooth feel. However, with the currently known solubilization types, the amount that can be solubilized into the product is extremely small, especially oils with large molecular weights such as ultraviolet absorbers. It is about 0.5 at most. If you try to add more UV absorbers than that,
Oil components, including ultraviolet absorbers, exceed the maximum amount that can be solubilized by surfactants, resulting in oil floating and clouding, and the product has no commercial value as a toner or lotion. In this way, when trying to incorporate a large amount of UV absorbers in consideration of the UV absorption effect, it is necessary to use a large amount of surfactant from the viewpoint of stability, but in this case, the surfactant itself may cause irritation. Gender becomes an issue. As described above, there is a limit to the amount of UV absorber that can be added in terms of stability and irritation, and it has not been possible to achieve a sufficient amount of UV absorber in a smooth base to achieve the UV absorption effect. The current situation is that there is no such thing.

However, there is a great need for lotions and lotion-type bases that can suppress stickiness and provide a smooth feel. The completion of a microemulsion base that can be contained with a small amount of surfactant has been a major challenge for researchers.

Purpose of the Invention The present invention was developed in view of the problems of the prior art, and has a relatively simple composition, is stable over a very wide temperature range, and has a large amount of The object is to provide a microemulsion capable of containing oil. More specifically, the objective is to provide a microemulsion that can uniformly dissolve much more oil with a small amount of surfactant, is stable over a wide temperature range, and is highly safe.

In particular, an object of the invention according to claim 2 or 3 is to provide a microemulsion that can contain an arbitrary amount of ultraviolet absorber at the same time as the above-mentioned object.

The application of the present invention is not limited, and can be used in all emulsification fields that require the above purpose, but it can be used in fields such as pharmaceuticals, quasi-drugs, cosmetics, etc., and has a light and good feeling of use. The purpose of the invention also includes providing a highly safe microemulsion (for example, as a base) that does not cause skin irritation. The purpose is to provide products (including anti-inflammatory cosmetics).

[Means for Solving the Problems] That is, the present invention according to claim 1 comprises: a hydrophilic surfactant; one or more oils satisfying the following conditions; Oil with a property of 0 and a carbon number of 17 or more, 0
Inorganic ≦20 and a carbon number of 18 or more, 20<inorganic≦50 and a carbon number of 19 or more, 50<inorganic≦100 and a carbon number of 20 or more, 100 Oil with a property≦150 and a carbon number of 21 or more, 150〈Inorganic≦200 and a carbon number of 22 or more, 200〈Inorganic〉Oil with a carbon number of ≦250 and a carbon number of 23 or more, 250〈Inorganic and an oil having a carbon number of 24 or more) containing at least a polyhydric alcohol and water, the content of the above oil is 0.005 to 60% by weight, and a hydrophilic surfactant and a total oily component in the system. Weight ratio is 1:0.5~
A microemulsion characterized in that the ratio is 1:10 and the average particle diameter is 0.01 to 0.15 μm.

The present invention according to claim 2 is characterized in that it contains at least a hydrophilic surfactant, an oil capable of dissolving an oil-soluble ultraviolet absorber, an oil-soluble ultraviolet absorber, and water, and a hydrophilic surfactant. The sum of the agent, the oil that can dissolve the oil-soluble ultraviolet absorber, and the oil-soluble ultraviolet absorber is 0.
5 to 7, and an average particle diameter of 0.01 to 0.15 μm. The present invention according to claim 4 is a cosmetic or quasi-drug containing the microemulsion according to claim 1.2 or 3.

Hereinafter, the configuration of the present invention will be explained in detail.

As the surfactant used in the present invention, HLB must be hydrophilic because it is necessary to obtain an oil-in-water microemulsion, but other than that, ordinary nonionic surfactants and ionic surfactants may be used. Can be used.

To give specific examples, examples of nonionic surfactants include polyoxyethylene (hereinafter referred to as POE) sorbitan monooleate, POE sorbitan monostearate,
POE sorbitan fatty acid esters such as POE sorbitan trioleate, POE sorbitan monooleate,
POE sorbitol fatty acid esters such as POE sorbitol pentaoleate and POE sorbitol monostearate, POE glycerol fatty acid esters such as POE glycerol monostearate, POE glycerol monoisostearate, POE glycerol triisostearate,
POE monooleate, POE distearate, POE
POE fatty acid esters such as dioleate, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE 2-octyl dodecyl ether,
POE 2-hexyl decyl ether, POE 2-heptyl undecyl ether, POE 2-decyl tetradecyl ether, POE 2-decyl pentadecyl ether,
POE alkyl ethers such as OE cholestanol ether, POE alkyl phenyl ethers such as POE nonylphenyl ether, POE-POP block copolymers, p.

POE-POP alkyl ethers such as E-POP cetyl ether, POE-POP2-decyltetradecyl ether, POE-POP hydrogenated lanolin, POE castor oil or hydrogenated castor oil derivatives such as POE castor oil, POE
Examples include POE beeswax and lanolin derivatives such as sorbit beeswax, sucrose esters such as sucrose oleic acid monoester, polyglycerin monoalkyl esters and monoalkyl ethers.

