JPH0513924B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a water-in-oil emulsion cosmetic that is stable and has an excellent feeling of use. More specifically, the present invention relates to a water-in-oil emulsion cosmetic that contains a large amount of silicone oil and is stable and has an excellent feeling of use. [Conventional technology] Traditionally, water-in-oil emulsion cosmetics cover the skin surface with an oil film to prevent water evaporation, which is effective against rough skin, and because they are water-repellent, they are effective in preventing makeup from fading. Because of this, it is often used in facial cosmetics and makeup cosmetics. On the other hand, silicone oil is often used because it is smooth to use and has excellent water repellency, and in particular, those containing volatile silicone spread well when applied, and the volatile silicone oil evaporates as it is spread, so it adheres well. It has been widely used because it has good elasticity and is resistant to sebum and sweat, making it difficult to break down. [Problems to be Solved by the Invention] However, silicone oil has the disadvantage that it is difficult to emulsify and it is difficult to obtain a stable water-in-oil emulsion system, and despite the strong demand for silicone oil, However, no water-in-oil emulsion cosmetic has been obtained which contains a large amount of this and has stability sufficient for commercial use. Up until now, there have been methods for obtaining water-in-oil emulsified cosmetics using silicone oil with good stability, such as adding waxes to solidify the entire system, and using silicone to thicken the system. All of them have drawbacks such as being heavy and sticky. [Means for Solving the Problems] In view of the above circumstances, the present inventors have made extensive studies and found that even in an oil phase containing silicone oil at a high blending ratio of 30% or more, water-soluble organic acids and water-soluble We have discovered that a water-in-oil emulsion cosmetic that is stable and has an excellent feel when used can be obtained by using an aqueous phase containing one or more types of organic acid salts and a specific surfactant. The invention was completed. That is, in the present invention, (A) silicone oil is in the oil phase component.
If the amount is 30% by weight or more, the oil phase and (B) 1 selected from the group consisting of a water-soluble organic acid and a water-soluble organic acid salt;
It consists of an aqueous phase in which the species or two or more species are 0.1% by weight or more in the aqueous phase component and (C) a lipophilic ionic surfactant, in which the weight ratio of (A):(B) is 2:1 to 1: 5, and is a water-in-oil emulsion cosmetic in which (C) is 1% by weight or more of the total components. The configuration of the present invention will be explained in detail below. The first point of the present invention is to select a lipophilic nonionic surfactant that is good for silicone oil. Conventionally, water-in-oil emulsified cosmetics using hydrocarbon oils include lipophilic emulsifiers such as sorbitan monofatty acid ester, sorbitan difatty acid ester, glyceryl monofatty acid ester, glyceryl difatty acid ester, POE addition hydrogenated castor oil, Polyglycerin fatty acid esters and the like have been used. However, even if an attempt is made to create a water-in-oil emulsion system containing a large amount of silicone oil using these activators, it is not always possible to obtain a good emulsion system due to the different properties of the oil phase. On the contrary, according to the inventors' research, it was found that most of them have stability problems. However, if a specific surfactant discovered by the present inventors is used and one or more selected from the group consisting of water-soluble organic acids and water-soluble organic acid salts are used in combination. For example, a large amount of silicone oil can be emulsified stably. This is the first finding discovered by the present inventors. The silicone oil used in the present invention may be any conventionally used silicone oil, but specifically, dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane,
Examples include those obtained by dissolving silicone resin or trimethylsiloxysilicate in the above-mentioned silicone oil. In the present invention, particularly volatile low-molecular silicone oils or cyclic silicone oils can be stably blended, which is truly advantageous in terms of the feel of use. When volatile silicone oil is blended, the product has a particularly refreshing feel when used. That is, it spreads easily during application, and after application, the oil content evaporates, resulting in a refreshing product without the stickiness of oil. This effect becomes more pronounced as the amount of volatile silicone oil in the oil phase increases, but it is particularly good when 50% or more of the silicone oil in the oil phase is volatile silicone. Although the amount of silicone oil to be blended is related to the amounts of other oil phase components, the present invention is most useful when silicone oil accounts for 30% or more of the oil phase components. That is, if it is 30% or less, other common surfactants can be used. Note that the oil phase components other than silicone oil are general oil phase components used in cosmetics, as will be described later. The proportion of the oil phase component containing silicone oil in the water-in-oil emulsion cosmetic of the present invention is preferably 17 to 1.
