OIL/WATER MIXTURE COMPOSITION

Abstract: An oil/water mixture composition comprising an oil phase which is solid or semisolid at ordinary temperature and a water phase dispersed in the oil phase. Preferably, the water phase contains a humectant and is solid or semisolid at ordinary temperature and the oil phase contains hydrophobic silica, dextrin/fatty acid ester or oligoester of long-chain mono- and dicarboxylic acids with polyhydric alcohol. The composition is excellent in long-term stability and safety, reduced in stickiness and a sense of inocuity with the skin, enhanced in the humectant effect of preventing skin drying, and excellent in the persistence of the effect.

Description: [TECHNICAL FIELD] This invention relates to an oil- water mixed composition, and in particular, relates to an improvement of oil- water mixed mechanism of the composition. [BACKGROUND ART] Some cosmetics and drugs has a formulation of an oil- in- water or a water- in- oil emulsion mainly composed of a water phase and an oil phase component such as milky lotion, cream or ointment. Conventionally, a surfactant is required in order to manufacture such an oil- in- water or water- in- oil emulsion. Patent document EP-A-0 216 557 discloses in example 4 a W/O-emulsion containing 50% petroleum jelly, 28.80% sorbitol, 20% water. The composition further contains 1% surfactant (polyglyceryl oleate). However, a surfactant used in conventional often causes skin irritation, so not a few consumers feel misgivings. In addition, an oil- in- water or water- in- oil emulsion containing a surfactant is often criticized as being unstable with passage of time, sticky, and poor in water resistance. Under these circumstances, several emulsions containing little or no surfactant have recently been developed. For example, instead of using a surfactant, it is known the emulsion which uses clay mineral (Japanese Unexamined Patent Publication No.56-150007, No.57- 16812, No.58- 124535 and Japanese Patent Publication No.64- 3529), silicone oil (Japanese Unexamined Patent Publication No.61- 66527), glycyrrhizin (Japanese Unexamined Patent Publication No57- 62214), and the like as emulsifier or assistant emulsifier. Nevertheless, the emulsions shown above do not appear to have improved the stability of the emulsions with passage of time, and, it is too early to speculate at this time that the emulsions shown above have solved the problems relating to skin irritation, stickiness and water resistance. [DISCLOSURE OF INVENTION] In view of the foregoing problems of the prior art, the objective of this invention is to provide an oil- water mixed composition which is superior in stability and safety, without relying upon the use of a high amount of surfactant. As a result of diligent studies of the inventors to attain the above-mentioned object, it has been found that an oil- water mixed composition which has excellent stability without a surfactant can be acquired by dispersing a water phase into solid or semisolid oil phase uniformly at room temperature, and thus this invention has been accomplished. Namely, an water-in-oil dispersion in accordance with the present invention is characterized in that it comprises an oil phase which is solid or semi-solid at ambient temperature; a water phase which contains 10 to 70% by weight of humectant with respect to the dispersion and is solid or semi-solid at ambient temperature; and wherein the dispersion is free of surfactant; and the humectant is selected from a group consisting of polyethylene glycol, sorbitol, maltitol, hyaluronic acid, chondroitin sulfate, erythritol, trimethyl glycin, sodium lactate and pyrrolidonecarboxylic acid. Preferably, the oil, phase contains a solid or semi-solid oil component and is solid at room temperature, and said component constitutes 10 to 70% by weight of the dispersion. Further, the expression "solid or semisolid" as used herein means the conditions that can maintain the same configuration in the case of leaving an oil phase, a water phase or a composition under the room temperature. [BEST MODE FOR CARRYING OUT THE INVENTION] The preferred embodiments of this invention are