JPH0667469B2 - Micro emulation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a two-phase microemulsion which comprises a hydrophilic ionic surfactant and is capable of stably blending a large amount of oil in a wide temperature range. For example, it is used in fields such as pharmaceuticals and cosmetics.

[Prior Art] Conventionally known microemulsions are as follows. That is, the first is obtained by using an ordinary nonionic surfactant and oil, the second is a combination of anionic surfactant and cosurfactant, and the third is an anionic surfactant and nonionic. It is a combination of a cationic surfactant or an electrolyte.

The first is to add a hydrocarbon such as cyclohexane or n-heptane to an aqueous solution of a nonionic surfactant such as iso-R ₉ C ₆ H ₄ O (CH ₂ CH ₂ O) ₉ H and raise the temperature. It is said that a region where the amount of solubilization of hydrocarbons (oil) increases sharply appears before the cloud point of the nonionic surfactant (Kozo Shinoda, 209-225, Solution and Solubility, Maruzen). ). It is known that in the Iw region from the solubilization limit temperature to the cloud point shown in the phase diagram, the solubility of oil in the aqueous phase dramatically increases, forming a so-called microemulsion. But,
A microemulsion (Iw region) obtained by a nonionic surfactant-hydrocarbon system which has been conventionally studied and having an increased oil solubilization amount, that is, a thermodynamically stable one-phase microemulsion is It exists only in a very narrow temperature range (several ℃ ~ 10 ℃) where the hydrophilic-lipophilic balance of the system is maintained. Outside this range, the system becomes cloudy immediately or over time, and eventually separates into water and oil. It has a drawback that it does. Therefore, it is very difficult to apply to cosmetics and pharmaceuticals.

The second is to balance the hydrophilic-lipophilic balance of the system by combining anionic surfactants and cosurfactants such as pentanol, hexanol, octanol, etc., within a very narrow range of hydrocarbon (oil) It is intended to utilize the region where the amount of solubilization increases rapidly. Third,
An electrolyte is added 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, and the hydrophilicity of the system It aims to utilize the region where the amount of solubilization of hydrocarbons (oil) increases rapidly within a very narrow ratio range where the oil balance is balanced (Kozo Shinoda, Hiroyuki Saijo, 308-314, 35, 1986). , JP-A-58-128311, JP-A-58-58
-131127). In the second and third methods, the stability against temperature has been solved, but the composition in which such a one-phase solubilized microemulsion is stably present is very limited, and the actual product There is a concern that the prescription will be considerably limited or complicated in the system. Further, in the second method, cosurfactant such as hexanol is used, so that there is a problem in safety.

[Problems to be Solved by the Invention] Therefore, it is difficult to use the microemulsion for cosmetics or pharmaceuticals intended for use at normal temperature in the first method from the viewpoint of stability. The second and third methods have been regarded as problematic in terms of prescription. However, the characteristics of a microemulsion having a particle size of several tens of mμ capable of uniformly dissolving a large amount of oil with a small amount of surfactant are very useful and have high temperature stability and a wide formulation range. Completion was supposed to be a researcher's task.

In view of the current situation, the present inventors have conducted diligent research to obtain a microemulsion having excellent temperature stability and a wide prescription width, and as a result, together with a commonly used ionic surfactant, a carbon number and an organic conceptual diagram ( Organic conceptual diagram, Yoshio Koda, Sankyo Shuppan, 1984) By using a combination of oils with limited minerality, surprisingly, a two-phase microemulsion stable over a very wide temperature range. The inventors have found that the above can be easily obtained, and have completed the desired invention.

[Means for Solving Problems] That is, the present invention comprises a hydrophilic ionic surfactant,
Oil with 0 inorganicity and 15 or more carbon atoms in the organic conceptual diagram,
0 <Inorganicity <20 and oils with 16 or more carbons, 20 <Inorganicity <50 and oils with 17 or more carbons, 50 <Oil with minerals <100 and 18 or more carbons, 100 < Inorganic ≤ 150 and oils with 19 or more carbons, 150 <Inorganic ≤ 200 and oils with 20 or more carbons, 200 <Inorganic ≤ 250 and oils with 21 or more carbons, 25
0 <Inorganic and C22 or more oil containing 1 or 2 or more types of oil, and water, The content rate of the said oil is 0.005-60 weight%, and a hydrophilic ionic surfactant. The amount ratio of all oily components is 1: 0.5 to 1:10, and is obtained by applying a shearing force equivalent to a high pressure homogenizer treatment of 400 atm or more, the average particle diameter of oil droplets is 0.01 ~ 0.
Two-phase microemulsion with a size of 1 μm.