Examples of anionic surfactants include fatty acid soaps such as sodium laurate and potassium palmitate;
Higher alkyl sulfate salts such as sodium lauryl sulfate and potassium lauryl fluorosulfate, polyoxyethylene (hereinafter referred to as POE), alkyl ether sulfate salts such as triethanolamine lauryl sulfate, N-acyl sarcosinates such as sodium lauroyl sarcosinate, N - Higher fatty acid amide sulfonates such as sodium myristoyl-N-methyltaurate, phosphate ester salts such as POE sodium oleyl ether phosphate, POE stearyl ether phosphate, and sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate. , alkylbenzene sulfonates such as sodium linear dodecylbenzenesulfonate, linear dodecylbenzenesulfonic acid triethanolamine, linear dodecylbenzenesulfonic acid, N-
Examples include N-acylglutamates such as monosodium lauroylglutamate, disodium N-stearoylglutamate, and monosodium N-myristoylglutamate.

Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride, dialkyldimethylammonium salts, alkyl quaternary ammonium salts, and alkylamine salts.

As the amphoteric surfactant, for example, 2-undecyl-N
, N, N-(hydroxyethylcarboxymethyl)-2
- imidacillin-based amphoteric surfactants such as imidacillin sodium, 2-cocoyl-2-imitazolinium hydroxide-1-carboxyethyloxy disodium salt, 2
-Betaine surfactants such as heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amidobetaine, sulfobetaine, N-lauryl β-alanine, N-stearyl β - Amino acid salts such as alanine and the like can be mentioned.

These hydrophilic surfactants may be used alone or in combination of two or more.

In order to obtain a good microemulsion according to the present invention, the structure of the lipophilic group of the surfactant is preferably an aliphatic hydrocarbon having 12 or more carbon atoms, more preferably 16 carbon atoms. The above is good. Furthermore, in order to improve the stability at low temperatures, it is preferable that the Kraft point be below room temperature, preferably below 0°C.

The oil used in the present invention is an oil with an inorganic property of 0 on the Organic Concept Diagram (Organic Concept Diagram, Yoshio Koda, Sankyo Publishing, 1984) and a carbon number of 17 or more; Oil with a carbon number of 18 or more, 20 inorganic ≦50 and a carbon number of 19 or more, 50 inorganic ≦100 and a carbon number 2
Oil of 0 or more, 100, inorganic ≦150, and carbon number 2
1 or more oil, 150, inorganic ≦200, and carbon number 2
2 or more oil, 200〈Inorganic≦250 and carbon number is 2
3 or more oils, 250 oils that are inorganic and have 24 or more carbon atoms.

It is preferable that these oils are in a liquid state at room temperature, but even if they are solid, there is no problem as long as they are dissolved and become a liquid state when mixed.

As a specific example, oils with an inorganic property of 0 and a carbon number of 17 or more include hydrocarbons such as liquid paraffin, squalane, blistane, paraffin, petrolatum, etc.
Examples of oils that are inorganic≦20 and have a carbon number of 18 or more include hydrocarbons such as squalene, ethers such as dinonyl ether, and oils that are inorganic≦50 and have a carbon number of 19.
Examples of the above-mentioned oils include diethers such as ethylene glycol dioctyl ether, and examples of oils that are inorganic ≦100 and have a carbon number of 20 or more include myristic octyldodecyl, butyl stearate, myristyl myristate, and decyl oleate. , monoesters such as oleyl oleate, higher alcohols such as octyldodecanol, etc., which are 100 <inorganic ≦ 150 and have a carbon number of 2
Examples of one or more oils include unsaturated higher alcohols such as lanolin alcohol, and examples of oils that are 150<inorganic≦200 and have a carbon number of 22 or more include higher fatty acids such as erucic acid, and di-2-ethylhexyl cepacate. , diethyls such as di-2-ethylhexyl adipate, etc., 20
Examples of oils that are inorganic≦250 and have a carbon number of 23 or more include chryceryl monoethers such as chrycerol monooleyl ether, acid amides such as lauroyl lauryl amine, etc. Examples of oils of 24 or higher include avocado oil, camellia oil, turdle oil,
Macadamia oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, basic oil, wheat germ oil, sasanquat oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil , tea seed oil, kaya oil, rice bran oil, Chinese palm oil, Japanese tung oil, jojoba oil, germ oil, cacao butter, coconut oil, and other plant and animal fats and oils. One or more of these are used.

The stability of microemulsions tends to improve as oils with larger carbon numbers and more non-polar properties are used.In order to make microemulsions more stable, oils with carbon numbers that are at least 1 larger than the above-mentioned limitations are recommended. preferable. More preferably, one larger than 2 is used.

Furthermore, the present inventors discovered that cyclohexane, n-hebutane, isopropyl myristate, and
Even for low molecular weight oils such as dibutyl sepatate, stable microemulsions can surprisingly be obtained by adding the oil according to the limitations of the present invention.

The quantity ratio of such oil and the oil according to the limitations of the present invention is 1:
0.001 to 1:0.7, and the weight ratio of the hydrophilic surfactant to the total oily components in the system is 1:0.5 to 1.
:10.

The total oily component in the system means the sum of the oil according to the limitations of the present invention and the total amount of other oils including such oil.