shown as follows: In order to disperse a water phase into a semisolid or solid oil phase uniformly at room temperature, the following way is recommended: 1. Adding a humectant into a water phase to make it solid or semisolid at room temperature. In the circumstances of adopting the above way, when manufacturing an oil- water mixed composition, a solid or semisolid oil phase and a water phase are dispersed uniformly and stabilized. Next, the results from the use of the above four ways are shown as follows: Embodiment 1 Adding a humectant into a water phase to make it solid or semisolid at room temperature. In this embodiment, both of the oil phase and the water phase are "solid or semisolid at room temperature". The experiments are carried out by dissolving the oil phase and the water phase, separately and uniformly, under heat. After adding the dissolved water phase to the oil phase, the two phases are mixed together under constant stirring and gradually cooled down. The results of this procedure would produce "a solid or semisolid oil-water mixed composition at room temperature" with the oil phase and water phase dispersed uniformly. A solid or semisolid oil component used to make the oil phase solid or semisolid at room temperature is selected from a group comprising wax esters (e.g. microcrystalline wax, beeswax), solid paraffin, hydrogenated oil, tallow, Japan wax, beeswax, candelilla wax, carnauba wax, ceresin, vaseline, lanolin, lanolin derivatives, cholesterol, cholesterol derivatives and the like. Among these oil component, microcrystalline wax or vaseline are especially preferable in view of the effect. Although the amount of the compounding of these solid or semisolid oil component relates to another oil phase component, the amount is essential in making the oil phase solid or semisolid. Preferably, the amount of this oil component is made of 10 to 70%by weight and more preferably 10 to 40% by weight with respect to the whole amount of the oil- water mixed composition. If the amount of this oil component is less than 10% by weight, the composition would be unstable at high temperature. If the amount of this oil component is more than 70% by weight, the oil-water mixed composition would be too rigid and difficult to use. The humectant that added in the water phase to make the water phase solid or semisolid is selected from a group consisting of polyethylene glycol, sorbitol, maltitol, hyaluronic acid, chondroitin sulfate, erythritol, trimethyl glycin, sodium lactate, pyrrolidonecarboxylic acid and the like. Polyethylene glycol is the most preferable humectant in view of the effect. Although the amount of the compounding of these humectants relates to another water phase component, the amount is essential in making the oil phase solid or semisolid. The amount of the humectant is composed 10 to 70% by weight and preferably 10 to 40% by weight with respect to the whole amount of the oil-water mixed composition. If the amount of humectant is less than 10% by weight, the oil-water mixed composition would be unstable. If the humectant exceeds 70% by weight, the oil- water mixed composition would be too rigid and difficult to use. Some ingredients, which are commonly used in external preparation of cosmetics or drugs, can also be added to the oil- water mixed composition without directly spoiling the desired effect of this invention. These ingredients include powder components (e.g., titanium dioxide, mica, talc, silk powder, nylon powder, cellulose powder, silicone powder, polytetrafluoroethylene powder, hydrophobic treated powder and the like), hydro carbon (e.g., liquid paraffin, squalane and the like), extra oil from animals or plants tissue (e.g., olive oil, macadamia nut oil, tsubaki oil, jojoba oil, liquid lanolin and the like), and liquid oil components (e.g., silicone oil, perfluoro oil, fatty acid, higher alcohol, ester oils and the like which is obtained from the reaction thereof and the like which re obtained from the reaction thereof and the like). There are also other ingredients that can be added to the oil- water mixed composition. These include liquid humectants (e.g., propylene