67% by weight, particularly preferably 20-33% by weight. The lipophilic surfactants used in the present invention include sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan sesquiolate, sorbitan diolate, glyceryl diolate, glyceryl diisostearate and the following [1],
One or more surfactants selected from the group consisting of surfactants having structures [2] and [3]. {In the general formulas [1][2][3], R is a methyl group or partially a phenyl group, R' is hydrogen or an alkyl group having 1 to 12 carbon atoms, p is a number of 1 to 5, and q is 2 ~
The numbers 3, x, m, and n are average numbers, and the polyoxyalkylene-modified organopolysiloxane contains 5 to 40% by weight of polyoxyalkylene groups in the molecule, and the molecular weight of the polyoxyalkylene-modified organopolysiloxane is 2000 or more. Represents a numerical value such that . } The blending amount of the lipophilic surfactant is 1 to 50% by weight in the water-in-oil emulsion cosmetic. The water-soluble organic acids used in the present invention include hydroxy acids having 6 or less carbon atoms, polybasic acids, hydroxy polybasic acids, such as hydroxyacetic acid, lactic acid, β-
Hydroxypropionic acid, α-hydroxybutyric acid,
β-hydroxybutyric acid, α-hydroxyisobutyric acid,
Oxalic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, malic acid, tartronic acid,
Citric acid, isocitric acid, tartaric acid, etc. can be mentioned. If the number of carbon atoms is 7 or more, the solubility in water will be poor, which is not preferable. The water-soluble organic acid salts used in the present invention include hydroxy acids having 14 or less carbon atoms, polybasic acids, hydroxy polybasic acids, such as hydroxyacetic acid, lactic acid,
β-hydroxypropionic acid, α-hydroxybutyric acid, β-hydroxybutyric acid, α-hydroxyisobutyric acid, α-hydroxyisocaproic acid, oxalic acid,
malonic acid, succinic acid, glutaric acid, adipic acid,
Examples include sodium, potassium, triethanolamine, or ammonium salts of pimelic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, malic acid, tartronic acid, citric acid, isocitric acid, tartaric acid, and the like. If the number of carbon atoms exceeds 14, the solubility in water will be poor, which is not preferable. The concentration of the water-soluble organic acid and water-soluble organic acid salts used in the present invention is 0.1% by weight or more in the aqueous phase, but if the concentration is less than 0.1% by weight, no effect will be exhibited. On the other hand, if too large a quantity is blended and the solubility is exceeded, precipitation may occur, which is not preferable. Therefore, the amount of water-soluble organic acids and water-soluble organic acid salts used in the present invention is preferably 0.1 to 50% by weight in the aqueous phase. The total amount of the aqueous phase containing one or more of water-soluble organic acids and water-soluble organic acid salts is preferably 33 to 83% by weight of the total water-in-oil emulsion cosmetic, Particularly preferred is 50 to 80% by weight. (A) an oil phase in which silicone oil accounts for 30% by weight or more of the oil phase components; and (B) an aqueous phase in which one or more of a water-soluble organic acid and a water-soluble organic acid salt are used in the present invention. The mixing ratio with the aqueous phase, which is 0.1% by weight or more in the ingredients, is
From the viewpoint of stability and feeling in use, the weight ratio of (A):(B) is preferably 1:1 to 1:5. In addition to the above-mentioned essential ingredients, the emulsified cosmetic composition of the present invention may contain, if necessary, components that are included in ordinary cosmetic compositions. For example, moisturizers such as propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, maltitol, sorbitol, polyethylene glycol, pyrrolidone carboxylate, sodium chondroitin sulfate, sodium hyaluronate, petrolatum,
Solid and semi-solid oils such as lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols,
Liquid oils such as squalane, liquid paraffin, ester oils, triglycerides, inorganic and organic pigments, inorganic and organic pigments whose surface has been treated with metal soap or silicone, coloring materials such as organic dyes, cationic activators, anionic activators. surfactants such as nonionic surfactants, vitamin E, vitamin E
Chemicals such as acetate, astringents, antioxidants, preservatives, fragrances, PH regulators such as dibasic sodium phosphate, thickeners such as carboxyvinyl polymers, methylcellulose, organically modified montmorillonite, and ultraviolet absorbers are not included in this book. They can be blended within a qualitative and quantitative range that does not impair the purpose and effect of the invention. [Effects of the Invention] The emulsified cosmetic of the invention is stable, has a non-sticky and refreshing feel when used, is water repellent after application, and has good durability over time. [Example] Next, the present invention will be explained in detail with reference to an example.