Examples of such oils include oils whose inorganicity on the organic conceptual diagram is O and whose carbon number is 5≦carbon number≦16; Inorganic ≦5
0 and the number of carbon atoms is 7≦carbon number≦18, 50; Inorganic≦100 and the number of carbon atoms is 8≦carbon number≦19, 100
An oil that is inorganic≦150 and has a carbon number of 10≦carbon number≦20; 14≦carbon number≦22 oil, 250〈inorganic and carbon number 16≦carbon number≦23 oil, and specific examples include: Inorganic is O and carbon number is 5
Examples of oils with ≦carbon number≦16 include n-hebutane, n-hebutane,
- Hydrocarbons such as octane, 0<inorganic≦20 and 6≦carbon count≦17 oils include hydrocarbons such as cyclohexane, ethers such as diheptyl ether, etc. 20≦inorganic≦ 50 and carbon number is 7≦carbon number≦1
Examples of the oil of No. 8 include diethers such as ethylene glycol dibutyl ether, etc., and oils having an inorganic property of ≦100 and a carbon number of 8≦carbon number of ≦19 include, for example, isopropyl myristate, ethyl caprate, and ethyl laurate. Monoesters such as esters, alcohols such as 2-hebutylnonanol, etc., and oils that are 100 <inorganic ≦ 150 and have a carbon number of 10≦carbons ≦20 include isomyristic acid, isostearic acid, capric acid, etc. Fatty acids such as acids, dialcohol monoethers such as ethylene glycol monolauryl ether, etc., oils that are inorganic ≦200 and have a carbon number of 12≦carbon≦21 include, for example, dibutyl adipate, diisopropyl sepatate, etc. , diesters such as dibutyl sepatate, etc., 200 < inorganic < 2
Examples of the oil having a carbon number of 50 and a carbon number of 14≦carbon number≦22 include acid amides such as lauric acid butylamide, etc.
Examples of the oil which is inorganic and has a carbon number of 16≦carbon number≦23 include triglycerides such as tricabroin, and one or more of these may be used.

Of course, it is also possible to use only oil according to the limitations of the present invention.
Other oils are not necessarily necessary.

Further, the type of polyhydric alcohol used in the present invention may be one commonly used, and specifically, for example, propylene glycol, 1,3-butylene glycol, 1,
Divalent alcohols such as 4-butylene glycol, trivalent alcohols such as glycerin, hexavalent alcohols such as sorbitol and mannitol, diethylene glycol, dipropylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, polyglycerin, etc. Examples include polyhydric alcohol polymers, sugar alcohols such as sorbitol, maltitol, maltotriose, mannitol, etc., and one or more of these may be used.

The microemulsion in the present invention contains 0.1-30% surfactant, 0.005-60% oily component, 10-99.8% water, and 5-90% polyhydric alcohol. The weight ratio of the surfactant to the total oily components in the system is 1:0.5 to 1:10, and the emulsion particle size is 0.5 to 1:10.
01 to 0.15 μm. Outside this range, the effects of the present invention will not be exhibited.

All average particle diameters used here were measured by dynamic light scattering, and specifically, NI GOMP-
270 (manufactured by HIAC/ROYCO).

Such microemulsions can be prepared using an emulsifier that can apply strong shearing force, such as a high-pressure homogenizer or an ultrasonic emulsifier, but the ratio of polyhydric alcohol to water during emulsification is 1:5 to 1:5. It is preferable to emulsify at a ratio of 19:1 and, if necessary, add water to a predetermined polyhydric alcohol concentration after emulsification. Another 0.
In order to obtain particles of 0.05 μm or less, it is preferable to use a method in which the ratio of polyhydric alcohol:water during emulsification is 1:4 to 8:2, and water is added after emulsification to a predetermined polyhydric alcohol concentration. In addition, when using a high-pressure homogenizer, 1
It is preferable to emulsify under a pressure of 0.00 atm or more, but when obtaining particles of 0.05 μm or less,
It is preferable to emulsify at a temperature of 0.degree. C. or less and a pressure of 300 atm or more.

Various other components can be added to the microemulsion of the present invention. Among such components, those listed as water phase components include methyl alcohol,
There are ethyl alcohol, propyl alcohol, isopropyl alcohol, sodium hyaluronate, etc., which are arbitrarily selected and used in actual product systems.

Microemulsion according to claim 2 or 3Claim 2
The hydrophilic surfactants used in the invention described are:
This is the same as that described in claim 1.

On the other hand, the invention according to claim 3 is a microemulsion using a hydrophilic nonionic surfactant. Although this can also be manufactured by the method according to the invention of claim 2,
The manufacturing method has advantages of extremely high technical value as described below.