glycol, dipropylene glycol, 1,3- butylene glycol, glycerin, diglycerine, lactic acid and the like), antiseptics (e.g., ester parahydroxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol and the like), ultraviolet absorbers (e.g., p- aminobenzoic acid, homomenthyl- 7N- acetyl anthranilate, butyl methoxy benzoylmethane, glyceryl di- p-methoxy cinnamate, amyl salicylate, octyl methoxycinnamate, 2,4- dihydroxybenzophenone and the like), vitamin A and its derivatives, vitamin B (e.g., vitamin B 6 hydrochloride, vitamin B 6 tripalmitate, vitamin B 6 dioctanoate, vitamin B 2 and its derivatives, vitamin B 12 , vitamin B 15 and its derivatives and the like), vitamin C (e.g., ascorbic acid, ascorbyl sulfate [salt], ascorbyl phosphate [salt], ascorbyl dipalmitate, ascorbyl glucoside and the like), vitamin E (e.g., α - tocopherol, β - tocopherol, γ - tocopherol, vitamin E acetate, vitamin E nicotinate and the like), vitamin D, vitamin H and others such as pantothenic acid, pantethine, nicotin amide, benzyl nicotinate, γ - oryzanol, allantoin, glycyrrhizinic acid [salt], glycyrrhezinic acid and its derivatives, hinokitiol, rumex japonicus houtt , bisabolol, eucalyptol, thymol, inositol, saponins (e.g., saiko saponin, ginseng saponin, sponge cucumber gourd saponin, mukurossi saponin, pantothenyl ethyl ether, ethynylestradiol, tranexamic acid, cephalanthin, placental extract, pigments, sequestering agents, antioxidants, fragrances, film formers and the like. Also the oil- water mixed composition in this invention shows superior effects in stability, safety and emollient (i.e., to prevent the skin from dryness), and is long- lasting, as compared to other existing oil- water mixed emulsions. This newly invented oil- water mixed composition can be used in cosmetics drugs and quasi- drugs, and can be applied to epidermis and hair. The test results of this embodiment are shown in Table 1 and 2. The manufacturing process of each test sample is described as follows: The water phase and the oil phase are respectively heated at 80°C until complete dissolution. Then, the completely dissolved water phase is uniformly dispersed into the completely dissolved oil phase using a homodisperser in high speed. The mixture is allowed to cool down to 40°C under constant stirring. To test the stability, each sample is evaluated by the changes of color tone, smells, external appearance and sensation of use after storage at - 15°C, 0°C, 5°C, 30°C and 45°C for three months. ○ : No change in color tone, smells, external appearance and sensation of use. × : Some change in color tone, smells, external appearance and sensation of use. Test examples 1- 1 1- 2 1- 3 1- 4 1- 5 1- 6 1- 7 1- 8 1- 9 Oil phase (60%) liquid paraffin 60 50 40 30 20 10 5 1 0 microcrystalline wax 0 10 20 30 40 50 55 59 60 Properties of oil phase liquid liquid semi-solid semi-solid solid solid solid solid solid Melting point of oil phase - - Water phase (40%) purified water 10 10 10 10 10 10 10 10 10 polyethylene glycol 6000 30 30 30 30 30 30 30 30 30 Properties of oil phase solid solid solid solid solid solid solid solid solid Properties of the products liquid liquid semi-solid solid solid solid solid solid solid Stability × × ○ ○ ○ ○ ○ ○ ○ Test examples 1- 10 1- 11 1- 12 1- 13 1- 14 1- 15 1- 16 1- 17 1- 18 Oil phase (60%) liquid paraffin 20 20 20 20 20 20 20 20 20 microcrystalline wax 40 40 40 40 40 40 40 40 40 Properties of oil phase solid solid solid solid solid solid solid solid solid Water phase (40%) purified water 40 30 20 15 10 5 3 1 0 polyethylene glycol 6000 0 10 20 25 30 35 37 39 40 Properties of water phase liquid liquid liquid semi-solid solid solid solid solid solid Properties of the products liquid semi-solid semi-solid solid solid solid solid solid solid Stability × × × ○ ○ ○ ○ ○ ○ As demonstrated in Table 1, the oil- water mixed composition is less stable when its oil phase in liquid form, regardless of whether its water phase is solid or semisolid. However, when the oil phase is semisolid or solid, the stability of the oil- water mixed composition is much enhanced if the water phase is in solid form. Also as shown in Table 2, the oil- water