JP2684188B2 - Micro emulsion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a stable microemulsion containing a silicone oil containing a hydrophilic surfactant, such as cosmetics, toiletries, households, and the like. Used in fields such as pharmaceuticals.

[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 an anionic surfactant and cosurfactant, and the third is
Is a combination of an anionic surfactant and a nonionic surfactant or electrolyte.

First, add hydrocarbons such as cyclohexane and 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.

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
Is a combination of a lipophilic nonionic surfactant and a specific anionic surfactant, or a combination of a lipophilic nonionic surfactant and an ionic surfactant with an electrolyte, and the hydrophilicity of the system -It aims to utilize the region where the amount of solubilization of hydrocarbons (oil) increases sharply within a very narrow range of lipophilic balance (Kozo Shinoda, Hiroyuki Nishiki, 308-314, 35, 1986, JP-A-58-128311, JP-A-58-131127).

However, it is not possible to obtain a silicone oil microemulsion by any of the methods mentioned here.

[Problems to be Solved by the Invention] However, the property of a microemulsion capable of uniformly dissolving a large amount of silicone oil with a small amount of a surfactant is very useful, and the microemulsion itself has high stability, and other aqueous solutions. The completion of a microemulsion that is stable even when added to the system formulation has been an issue for researchers.

In view of such a current situation, the present inventors have conducted earnest research to obtain a microemulsion which itself has high stability and is stable even when it is added to another aqueous system formulation. The number of active surfactants and silicon
At least one or two or more of 12 or more silicones
By emulsifying a system containing at least 0.5% by weight of silicone oil and a water-soluble monohydric alcohol, polyhydric alcohol and / or one or more saccharides and water, surprisingly, emulsified particles Since the inventors have found that a microemulsion having a small diameter and stable over a very wide temperature range and capable of containing a large amount of silicone oil can be easily obtained, the present invention has been completed as desired. is there.

[Means for Solving the Problems] That is, the present invention provides: a hydrophilic surfactant; and a silicone oil containing at least 0.5% by weight of one or more silicones having 12 or more silicon atoms. It contains at least water and one or more water-soluble monohydric alcohols, water-soluble polyhydric alcohols and water-soluble saccharides, and at least a hydrophilic surfactant / oil component weight ratio of 1: 0.5-. It is 1:10, and the average particle diameter is 0.01 to 0.1 μm, which is a microemulsion.

The average particle size used here is all measured by the dynamic light scattering method, and specifically, NICOMP-2
70 (manufactured by HIAC / ROYOC).

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

As the surfactant used in the present invention, since it is necessary to obtain an oil-in-water type microemulsion, HLB must be hydrophilic, but otherwise a normal nonionic surfactant or ionic surfactant is used. Can be used.

Specific examples include POE sorbitan fatty acid esters such as polyoxyethylene (hereinafter referred to as POE) sorbitan monooleate, POE sorbitan monostearate, POE sorbitan trioleate, and POE sorbit mono as nonionic surfactants. POE sorbit fatty acid esters such as oleate, POE sorbit pentaoleate, POE sorbit monostearate, POE glycerin monostearate, POE glycerin monoisostearate, P
OE glycerin Isostearate and other POE glycerin fatty acid esters, POE monooleate, POE distearate, POE dioleate and other POE fatty acid esters, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE2-octyldodecyl ether, POE2-hexyldecyl POE alkyl ethers such as ether, POE 2-heptyl undecyl ether, POE 2-decyl tetradecyl ether, POE 2-decyl pentadecyl ether, POE cholestanol ether, POE alkylphenyl ethers such as POE nonylphenyl ether, POE / POP block Copolymers, POE / POP cetyl ether, POE / POP
2-decyl tetradecyl ether, POE / POP hydrogenated lanolin and other POE / POP alkyl ethers, POE castor oil and other P
OE castor oil or hydrogenated castor oil derivative, POE beeswax lanolin derivative such as POE sorbit beeswax, sugar ester such as sucrose oleic acid monoester, polyglycerin monoalkyl ester and monoalkyl ether, polyether modified silicone surfactant And the like. 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 triethanolamine lauryl sulfate, lauroyl N-acyl sarcosinic acid such as sarcosine sodium, higher fatty acid amide sulfonate such as N-myristoyl-N-methyldaurine sodium, phosphate ester salt such as sodium POE oleyl ether phosphate, POE stearyl ether phosphate, di- 2-ethylhexyl sulfosuccinate such as sodium sulfosuccinate, sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecyl benzene sulfonate, linear dodecyl benzene sulfonate, etc. Le Kill benzenesulfonate, monosodium N- lauroyl glyceride Rita Min acid, N-
Examples thereof include N-acylglutamates such as disodium stearoylglutamate and monosodium N-myristoyl-L-glutamate.