As the ultraviolet absorber used in the present invention according to claims 2 and 3, any ordinary ultraviolet absorber can be used as long as it is oil-soluble. That is, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-jethoxy PABA ethyl ester, N,
, benzoic acid-based UV absorbers such as todimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N, todimethyl PABA octyl ester, anthranilic acid-based UV absorbers such as homomenthyl N-acetylanthranilate, amyl salicylate, Salicylic acid UV absorbers such as menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, pendyl salicylate, p-isobrobanol phenyl salicylate, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl Cinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate,
Isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cycloto xyl-p-methoxycinnamate,
Ethyl-α-cyano-β-phenylcinnamate, 2-
Cinnamic acid-based ultraviolet absorbers such as ethylhexyl-α-cyano-β-phenylcinnamate, chryceryl mono-2-ethylhexanoyl-monobaramethoxycinnamate, chryceryl-2-ethylhexanoyl-monobaramethoxycinnamate, 2 , 4-dihydroxybenzophenone,
2,2°-dihydroxy-4-methoxybenzophenone, 2,2°-dihydroxy-4,4′-dimethoxybenzophenone, 2,2°,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-Hydroxy-4-methoxy-4°-methylbenzophenone, 2-hydroxy-4=methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4"-phenyl-benzophenone-2-carboxy rate, 2-hydroxy-4-
n-octoxybenzophenone, 4-hydroxy-3-
Benzophenone ultraviolet absorbers such as carboxybenzophenone, 3-(4°-methylbenzylidene)-d,
l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-
Phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2
-(2°-hydroxy-5°-1-octylphenyl)
Benzotriazole, 2-(2"-hydroxy-5'-methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5-(3,3-dimethyl-2
-norbornylidene)-3-pentan-2-one, and the like.

One type or a combination of two or more of these ultraviolet absorbers are used within a range that dissolves in the oil described below.

The oil used in the present invention may be any oil that can dissolve these ultraviolet absorbers, and specific examples include:
For example, n-hebutane, n-octane, liquid paraffin,
Hydrocarbons such as squalane, bristane, paraffin, petrolatum, squalene, etc., hydrocarbons such as cyclohexane, ethers such as dioctyl ether, dioctyl ether, etc.1, diethers such as ethylene glycol dibutyl ether, isopropyl myristate, Monoesters such as octyldodecyl myristate, isopropyl valmitate, decyl oleate, oleyl oleate, 2-hebutylnonanol, isostearyl alcohol, octyldodecanol, oleyl alcohol,
Alcohols such as lanolin alcohol, fatty acids such as isomyristic acid, isostearic acid, capric acid, eicosenoic acid, dialcohol monoethers such as ethylene glycol monolauryl ether, dibutyl adipate, diisopropyl sepatate, dibutyl sepatate ,
Sebacin brewed di-2-ethylhexyl, adipic acid di-2
- diesters such as ethylhexyl, chryceryl monoethers such as chrycerol monooleyl ether, etc.
Acid amides such as lauroyl laurylamine and butyramide lauric acid, triglycerides such as tricabroin, avocado oil, camellia oil, turdle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, buma oil, versic oil, wheat germ oil,
Sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, sinensis oil, Japanese tung oil, jojoba oil, germ oil,
Plant and animal fats and oils such as cacao butter and coconut oil, etc.
One or more of these are used.

However, even if the ultraviolet absorber used here is not an oil defined in the organic conceptual diagram of claim 1, or is an oil defined in the organic conceptual diagram of claim 1, the amount described in claim 1 may not be blended. If not, it is necessary to further blend the oil defined in the organic conceptual diagram of claim 1 in the amount stated in claim 1.

The microemulsion in the present invention contains 0.1 to 30% surfactant, 0.005 to 30% ultraviolet absorber,
Oil component 0.005-60%, water 10-99.8%
Contains vines. Also, the ratio of surfactant and oily component is 1:
The ratio is 0.5 to 1:10, and the emulsion particle system is 0°01 to 0.
It is 15 μm.

Such a microemulsion can be prepared using an emulsifier capable of applying strong shearing force, such as a high-pressure homogenizer or an ultrasonic emulsifier. When using a high-pressure homogenizer, it is preferable to emulsify under a pressure of 300 atmospheres or higher, and more preferably, to emulsify at a temperature of 50° C. or lower and a pressure of 600 atmospheres or higher. Furthermore, in order to obtain a microemulsion with a smaller particle size, it is preferable to add a polyhydric alcohol during emulsification. It is preferable to emulsify the polyhydric alcohol at a polyhydric alcohol:water ratio of 1:5 to 19:1, and then add water to a predetermined polyhydric alcohol concentration after emulsification. More preferably, the emulsification is carried out at a polyhydric alcohol:water ratio of 1=4 to 8:2, and water is added after emulsification to a predetermined polyhydric alcohol concentration. The polyhydric alcohol may be one commonly used, such as dihydric alcohols such as propylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol;
Trihydric alcohols such as glycerin, hexahydric alcohols such as sorbitol and mannitol, polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, and polyglycerin, sorbitol, and multifunctional alcohols. It is used singly or in combination of two or more of toll, maltotriose, mannitol and the like.