The average particle diameters used here are all measured by the dynamic light scattering method, and specifically, NICOMP-27.
0 (manufactured by HIAC / ROYCO).

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

As the ionic surfactant used in the present invention, HLB must be hydrophilic because it is necessary to obtain an oil-in-water type two-phase microemulsion, but otherwise an ordinary ionic surfactant is used. You can

As a specific example, as the anionic surfactant,
For example, fatty acid soaps such as sodium laurate and potassium palmitate, higher alkyl sulfate ester salts such as sodium lauryl sulfate and potassium lauryl sulfate, polyoxyethylene (hereinafter referred to as POE) alkyl ether sulfate salts such as trilyethanolamine lauryl sulfate. , N-acyl sarcosinic acid such as sodium lauroyl sarcosine, higher fatty acid amide sulfonates such as N-myristoyl-N-methyl taurine sodium, phosphate ester salts such as sodium POE oleyl ether phosphate and POE stearyl ether phosphate, diester 2-ethylhexyl sulfosuccinate such as sodium sulfosuccinate, sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecylbenzene sulfonate, linear dodecyl benzene sulphate Alkylbenzene sulfonates such as phosphate, N- lauroyl glutamate monosodium, disodium N- stearoylglutamic acid, N-
N such as myristoyl-L-monosodium glutamate
-Acyl glutamate and the like.

Examples of the cationic surfactant include alkyl trimethyl ammonium salts such as stearyl trimethyl ammonium chloride and lauryl trimethyl ammonium chloride, dialkyl dimethyl ammonium salts, alkyl quaternary ammonium salts, and alkyl amine salts.

Examples of the amphoteric surfactant include 2-undecyl-N,
N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc. imidazoline-based double-sided surfactant, 2-heptadecyl-N-carboxyl Betaine-based surfactants such as methyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amidobetaine and sulfobetaine, amino acid salts such as N-lauryl β-alanine and N-stearyl β-alanine Etc.

It is used in one kind or a combination of two or more kinds of these ionic surfactants.

In order to set the oil content of the two-phase microemulsion according to the present invention to an ionic surfactant: oil ratio of 1: 2 or more, the structure of the lipophilic group of the ionic surfactant is used. Is preferably an aliphatic hydrocarbon in which the lipophilic group has 12 or more carbon atoms. Furthermore, to improve stability at low temperatures,
It is preferable that the Kraft point is room temperature or lower, preferably 0 ° C. or lower.

The oil used in the present invention is an oil having an inorganicity of 0 and a carbon number of 15 or more on the organic conceptual diagram (Organic conceptual diagram, Yoshio Koda, Sankyo Publishing, 1984), 0 <inorganicity ≦ 20 and Oils with 16 or more carbons, 20 <inorganic <50 and oils with 17 or more carbons, 50
<Inorganicity <100 and oil with 18 or more carbons, 100 <Inorganicity <150 and oil with 19 or more carbons, 150 <Inorganic <200 and oil with 20 or more carbons, 200 <Inorganic One or two or more of oils having a property of ≦ 250 and a carbon number of 21 or more, 250 <inorganic oils having a carbon number of 22 or more.

These oils are preferably in a liquid state at room temperature, but even if they are solid, there is no problem as long as they are dissolved in the liquid state when mixed.

As a specific example, as the oil of which the inorganicity is 0 and the number of carbon atoms is 15 or more, for example, hydrocarbons such as liquid paraffin, squalane, pristane, paraffin, and petrolatum, 0 <
Oils having an inorganicity of ≤20 and having 16 or more carbon atoms include hydrocarbons such as squalene, ethers such as dioctyl ether, and 20 <inorganicity ≤50 and having 17 or more carbon atoms such as ethylene. Diethers such as glycol dioctyl ether, 50 <inorganicity <100 and carbon number 18
Examples of the above oils include cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, myristyl myristate, decyl oleate, monoesters such as oleyl oleate, isostearyl alcohol, higher grades such as octyldodecanol. Examples of oils such as alcohols having 100 <inorganicity <150 and carbon number of 19 or more include unsaturated higher alcohols such as oleyl alcohol and lanolin alcohol, and the like, 150 <inorganicity <200 and carbon number of 20 or more. As the oil, for example, higher fatty acids such as eicosenoic acid, diesters such as di-2-ethylhexyl sebacate, diesters such as di-2-ethylhexyl adipate, etc., 200 <inorganicity <250 and as an oil having 21 or more carbon atoms, For example, glyceryl monoethers such as glycerol monooleyl ether, Uronium yl laurylamine acid amides such as such as 250 <inorganic and and are, for example avocado oil as the oil number is more than 22 carbon atoms, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil,
Olive oil, rapeseed oil, egg yolk oil, sesame oil, persic 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 , Cinnamon oil, Japanese tallow oil, jojoba oil, germ oil, cacao butter, coconut oil and other plants, and animal oils and fats. One or more of these are used.