The present invention is not limited thereby. The blending amounts in the examples are weight %. Prior to the examples, evaluation methods adopted in each example will be explained. (Stability) A water-in-oil emulsion cosmetic prepared by a specified method is
℃, room temperature, and in a constant temperature bath at 37℃, and the stability was evaluated immediately after trial production and after one month according to the following evaluation criteria. No separation or aggregation 〇 Slight separation or aggregation Δ Separation or aggregation × (Usability) A panel of 20 women evaluated usability such as spreadability, crispness, stickiness, and firmness according to the following evaluation criteria. I evaluated it. 15 or more people answered good 〇 7 to 14 people answered good Δ 6 or less people answered good × Example 1 Cream Weight % Decamethylcyclopentasiloxane dimethyl polysiloxane (6cs) Fluid Paraffin (120sec) Polyoxyalkylene modified organopolysiloxane [General formula 1] (Polyoxyalkylene weight 20%, average molecular weight 6200) Fragrance 10.0 5.0 5.0 5.0 0.2 Ion exchange water Sodium citrate 1,3-butylene glycol Preservative 67.6 2.0 5.0 0.2 (Production method) Heat the oil phase to 70℃. To this is added previously heated to 70°C, and after emulsification and dispersion, the mixture is stirred and cooled to room temperature to obtain the desired cream. The manufacturing methods of Examples and Comparative Examples below are based on the method of Example 1. (Results) As shown in Table 1, the cream of this example showed good results in both stability and usability. Example 2 Hand cream (% by weight) Octamethylcyclotetrasiloxane 5.0 Decamethylcyclopentasiloxane 5.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (70sec) 5.0 Sorbitan diisostearate 8.0 Fragrance 0.2 Ion exchange water 63.5 Potassium sodium tartrate 3.0 Propylene glycol 5.0 Preservative 0.3 (Results) As shown in Table 1, the hand cream of this example showed good results in both stability and usability. Comparative Example 1 (% by weight) Decamethylcyclopentasiloxane 10.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (120sec) 5.0 Polyoxyalkylene-modified organopolysiloxane [General formula 1] (Polyoxyalkylene weight
20%, average molecular weight 6200) 5.0 Fragrance 0.2 Ion exchange water 69.6 1,3-butylene glycol 5.0 Preservative 0.2 (Results) Table 1 shows the evaluation results of stability and usability. Comparative example 2 (wt%) Octamethylcyclotetrasiloxane 5.0 Decamethylcyclopentasiloxane 5.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (70sec) 5.0 Glyceryl monooleate 8.0 Fragrance 0.2 Ion exchange water 63.5 Potassium sodium tartrate 3.0 Propylene glycol 5.0 Preservative Agent 0.3 (Results) The evaluation results of stability and usability are shown in Table 1. Comparative example 3 (wt%) Liquid paraffin (70sec) 20.0 Sorbitan diisostearate 8.0 Fragrance 0.2 Ion exchange water 63.5 Potassium sodium tartrate 3.0 Propylene glycol 5.0 Preservative 0.3 (Results) The evaluation results of stability and usability are shown in Table 1. Indicated.