Furthermore, when the nonionic surfactant according to claim 3 is used, production is possible by the method described above, but in further production, the temperature of the system is once lowered to the solubilization limit temperature According to the production method of raising the temperature above to uniformly solubilize and then cooling it, there is no need to use a special emulsifier, and a simple stirrer and a temperature-controlled tank can easily contain the UV absorber. Not only can a microemulsion be prepared, but also the turbidity of a microemulsion containing an ultraviolet absorber can be precisely controlled by changing the ratio of emulsifier to oil. In addition, if the solubilization limit temperature of the system is 90°C or higher and it is difficult to make it uniform, the cloud point of polyhydric alcohols of trivalent or higher valence, sugars, amino acids and their salts, parabens, and fragrances may be reduced. Production is facilitated by lowering the solubilization threshold temperature of the system by pre-adding additives that lower the solubilization temperature. The polyhydric alcohols used at this time include polyhydric alcohols:
It is preferable to use a method of using water at a ratio of 1:5 to 19:1 and adding water to a predetermined polyhydric alcohol concentration after emulsification. More preferably, a method is adopted in which solubilization is carried out at a polyhydric alcohol:water ratio of 1:4 to 8:2, and water is added after emulsification to a predetermined polyhydric alcohol concentration. The polyhydric alcohols having a valence of three or more may be those commonly used, such as trihydric alcohols such as glycerin, hexahydric alcohols such as sorbitol and mannitol,
One or more polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, and polyglycerin, and sugar alcohols such as sorbitol, maltitol, maltotriose, and mannitol. used in combination. Sugars, amino acids and their salts, parabens, fragrances, etc. may also be commonly used, and are used in a weight ratio of 0.01 to 1 to the surfactant, depending on the temperature required for production.

As described above, the feature of this method is that a more stable system can be easily obtained without relying on mechanical shearing force, and at the same time, it is possible to save labor in the manufacturing process.

The ultraviolet absorber-containing microemulsion of the present invention may contain various components in addition to the nonionic surfactant, oil, and water. Among such components, those listed as water phase components include methyl alcohol,
Ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1゜3-butylene glycol, glycerin, sorbitol, mannitol, diethylene glycol, dipropylene glycol, polyethylene glycol, sorbitan, sorbitol, maltitol, maltotriose,
There are mannitol, sodium hyaluronate, etc., which are arbitrarily selected and used in actual product systems.

[Geki no Cosmetics 0 is a quasi-drug. In addition, since the microemulsion according to the present invention has the excellent properties described above, it can be used as needed with other additives normally added to cosmetics, such as fragrances, pigments, and buffers. Agents, salts, whitening agents, preservatives, antioxidant fragrances, coloring agents, other powders, drugs, thickeners, ultraviolet absorbers, other oils, surfactants, active aids, etc. are added as appropriate, and are used in cosmetics and pharmaceutical departments. It can be applied as an external product. Although it is often blended as a base, it is not particularly limited, and a microemulsion may be included as a part of other bases. .

[Example] Next, the microemulsion according to the present invention will be described in detail with reference to Examples and Comparative Examples. The present invention is not limited thereby.

[Examples 1 to 13] 2 parts by weight of potassium dodecyl sulfate as a surfactant,
Put 10 parts by weight of the oil in the table (see the table for inorganicity and carbon number), 20 parts by weight of glycerin, and 20 parts by weight of water into a beaker, pre-emulsify it, and then use a high-pressure homogenizer (3 parts by weight) at 50°C.
After emulsifying at 00 atm), the temperature was returned to room temperature, and 48 parts by weight of water was added.

This was left at room temperature and the condition evaluated after one month is shown in Table 1. The evaluation is ○ if the average particle size is 0.15 μm or less, which remains transparent even after one month, and is clearly stable as a microemulsion, and if the average particle size is 0.15 μm or more, immediately or over time. The product that becomes cloudy and separated is designated as X.

(The following is a blank space) The average particle diameter of all the samples prepared above was 0.08 μm. As shown in Table 1, Examples 1 to 1 according to the present invention
In No. 13, a good microemulsion was obtained.

[Comparative Examples 1 to 13] 2 parts by weight of potassium dodecyl sulfate as a surfactant,
10 parts by weight of the oil in the table (see table for inorganicity and carbon number) and 8 parts by weight of water
5 parts by weight were placed in a beaker, pre-emulsified, emulsified at 50°C with a high-pressure homogenizer (300 atm), returned to room temperature, and the state evaluated after one month at room temperature is shown in Table 2. The evaluation is the same as in Examples 1 to 13.

(The following is a blank space) As shown in Table 2 and Table 2, the superiority of Examples 1 to 13 in which the polyhydric alcohol according to the present invention was blended was revealed.

[Comparative Examples 14 to 27] The surfactant was 2 parts by weight of potassium dodecyl sulfate as in Examples 1 to 13, and 10 parts by weight of oil, 20 parts by weight of glycerin, and 68 parts by weight of water in Table 3 were used. . The preparation method and evaluation method were based on Examples 1 to 13, but the changes over time were immediately after preparation and 1 day later.

(The following is a blank space) As shown in Table 1 and Table 3, the excellent effects of the inorganic nature and limited carbon number of the oil according to the present invention were demonstrated.

[Examples 14 to 27] As ionic surfactants, 2 parts by weight of potassium dodecyl sulfate, 0.25% by weight of squalane, and 9.75% of the oil in the table.
Parts by weight, 20 parts by weight of glycerin, and 20 parts by weight of water were placed in a beaker and pre-emulsified, followed by emulsification at 50° C. with a high-pressure homogenizer (300 atm), then returned to room temperature, and 48 parts by weight of water was added. Table 4 shows the evaluation of the harvest one month later. The evaluation is the same as in Examples 1-13.

(Hereinafter, 41 white) As shown in Table 4, good microemulsions were obtained in Examples 14 to 27 according to the present invention. This revealed the effectiveness of the combination of low molecular weight unstable oils and oils according to the limitations of the invention.