The stability of the two-phase microemulsion tends to improve as the number of carbon atoms increases and the more non-polar oil is used.
In order to further stabilize the two-phase microemulsion, it is preferable to use one having a carbon number larger than the above-mentioned limit by 1 or more.

Further, according to the discovery of the present inventors, it was difficult to obtain a stable microemulsion, cyclohexane, n-heptane, isopropyl myristate,
Even for low molecular weight oils such as dibutyl sebacate, it is surprisingly possible to obtain stable two-phase microemulsions by adding the oil according to the limitation of the invention. Such oils and the oils according to the limits of the invention are used in a quantitative ratio of 1: 0.001 to 1: 0.7. Examples of such oils are, for example, oils having an inorganicity of 0 on the organic conceptual diagram and having a carbon number of 5 ≦ C ≦ 14, 0 <inorganicity ≦ 20 and 6 ≦
Oil with carbon number ≤15, oil with 20 <inorganicity ≤ 50 and carbon number 7 ≤ carbon number ≤ 16, oil with 50 <inorganicity ≤ 100 and carbon number 8 ≤ carbon number ≤ 17, 100 <inorganic Oil with a property of <150 and a carbon number of 10 <= 18, 150 <inorganicity <200 and an oil of 12 <carbon number <19, 200 <an inorganic <250 and a carbon number of 14 <= One or more oils having a carbon number of ≦ 20, 250 <inorganic and having a carbon number of 16 ≦ carbon number ≦ 21, and specific examples thereof are 0 inorganic and carbon number Examples of oil having 5 ≦ C ≦ 14 include hydrocarbons such as n-heptane and n-octane, and examples of oil having 0 <inorganicity ≦ 20 and 6 ≦ C ≦ 15 include cyclohexane and the like. Examples of oils such as hydrocarbons and ethers such as diheptyl ether having 20 <inorganicity ≦ 50 and having 7 ≦ C <16 carbons include, for example, ethylene glycol dibutyl ether and the like. 50, etc.
<Inorganic ≦ 100 and C8 ≦ C17 oils include, for example, isopropyl myristate, ethyl caprate, monoesters such as ethyl laurate, alcohols such as 2-heptylnonanol, and the like, 100 <inorganic <150
And the number of carbon atoms as the oil of 10 ≤ carbon number ≤ 18, for example, isomyristic acid, isostearic acid, fatty acids such as capric acid, dialcohol monoethers such as ethylene glycol monolauryl ether, 150 <inorganic ≤ Examples of the oil having a carbon number of 200 and a carbon number of 12 ≦ C ≦ 19 include, for example, diester adipate, diisopropyl sebacate, dibutyl sebacate, etc., 200 <inorganicity ≦ 250 and a carbon number of 14 ≦ carbon number. Examples of the oil of ≦ 20 include acid amides such as lauric acid butylamide, and the like, examples of oils of 250 <inorganic and 16 carbon atoms ≦ 21 carbon atoms include, for example, triglycerides such as tricaproin, and the like. One or two or more types are used.

The two-phase microemulsion in the present invention may contain 0.1 to 30% of an ionic surfactant, 0.005 to 60% of an oily component, and 20 to 99.8% of water. The ratio of ionic surfactant to oily component is 1: 0.5 to 1:10, and the emulsion particle system is
It is 0.01 to 0.1 μm.

Such a two-phase microemulsion can be prepared using an emulsifying machine that can give a strong shearing force, such as a high pressure homogenizer or an ultrasonic emulsifying machine. When a high-pressure homogenizer is used, it is preferable to emulsify under a pressure of 400 atm or higher, and more preferably at a temperature of 50 ° C. or lower and a pressure of 600 atm or higher.

The two-phase microemulsion according to the present invention does not cause clouding or separation in any ordinary stability test.