[Table] Examples 3 to 6 The compositions shown in Table 2 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 2. Comparative Examples 4 and 5 Compositions shown in Table 2 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 2. Examples 7 to 10 The compositions shown in Table 3 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 3. Comparative Example 6 Compositions shown in Table 3 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 3.

【table】

【table】

[Table] Example 11 Emulsion (wt%) Dimethylpolysiloxane (6cs) 19.0 Dimethylpolysiloxane (100cs) 2.0 Polyoxyalkylene-modified organopolysiloxane [General formula 3] (Polyoxyalkylene weight
(17% by weight, average molecular weight 6000) 5.0 Flavor (appropriate amount) Ion-exchanged water 64.0 Sodium malate 5.0 Potassium acetate 5.0 Preservative (appropriate amount) This emulsion had good usability and stability. Example 12 Hair cream (% by weight) Octamethylcyclotetrasiloxane 10.0 Phenylpolysiloxane 5.0 Squalane 4.0 Silicone resin 1.0 Glyceryldiolate 2.0 Polyoxyalkylene-modified organopolysiloxane [General formula 2] (Polyoxyalkylene weight
15% by weight, average molecular weight 9000) 4.0 Antioxidant 0.05 Vitamin E acetate 0.1 Ion exchange water 66.95 Sodium succinate 2.0 Sodium isocitrate 1.0 Tartaric acid 0.5 Dipropylene glycol 3.0 Fragrance 0.1 Preservative 0.3 This hair cream has excellent usability and stability. All were good. Example 13 Emulsified foundation decamethylcyclopentasiloxane 15.0 Dimethylpolysiloxane 5.0 Polyoxyalkylene-modified organopolysiloxane [General formula 1] (Polyoxyalkylene weight
20% by weight) 5.0 Antioxidant Appropriate amount Fragrance Appropriate amount Mixed pigment (silicon treated pigment) 30.0 Ion exchange water 41.9 1,3-butylene glycol 5.0 Methyl paraben 0.1 Sodium lactate 3.0 This emulsified foundation has good usability and stability. It was hot. Example 14 Makeup base (weight %) Trimethylsiloxysilicate 5.0 Octamethylcyclotetrasiloxane 5.0 Decamethylcyclopentasiloxane 12.0 Dimethylpolysiloxane (6cs) 5.0 Polyoxyalkylene modified organopolysiloxane [General formula 2] (Polyoxyalkylene weight
15% by weight, average molecular weight 9000) 4.0 Perfume (appropriate amount) Ion-exchanged water 30.0 Sodium lactate 29.0 Ethanol 10.0 Preservative (appropriate amount) This makeup base had good usability and stability.

Claims (1)

[Scope of Claims] 1 (A) an oil phase in which silicone oil accounts for 30% by weight or more in the oil phase component; (B) a water-soluble hydroxy acid, polybasic acid, or hydroxy polybasic acid having 6 or less carbon atoms; one or more selected from water-soluble organic acids, and water-soluble organic acid salts which are sodium, potassium, triethanolamine, or ammonium salts of hydroxy acids, polybasic acids, and hydroxy polybasic acids having 14 or less carbon atoms. (C) sorbitan diisostearate, sorbitan diolate, glyceryl diisostearate,
Glyceryldiolate, or the following general formula [1],
A lipophilic nonionic surfactant consisting of one or more selected from the polyoxyalkylene-modified polysiloxanes shown in [2] and [3], where (A):(B) is 2: 1 to 1:5, and a water-in-oil emulsion cosmetic in which (C) is 1% by weight or more of the total components. (In general formulas [1], [2], [3], R is a methyl group or partially phenyl group, R' is hydrogen or has 1 carbon number)
~12 alkyl group, p is a number from 1 to 5, q is a number from 2 to 3
The numbers x, m, and n are average numbers, and the polyoxyalkylene-modified organopolysiloxane contains 5 to 40% by weight of polyoxyalkylene groups in the molecule, and the molecular weight of the polyoxyalkylene-modified organopolysiloxane is 2000 or more. Represents a numerical value such that )