[Examples 28 to 37] As a surfactant, 5 parts by weight of POE(20) decyltetradecyl ether, 0.25 parts by weight of squalane, 5.75 parts by weight of the oil in Table 3, and N as a UV absorber. , N
-4 parts by weight of dimethyl PABA octyl ester, 8 parts by weight of water
Put 5 parts by weight into a beaker and bring the temperature to 'I! : The mixture was heated to 80°C, thoroughly stirred, and after confirming that it became transparent, it was returned to room temperature. This was left at room temperature and the condition evaluated after one week is shown in Table 3.

The evaluation is rated O if it remains transparent even after one week and is clearly stable as a microemulsion, and if it becomes cloudy and separates immediately or over time, it is rated x.

(Hereinafter, all white) As shown in Table 5, good microemulsions were obtained in Examples 28 to 37 according to the present invention. This revealed the effect of the combination with high molecular weight oils.

[Examples 38 to 41] POE (16) 2-off l)'7'shi/L, knee f/
Iz (A') 10% by weight, squalane and N
, N~dimethyl PABA octyl ester fj nia: 3
Add mixed oil (B) and purified water in the amount shown in the sixth coating, raise the temperature above the solubilization limit temperature (95 ° C.), and then cool to room temperature while stirring to form a microemulsion. Obtained. As shown in Table 4, the average particle size of the microemulsion increased as the amount of mixed oil relative to the amount of surfactant increased. Since there is regularity in the ratio, a microemulsion with an arbitrary average particle size can be easily prepared by changing the ratio of the surfactant to the mixed oil.

[Example 42] Cleansing jelly (parts by weight) 1) Liquid paraffin 30.02) Squalane 10.03) Fragrance
Appropriate amount 4) Preservatives
Appropriate amount 5) Oleic acid triethanolamine salt 10.0 6) Water 40.07) Propylene glycol 10.01) - Mix 4) and make 7
Heat and dissolve at 0°C.

This is f! : The mixed solution of 5) to 7) was heated and dissolved at 70° C. and added with stirring to emulsify. 2 of this emulsion
The mixture was emulsified using a high-pressure homogenizer at 60° C. under a pressure of 0.00 atm to obtain a cleansing jelly with a transparent feel.

The average particle diameter of the oil droplets of the resulting cleansing jelly was measured by dynamic light scattering and was found to be 0.07 μm.

[Example 43 Aqueous translucent topical drug (parts by weight) 1) Indomethacin 1.02) Dibutyl phthalate 8.03) Isopropyl myristate 10.04) Squalane
2.05) Potassium isostearate
5.06) Water 20.07)
1.3 Butanediol 10.08) Water
44. Mix 1) to 4) and heat to 70℃
Dissolve by heating.

This is added to a mixture of 5), 6) and 7) which has been heated and dissolved at 70°C and emulsified. 50% of this emulsion
The mixture was emulsified using a high-pressure homogenizer at 30° C. under a pressure of 0 atm, and then 8) was added to obtain an aqueous translucent topical drug of indomethacin with a transparent feel.

The average particle diameter of the oil droplets of the obtained aqueous translucent external medicine was measured by dynamic light scattering and was found to be 0.04 μm.

[Example 44] Aqueous translucent topical drug (parts by weight) 1) Clotrimazole 1.02) Dibutyl sebacate 10.03) Cetyl isooctanoate 2.54) Squalane
0.55) Myristyltrimethylammonium chloride 5.0 6) Water 10.07) Glycerin 40.08) Water
31.01) to 4) are mixed and heated to 70°C to dissolve.

This is added to a mixture of 5), 6), and 7) heated and dissolved at 70° C. while stirring, and emulsified.

This emulsion was emulsified using a high-pressure homogenizer at 30° C. under a pressure of 500 atm, and then 8) was added to obtain a translucent aqueous clotrimazole external preparation.

The average particle diameter of the oil droplets of the obtained aqueous transparent external medicine was measured by a dynamic light scattering method and was found to be O.Oaμm.

[Example 45] Hair transparent rinse agent (parts by weight) 1) Liquid paraffin 12.02) Cetyltrimethylammonium bromide 8.03) Water
20.04) Propylene glycol
15.05) Water 45.0
1) is heated at 70°C. This is added to the mixture of 3) to 4) heated and dissolved at 70° C. while stirring, and emulsified. This emulsion was emulsified using a high-pressure homogenizer at 30° C. under a pressure of 700 atm, and then 5) was added to obtain a transparent rinse agent.

The average particle diameter of the oil droplets of the obtained transparent rinse agent was measured by dynamic light scattering and was found to be 0.025 μm.

[Example 46] Hair treatment agent (parts by weight) 1) Isopropyl myristate 29.02) Squalane 5.03) Dicetyldimethylammonium bromide 8.04) Water
30゜05) Glycerin
30.01) to 3) are stirred and mixed at 70°C. This is added to the mixture of 4) and 5) dissolved by heating at 70°C, and emulsified. This emulsion was emulsified using a high-pressure homogenizer at 30° C. under a pressure of 700 atm to obtain a transparent, highly viscous hair treatment agent.

The average particle diameter of the oil droplets of the obtained bear treatment agent was measured by a dynamic light scattering method and was found to be 0.06 μm.