mixed composition is less stable when its water phase is in liquid form, regardless of whether its oil phase is solid or semisolid. However, when the water phase is semisolid or solid, the stability of the oil- water mixed composition is much enhanced when its oil phase and water phase are both in semisolid or solid form. As a results of foregoing, it was observed excellent stability when its oil phase and water phase are both in semisolid or solid form. Next further, inventors have manufactured the various oil- water mixed composition and studied the stability and the usability of these compositions. The methods of manufacturing of various mixed composition and evaluating of the stability are described above. After applying these samples to 30 women, evaluating the stickiness, unsuitability for skin, emollient effect, and persistence of emollient effect under the following standard; <Evaluation Standard> obtained slightly obtained not obtained Stickiness 0 1 2 Unsuitability for the skin 0 1 2 Emollient effect 2 1 0 Persistence of emollient effect 2 1 0 ○ : representing evaluation point average of more than 1.5 Δ: representing evaluation point average between 0.5 and 1.5 × : representing evaluation point average of less than 0.5 Examples 1- 1 to 1- 5 and Comparative examples 1- a to 1- d Examples Comparative examples 1- 1 1- 2 1- 3 1- 4 1- 5 1- 6 1- a 1- b 1- c 1 -d Water phase purified water 5 10 5 10 5 10 30 45 3 7 glycerin 5 5 - 7 - 5 5 5 - 10 1,3-butylene glycol - 10 5 - - 10 - 10 - 5 polyethylene glycol 1500 25 20 5 10 5 20 - - - - polyethylene glycol 6000 5 15 - 10 10 25 5 - 20 - polyethylene glycol 20000 - - 5 - - - - - - - cellulose powder - - - 3 - - - - - - Oil phase liquid paraffin 20 15 30 - 20 15 20 35 2 3 squalane - - - 20 - - - - - - dimethyl polysiloxane 5cs 5 - 10 5 20 - 35 - - - decamethyl cyclopentasiloxane - 5 - 15 - - - - - - vaseline 15 10 15 10 20 - 5 - 30 50 microcrystalline wax 20 10 20 10 - 10 - 5 45 25 silicone powder - - 5 - 20 5 - - - - Stability ○ ○ ○ ○ ○ Δ × × ○ ○ Usability emollient effect ○ ○ ○ ○ ○ ○ ○ × ○ ○ persistence of emollient effect ○ ○ ○ ○ ○ ○ × × ○ Δ thickness ○ ○ ○ ○ ○ ○ Δ × ○ ○ stickiness ○ ○ ○ ○ ○ ○ ○ ○ × × As shown from foregoing, the oil- water mixed composition which is consisted of a humectant- containing solid or semisolid oil phase, and a water phase which contains no surfactant has superior stability with passage of time and safety. This same composition also shows very little stickiness and sensation of unsuitability, has excellent emollient effect (i.e., to prevent the skin from dryness), and is persistent in preserving its emollient effect.

Claims: A water-in-oil dispersion comprising: an oil phase which is solid or semi-solid at ambient temperature; a water phase which contains 10 to 70% by weight of humectant with respect to the dispersion and is solid or semi-solid at ambient temperature; and wherein the dispersion is free of surfactant; and the humectant is selected from a group consisting of polyethylene glycol, sorbitol, maltiol, hyaluronic acid, chondroitin sulfate, erythritol,. trimethyl glycin, sodium lactate, and pyrrolidonecarboxylic acid. A dispersion according to claim 1, wherein the oil phase contains a solid or semi-solid oil component and is solid at room temperature, and said component constitutes 10 to 70% by weight of the dispersion. A dispersion according to claim 2 wherein the oil phase component is selected from a group comprising wax esters (e.g. microcrystalline wax, carnauba wax, ceresin, vaseline, lanolin, lanolin derivatives, cholesterol, cholesterol derivatives. A dispersion according to claim 3 wherein the oil phase component is microcrystalline wax and/or vaseline. A dispersion according to any preceding claim wherein the humectant is poly(ethyleneglycol).

Inventors: ABE KOJI, ITO KENZO, NAKAMURA FUMIAKI, ABE, KOJI, ITO, KENZO, NAKAMURA, FUMIAKI, ABE, Koji, Shiseido Research Center(1), ITO, Kenzo, Shiseido Research Center(1), NAKAMURA, Fumiaki, Shiseido Research Center(1)
Applicants: SHISEIDO CO LTD, SHISEIDO COMPANY LIMITED
Application year: 1996
Main classification: A61K7
IPC codes: A61K8, A61Q19, B01J13, A61K9