As the cationic surfactant, for example, stearyl trimethyl ammonium chloride, alkyl trimethyl ammonium salt such as lauryl trimethyl ammonium chloride,
Examples thereof include dialkyl dimethyl ammonium salt, alkyl quaternary ammonium salt, and alkyl amine salt.

Examples of the amphoteric surfactant include 2-undecyl-
N, N, N- (hydroxyethylcarboxymethyl) -2-
Imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy 2
Imidazoline amphoteric surfactant such as sodium salt, 2-
Betaine-based surfactants such as heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amidobetaine, sulfobetaine, N-lauryl β-alanine, N-stearyl β- Examples thereof include amino acid salts such as alanine. It is used in one kind or a combination of two or more kinds of these hydrophilic surfactants.

In order to obtain a good microemulsion according to the present invention, a water-soluble polyether-modified silicone surfactant having silicone as a hydrophobic group is preferable. When the hydrophobic group is a hydrocarbon, a surfactant having a hydrocarbon having 12 or more carbon atoms is preferable, more preferably a surfactant having 16 or more carbon atoms, and further to improve stability at low temperature. Has a Kraft point of room temperature or lower, preferably 0 ° C. or lower.

The silicone used in the present invention is insoluble in water, specifically, dimethylpolysiloxane oil, cyclic dimethylpolysilixane oil, methylphenylpolysiloxane oil, amino-modified silicone oil, epoxy-modified silicone oil, Examples thereof include epoxy / polyether-modified silicone oil, carboxy-modified silicone oil, alcohol-modified silicone oil, alkyl-modified silicone oil, polyether-modified silicone oil, fluorine-modified silicone oil, and polymer dimethylsiloxane. However, the silicone used in the present invention is a silicone oil containing at least 0.5% by weight of one or more silicones having 12 or more silicon atoms.

According to the findings of the present inventors, it was difficult to obtain a stable microemulsion by adding 1% of dimethylpolysiloxane having a viscosity of 100 cps to cyclic dimethylpolysiloxane having a degree of polymerization of 5 was stable. Microemulsion. In this way, silicone containing 12 or more silicon does not contain 0.5% by weight or more,
It has been found that even a silicone oil in which a stable microemulsion cannot be obtained can be made into a stable microemulsion by adding 0.5% or more of silicone having 12 or more silicon.

The water-soluble alcohol, polyhydric alcohol and saccharides used in the present invention may be those normally used, and specific examples include methanol, ethanol, propanol, isopropanol, butanol, propylene glycol and 1,3- Butylene glycol, 1,4-butylene glycol, glycerin, diethylene glycol, dipropylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, polyglycerin, sorbitol, maltitol, maltotriose, mannitol, maltose, sucrose, etc. One of them or two or more of them are used.

The microemulsion in the present invention comprises a surfactant of 0.1 to 30%, silicone of 0.1 to 60%, water of 10 to 98%,
It may contain 1-90% monohydric alcohols, polyhydric alcohols and / or sugars. The ratio of the surfactant to the oily component is 1: 0.5 to 1:10, and the emulsion particle size is 0.01 to 0.1 μm.

Such a microemulsion can be prepared by using an emulsifying machine capable of giving a strong shearing force, for example, a high pressure homogenizer, an ultrasonic emulsifying machine or the like. Emulsify with a water ratio of 1: 5 to 19: 1. Further 0.05
To obtain particles with a size of less than μm, the ratio of monohydric alcohol, polyhydric alcohol and / or sugar: water at the time of emulsification is 1:
Emulsify as 4-8: 2. These microemulsions can be used by diluting them with water or mixing them with an aqueous product, if necessary. It is preferable to use a high-pressure homogenizer, but in order to obtain particles of 0.05 μm or less, it is preferable to emulsify at a temperature of 50 ° C. or less and a pressure of 300 atm or more.

Products to which the microemulsion according to the present invention is applied include other additives as required, for example, fragrances, dyes, buffers, salts, whitening agents, preservatives, antioxidant flavors, coloring agents and other powders, drugs, Thickeners, ultraviolet absorbers, other oils, surfactants, activating aids, etc. are appropriately added.

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

[Example 1] Furniture polish (part by weight) 1) Dimethyl silicone (5000 cps) 10.0 2) White kerosene 20.0 3) Preservative proper amount 4) Ammonium oleate 3.0 5) Water 25.0 6) Isopropyl alcohol 5.0 7) Water 40.0 Mix 1) to 3) and heat to dissolve at 70 ° C. This 4)
The mixture of (6) to (6) is heated and dissolved at 70 ° C. and added with stirring to emulsify. This emulsion is placed under pressure of 200 atm for 6
The mixture was emulsified at 0 ° C. using a high pressure homogenizer, and this was added with water 7) to obtain a transparent microemulsion.