[Example 47] (Parts by weight) 1) Liquid paraffin 5.02) 2-
Hydroxy-4-methoxybenzophenone 1.03) Preservative
Appropriate amount 4) Oleic acid triethanolamine salt 3.05) Water
81.06) Propylene glycol
10. .

1) to 3) are mixed and dissolved by heating at 70°C.

This is added to a mixture of 4) to 6) heated and dissolved at 70° C. while stirring, and emulsified. 200 yen of this emulsion
Emulsification was performed using a high-pressure homogenizer at 60° C. under atmospheric pressure to obtain a transparent lotion.

The average particle diameter of the oil droplets of the obtained lotion was measured by dynamic light scattering and was found to be 0.07 μm.

(Margin below) [Example 48] (Parts by weight) 1) Cicapurin-brewed neopentyl glycol 3.02) Chryceryl mono-2-ethylhexanoyl diparamethoxycinnamate 1.03) Liquid paraffin
0.24) Flavoring (appropriate amount) 5) Preservative (appropriate amount) 6) Potassium isostearate 3.07) Water
20.08) 1.3 Butanediol
10.09) Water 62.81
) to 6) are mixed and heated and dissolved at 70°C.

This is added to the mixed solution of 7) and 8) heated and dissolved at 70° C. while stirring, and emulsified. This emulsion was emulsified using a high-pressure homogenizer at 30° C. under a pressure of 500 atm, and then 9) was added to obtain a transparent lotion.

The average particle diameter of the oil droplets in the obtained lotion was measured by dynamic light scattering and was found to be 0.04 μm.

Moreover, this lotion had a smooth feel with no stickiness at all.

[Example 49] Lotion (parts by weight) 1) Neopentyl glycol capriate 3.02) Chryceryl di-2-ethylhexanoyl-monobaramethoxycinnamate 1.03) Urocanic acid
0.14) Liquid paraffin 0.25
) Appropriate amount of preservative 6) POE (
20) 2-decyltetradecyl ether 1.57) POE (
14) 2-octyldodecyl ether 1.58) Water
20.09) Propylene glycol
15.010) Water 57
．． 71) to 5) are mixed and heated and dissolved at 70°C.

This is added to a mixture of 6), 7), 8), and 9) heated and dissolved at 70° C. while stirring, and emulsified. This emulsion was emulsified using a high-pressure homogenizer at 30° C. under a pressure of 500 atm, and then 10) was added to obtain a lotion with a transparent feel and ultraviolet absorbing effect and a smooth feel.

The average particle diameter of the oil droplets of the obtained lotion was measured by dynamic light scattering and was found to be 0.03 μm.

[Example 50] Hair treatment agent (parts by weight) 1) Isopropyl myristate 29.02) Squalane 5.03) 4-Methoxy-4°-t-butyldibenzoylmethane 2.04) Dicetyldimethylammonium bromide 8. 05) Water
28.06) Glycerin
28. Stir and mix 01) to 4) at 70°C. This is added to the mixture of 5) and 6) heated and dissolved at 70° C. while stirring, and emulsified. This emulsion was emulsified using a high-pressure homogenizer at 30° C. under a pressure of 700 atm to obtain a transparent, highly viscous hair treatment agent with ultraviolet absorbing effect.

The average particle diameter of the oil droplets of the obtained hair treatment agent was measured by a dynamic light scattering method and was found to be 0.06 μm.

[Example 51] (Parts by weight) 1) Light liquid paraffin 5.02) 2-
Hydroxy-4-methoxybenzophenone 1.03) POE (
14)-2-octyldodecyl ether
3.04) Fragrance
Appropriate amount 5) Preservative appropriate amount 6)
Water 87.07) Propylene glycol 5.0゛ Mix 1) to 6) and 85
℃, cool while stirring, and when it reaches 70℃, 7
) is added.

Cooled to room temperature with rough stirring, resulting in a translucent lotion.

The average particle diameter of the oil droplets in the obtained lotion was measured by dynamic light scattering and was found to be 0.4 μm.

This lotion has a high ultraviolet absorption effect, can be easily washed off with water, and has a smooth and pleasant feeling when used.

[Example 52 (parts by weight) 1) Neopentyl glycol capriate 3.02) Glyceryl mono-2-ethylhexanoyl diparamethoxycinnamate 1.0 3) Liquid paraffin 0.14) Fragrance N
O, 15) Preservative
Appropriate amount 6) POE (20) 2
-decyltetradecyl ether
1.57) POE (14) 2-octyldodecyl ether 1.58) Water
92, 81) to 6) were mixed and heated to 90°C, 30 parts of 7) was heated to 90°C, and 1) to
6). Thereafter, the mixture was cooled to room temperature while stirring, and the remainder of step 7) was mixed to obtain a translucent serum.

The average particle diameter of the oil droplets of the obtained beauty serum was measured by dynamic light scattering and was found to be 0.03 μm. When the stability of this product over time was investigated, there was no change in appearance for more than 6 months under any conditions of 40°C, 25°C, and 0°C, and the average particle diameter also hardly changed. In addition, the feeling of use was good, with no stickiness.

[Example 53] (Parts by weight) 1) Octyl-p-methoxycinnamate 0.252) Tricabroin 6,753) POE
(14)-2-octyldodecyl ether
5.04) Water 83
．． 05) Glycerin 5.01) ~
5) was mixed and heated to 75°C, and cooled to room temperature while stirring to obtain a lotion.