In addition to the two-phase microemulsion of the present invention, various components can be blended. Among such components, those mentioned as the aqueous phase component include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin,
Sorbitol, mannitol, diethylene glycol,
There are dipropylene glycol, polyethylene glycol, sorbitan, sorbitol, maltitol, maltotriose, mannitol, sodium toaluronate, etc., which are arbitrarily selected and used in the actual product system.

In addition, in products to which the two-phase microemulsion according to the present invention is applied, if necessary, fragrances, coloring agents and other powders, preservatives, drugs, thickeners, ultraviolet absorbers, chelating agents, other oils, Surfactants, activation aids and the like are added as appropriate.

[Effects of the Invention] As described in detail above, the present invention relates to a two-phase microemulsion composed of a hydrophilic ionic surfactant and a specific oil, and is very practical in terms of safety and functionality. It can be said that it is expensive. In particular, the present invention, due to its advantages, includes liquid cleansers, shampoos,
It can be used for water-based products such as hairnic, hair lotion, after shave lotion, body lotion, hair oil, emollient oil, makeup lotion, cleansing oil, aerosol product, deodorant, deodorant, medicinal solution, bath agent. .

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

[Examples 1 to 13] As an ionic surfactant, 10% by weight of potassium dodecyl sulfate and 20% by weight of oil in the table (see table for inorganicity and carbon number)
Put water and water in a beaker, pre-emulsify it, emulsify it with a high-pressure homogenizer (500 atm) at 50 ℃, return to room temperature, and evaluate the condition after 5 months at 5 ℃, 25 ℃ and 40 ℃. Shown in Table 1. In the evaluation, those having transparency at each temperature even after 3 months and clearly stable as a microemulsion having a particle size of several tens of μm are marked with ◯, and those that have clouded or separated immediately after or over time are marked with x.

As shown in Table 1, in Examples 1 to 13 according to the present invention, good two-phase microemulsions were obtained.

[Comparative Examples 1 to 14] The ionic surfactant was 10% by weight of potassium dodecyl sulfate in the same manner as in Examples 1 to 13, and 20% by weight of the oil in Table 2 (see Table for inorganicity and carbon number). Water was used. The preparation method and the evaluation method are in accordance with Examples 1 to 13, but the change with time was immediately after preparation and after 1 day.

As shown in Tables 1 and 2, the excellent effect of the limited minerality and carbon number of the oil according to the present invention was demonstrated.

[Examples 14 to 27] As ionic surfactants, 10% by weight of potassium dodecyl sulfate, 0.5% by weight of squalane, 20% by weight of oil in the table and 6% of water.
9.5 wt% was placed in a beaker, pre-emulsified, emulsified with a high-pressure homogenizer (500 atm) at 50 ° C, then returned to room temperature, and evaluated at 5 ° C, 25 ° C, 40 ° C and after 3 months Is shown in Table 3. In the evaluation, a sample having a transparent feeling at each temperature even after 3 months and being clearly stable as a microemulsion is rated as ◯, and a sample which is cloudy or separated immediately after or over time is rated as x.

As shown in Table 3, Examples 14 to 27 according to the present invention provided good two-phase microemulsions. This revealed the effect of combination with low molecular weight oils.

[Example 28] Cleansing jelly Mix 1) to 3) and heat to dissolve at 70 ° C.

The mixed solution of 4) to 6) is heated and melted at 70 ° C. and added with stirring to emulsify. This emulsion was emulsified with a high pressure homogenizer at a pressure of 700 atm at 30 ° C to obtain a cleansing jelly having a transparent feeling.

The average particle size of the obtained cleansing jelly oil droplets was 0.1 μm as measured by the dynamic light scattering method.

[Example 29] Aqueous translucent external preparation Mix 1) to 4) and heat to dissolve at 70 ° C. The mixed solution of 5) and 6) is heated and melted at 70 ° C. and added with stirring to emulsify. This emulsion is emulsified under a pressure of 700 atm using a high pressure homogenizer at 30 ° C,
A translucent aqueous translucent indomethacin preparation was obtained.

The average particle size of the oil droplets of the obtained aqueous semitransparent external preparation was measured by a dynamic light scattering method and found to be 0.07 μm.

[Example 30] Aqueous translucent external preparation Mix 1) to 4) and heat to dissolve at 70 ° C. The mixed solution of 5) and 6) is heated and melted at 70 ° C. and added with stirring to emulsify. This emulsion is emulsified under a pressure of 700 atm using a high pressure homogenizer at 30 ° C,
An aqueous translucent external preparation of clotrimazole having a transparent feeling was obtained.