The average particle size of the oil droplets of the obtained microemulsion was measured by the dynamic light scattering method and found to be 0.08 μm. It has been stable for over a year and has not separated at all.

[Example 2] Lotion (parts by weight) 1) Dimethyl silicone (20 cps) 0.5 2) Isopropyl myristate 0.5 3) Preservative proper amount 4) Perfume proper amount 5) HCO-60 (Nikko Chemicals Co.) 1.5 6) Water 0.5 7 ) Glycerin 2.5 8) Water 89.59) Ethanol 5.0 1) -4) are mixed and heated to 70 ° C to dissolve. 5)
The mixture of (7) to (7) is heated and dissolved at 70 ° C. and added with stirring to emulsify. This emulsion is put under pressure of 500 atm for 3
The mixture was emulsified at 0 ° C. using a high-pressure homogenizer, and the aqueous ethanol solutions 8) and 9) were added thereto to obtain a transparent microemulsion. The average particle size of the oil droplets of the obtained lotion was measured by the dynamic light scattering method and found to be 0.02 μm.
This lotion is very stable and gives a refreshing and unique feeling.

[Example 3] Hair transparent rinse agent (parts by weight) 1) Cyclic dimethyl silicone (polymerization degree 5) 40.0 2) Polymer dimethyl silicone 2.0 3) Preservative proper amount 4) Perfume proper amount 5) Cetyltrimethyl ammonium bromide 6.0 6) Water 30.0 7) Glycerin 28.0 1) to 4) are mixed and dissolved by heating at 70 ° C. 5)
The mixture of (7) to (7) is heated and dissolved at 70 ° C. and added with stirring to emulsify. This emulsion is put under pressure of 500 atm for 3
The mixture was emulsified at 0 ° C using a high pressure homogenizer to obtain a microemulsion. The average particle size of the obtained oil droplets of the rinse agent was measured by a dynamic light scattering method and found to be 0.08 μm. This rinse agent is very stable and gives a feeling of use that has never been seen before.

[Example 4] Shampoo agent (parts by weight) 1) Dimethyl silicone (100 cps) 40.0 2) Polyether-modified silicone activator (Note) 15.0 3) Water 15.0 4) Propylene glycol 30.0 Heat 1) to 50 ° C. Add 50 to 2) to 4)
The mixture is heated and melted at ℃ and added with stirring to emulsify. This emulsion was emulsified with a high-pressure homogenizer at a pressure of 800 atm at 30 ° C to obtain a transparent microemulsion.

The average particle size of the oil droplets of the obtained microemulsion was measured by the dynamic light scattering method and found to be 0.05 μm.

A shampoo agent was obtained by mixing 5 parts of this microemulsion with 95 parts of the shampoo base shown below.

Shampoo base 1) Polyoxyethylene (average 1.0) Lauryl sulphate Na 8.0 2) Polyoxyethylene (average 2.0 lauryl sulphate Na 5.0 3) Lauryl dimethylaminoacetic acid betaine 1.5 4) Palm fatty acid diethanol amide 4.0 5) Preservative proper amount 6) Perfume qs 7) Dye qs 8) Water Residue This shampoo is stable for over a year,
I didn't separate at all. In addition, when a usage test was conducted in comparison with a base material to which no microemulsion was added, 20
Out of 20 people, this shampoo had a better wash-up and a better combing result.

[Effects of the Invention] As described in detail above, the present invention relates to a microemulsion comprising at least a hydrophilic surfactant, silicone oil, a monohydric alcohol, a polyhydric alcohol and / or a saccharide, and is stable and safe. It can be said that it is highly practical in terms of functionality and functionality.
In particular, the present invention, due to its advantages, is a hairnic, hair lotion, aftershave, shampoo, rinse, lotion, body lotion, hair oil, emollient oil, lotion, aerosol product, deodorant, deodorant, pharmaceutical liquid It can be used for water-based products such as bath agents.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area A61K 7/50 A61K 7/50 C08L 83/04 C08L 83/04

Claims (1)

(57) [Claims] 1. A hydrophilic surfactant, a silicone oil containing at least 0.5% by weight of one or more silicones having 12 or more silicon atoms, and a water-soluble monohydric alcohol or a water-soluble silicone oil. One or more polyhydric alcohols and water-soluble saccharides and at least water are contained, and the weight ratio of hydrophilic surfactant to oil component is 1: 0.5 to 1:10, and the average particle size is A microemulsion having a thickness of 0.01 to 0.1 μm.