The average particle diameter of the oil droplets of the obtained lotion was measured by dynamic light scattering and was found to be 0.03 μm.

(Left below) [Example 54] (Parts by weight) 1) Neopentyl glycol capriate 3.02) Chryceryl di-2-ethylhexanoyl-monobaramethoxycinnamate 1.03) Urocanic acid
0.14) Fragrance 0.15
) Preservative appropriate amount 5) PO
E(20) 2-decyltetradecyl ether
3.07) Water 8
7.88) Glycerin 5.01)
-6) are mixed and heated to 90°C. 30 parts of 7) are heated to 90°C and added to 1) to 6). Then, cool to room temperature while stirring, mix the remainder of 7) and 8),
A translucent serum was obtained.

The average particle diameter of the oil droplets of the obtained beauty serum was measured by dynamic light scattering and was found to be 0.03 μm. When the stability of this product over time was investigated, there was no change in appearance for more than 6 months under any conditions of 40°C, 25°C, and 0°C, and the average particle diameter also hardly changed.

〔Effect of the invention〕

As detailed above in Section 1, the present invention relates to a microemulsion consisting of a hydrophilic surfactant and a specific oil, and a large amount of oil can be blended in a transparent or translucent manner with a small amount of surfactant. It can be said that it has the advantage of being usable like a lotion or lotion, and is highly practical in terms of safety and functionality. Particularly preferably, because of the advantages it has, the present invention can be applied to liquid cleansers, shampoos, conditioners, hair tonics, etc.
Hair lotion, aftershave lotion, body lotion, hair oil, emollient oil,
It can be used in water-based products such as cosmetic lotions, cleansing oils, aerosol products, deodorants, deodorants, pharmaceutical liquids, and bath salts.

As described in detail above, the present invention relates to an ultraviolet absorber-containing microemulsion consisting of an ultraviolet absorber, a specific oil, and a hydrophilic surfactant, which is unlike conventional emulsions or cream types. In addition to providing a dry feel that was previously unavailable, it also significantly increases the concentration of ultraviolet absorbers, which was considered difficult to do with conventional lotions and lotions.V) Much smaller amount of surfactant than conventional solubilized systems. UV absorbers can be stably blended. Therefore, it is highly practical in terms of safety and functionality. Particularly preferably, because of the advantages it has, the present invention can be used in aqueous products such as cosmetic lotions, hair lotions, body lotions, emollient lotions, pharmaceutical solutions, etc.

As detailed above in Section 3, the present invention relates to an ultraviolet absorber-containing microemulsion comprising an ultraviolet absorber, a specific oil, and a hydrophilic nonionic surfactant. In addition to having a smooth feel that was unimaginable with conventional lotions and lotions, it also significantly improves the concentration of ultraviolet absorbers, which was difficult to achieve with conventional lotions and lotions. UV absorbers can be stably blended with surfactants. In addition, it can be manufactured using a water system that can easily control the temperature and a simple stirrer, and is extremely practical in terms of manufacturing cost. Therefore, it can be said that it is highly practical in terms of safety and functionality, and has high utility value. Particularly preferably, because of the advantages it has, the present invention can be used in aqueous products such as cosmetic lotions, hair lotions, body lotions, emollient lotions, pharmaceutical solutions, etc.

The invention according to claim 4 The present invention is a cosmetic or pharmaceutical product containing the microemulsion according to claims 1 to 3, and therefore provides a cosmetic or quasi-drug that is highly stable and safe and has a smooth feel when used. can be provided.

Patent applicant: Shiseido Co., Ltd.

Claims (1)

[Scope of Claims] 1. A hydrophilic surfactant, one or more oils that satisfy the following conditions, and (an oil with an inorganic property of 0 on an organic conceptual diagram and a carbon number of 17 or more) ,0
<Inorganic≦20 and an oil with a carbon number of 18 or more, 20<Inorganic≦50 and a carbon number of 19 or more, 50<Inorganic≦100 and a carbon number of 20 or more, 100<Inorganic Oil with a property ≦150 and a carbon number of 21 or more, 150<inorganic≦200 and an oil with a carbon number of 22 or more, 200<inorganicity≦250 and an oil with a carbon number of 23 or more, 250<inorganic and an oil having a carbon number of 25 or more) containing at least a polyhydric alcohol and water, the content of the above oil is 0.005 to 60% by weight, and a hydrophilic surfactant and a total oily component in the system. Weight ratio is 1:0.5~
A microemulsion characterized in that the ratio is 1:10 and the average particle diameter is 0.01 to 0.15 μm. 2. Containing at least a hydrophilic surfactant, an oil that can dissolve an oil-soluble ultraviolet absorber, an oil-soluble ultraviolet absorber, and water, and a hydrophilic surfactant and an oil-soluble ultraviolet absorber. The sum of the oil that can dissolve the absorbent and the oil-soluble ultraviolet absorber is 0.
5 to 7, and an average particle diameter of 0.01 to 0.15 μm. 3. The hydrophilic surfactant is a hydrophilic nonionic surfactant. 2. Cosmetics or quasi-drugs comprising the microemulsion 4 according to claim 1, 2 or 3.