The average particle diameter of the oil droplets of the obtained aqueous transparent external preparation was measured by the dynamic light scattering method and found to be 0.07 μm.

[Example 31] Hair transparent rinse agent Heat 1) at 70 ° C. Add this to the mixture of 3) -4)
Emulsify by adding to a mixture heated and dissolved at 70 ° C with stirring. This emulsion was emulsified under a pressure of 700 atm at 30 ° C using a high pressure homogenizer to obtain a transparent rinse agent.

The average particle size of the obtained oil drops of the transparent rinse agent was measured by the dynamic light scattering method and found to be 0.03 μm.

[Example 32] Hair treatment agent Stir-mix 1) to 3) at 70 ° C. Add this to a mixture of 4) and 5) heated and dissolved at 70 ° C with stirring,
Emulsify. This emulsion was emulsified under a pressure of 700 atm at 30 ° C using a high-pressure homogenizer to obtain a transparent and highly viscous hair treatment agent.

The average particle size of the oil droplets of the obtained hair treatment agent was measured by the dynamic light scattering method and found to be 0.1 μm.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C11D 3/16 17/08 (56) References JP-A-60-61030 (JP, A) Hirokichi Kaname (6 people outside) edited by "Handbook-Cosmetics / Pharmaceutical Raw Materials-Revised Edition" (Showa 52-2-1) Nikko Chemicals (1 outside) 192-195, P. 224 to 252 Fumio Kitahara (1 person from outside) “Chemistry of dispersion / emulsion system” (Sho 58-3-15) 72 ~ 75

Claims (2)

[Claims] 1. A hydrophilic ionic surfactant, an oil having an inorganicity of 0 and a carbon number of 15 or more in an organic conceptual diagram, an oil of 0 <inorganicity ≦ 20 and a carbon number of 16 or more, 20 <Inorganicity <50 and oils with 17 or more carbons, 50 <Inorganicity <100 and oils with 18 or more carbons, 100 <Oil with inorganicity <150 and 19 or more carbons, 150 < Oil with inorganicity ≤200 and carbon number of 20 or more, 20
One or two or more of 0 <inorganicity <250 and oil having 21 or more carbon atoms, 250 <inorganic oil having 22 or more carbon atoms,
Containing water and the oil content is 0.005 to 60% by weight,
The amount ratio of hydrophilic ionic surfactant and total oily component is 1:
The average particle diameter of oil droplets is 0.01 to 0.1 μm, which is 0.5 to 1:10 and is obtained by applying a shearing force equivalent to a high pressure homogenizer treatment of 400 atm or more.
Which is a two-phase microemulsion. 2. An ionic surfactant and an oil containing the following a), b), ha) and d), and the amount ratio of oil b) and oil c) is 1: 0.001 to 1: 0.7. B) and ha)
The average particle diameter of oil droplets is 0.01 to 0.1 μ, which is 1: 0.5 to 1: 7 and is obtained by applying a shearing force equivalent to a high pressure homogenizer treatment of 400 atm or more.
A two-phase microemulsion that is m. B) Hydrophilic ionic surfactant, b) Oil whose inorganicity is 0 and carbon number is 5 ≦ carbon number ≦ 14 on the organic conceptual diagram, 0 <inorganicity ≦ 20 and carbon number is 6 ≦ carbon Number ≤ 15 oil, 20 <inorganic ≤ 50 and carbon number 7 ≤ carbon number ≤
16 oils, 50 <inorganic <100 and carbon number <8 carbon number <1
7 oil, 100 <inorganic <150 and carbon number <10 carbon number <1
8 oils, 150 <inorganic ≤ 200 and carbon number 12 ≤ carbon number ≤ 1
9 oil, 200 <inorganic <250 and carbon number <14 carbon number <2
0 oil, 250 <inorganic and 1 or 2 or more kinds of oil having carbon number 16 ≤ carbon number ≤ 21 c) Oil having inorganicity 0 and carbon number 15 or more on the organic conceptual diagram, 0 <Inorganicity <20 and C16 or more oil, 20 <Inorganicity <50 and C17 or more oil, 50 <Inorganic <100
Oil with 18 or more carbons, 100 <inorganicity <150 and oil with 19 or more carbons, 150 <inorganicity <200 and 20 carbons
1 or 2 or more of the above oils, 200 <inorganicity <250 and C21 or more oil, 250 <inorganic and C22 or more oil d) Water