WO2020098355A1 - 皮肤外用剂组合物 - Google Patents

皮肤外用剂组合物 Download PDF

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Publication number
WO2020098355A1
WO2020098355A1 PCT/CN2019/105171 CN2019105171W WO2020098355A1 WO 2020098355 A1 WO2020098355 A1 WO 2020098355A1 CN 2019105171 W CN2019105171 W CN 2019105171W WO 2020098355 A1 WO2020098355 A1 WO 2020098355A1
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composition
thickener
oil
present
skin
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PCT/CN2019/105171
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English (en)
French (fr)
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韩扬
曲睿
渡边启
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株式会社资生堂
韩扬
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Priority to JP2021525559A priority Critical patent/JP7350067B2/ja
Publication of WO2020098355A1 publication Critical patent/WO2020098355A1/zh

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9794—Liliopsida [monocotyledons]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/592—Mixtures of compounds complementing their respective functions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/85—Products or compounds obtained by fermentation, e.g. yoghurt, beer, wine

Definitions

  • the invention belongs to the technical field of skin care products, and relates to a composition system having a synergistic viscosity-increasing effect, and more specifically, to a composition for external use of skin.
  • compositions for external use of skin are widely used in cosmetic products.
  • Such compositions usually include an aqueous system and an oily system.
  • Aqueous systems are widely used in cosmetic products. While playing a specific function, they can also give people a refreshing feeling.
  • water or an aqueous substance serves as a continuous phase, and the oily component serves as a dispersed phase, forming a liquid or semi-solid system.
  • the usual oil-in-water composition contains various active ingredients to achieve effects such as moisturizing, supplementing nutrition, protection or repair.
  • various additives such as various emulsifiers, stabilizers, thickeners, preservatives and other ingredients may be added.
  • the stability of the system is important for oil-in-water compositions containing multiple active ingredients.
  • phase separation within the system is likely to occur during production, transportation, storage, or use, resulting in a deterioration of the external appearance of cosmetics.
  • the presence of multiple active ingredients makes it difficult to operate when forming stable oil phase droplets suspended or dispersed in an aqueous continuous phase in a desired form.
  • the introduction of more active ingredients often leads to the use of more kinds or amounts of additives. Therefore, the safety of the product is also the focus of attention.
  • non-ionic surfactants such as polyoxyethylene alkyl ethers and sorbitan fatty acid partial esters are mainly used.
  • those surfactants inevitably have different degrees of stimulation to the skin. Therefore, the amount of surfactants should be reduced as much as possible, and sometimes try to emulsify without using these surfactants, but the uniformity and stability of the emulsion Problems such as sexuality are prone to occur, and it may not be possible to obtain an emulsion that meets the requirements.
  • emulsifiers derived from natural substances is discussed.
  • the use of fermented grains of grains as emulsifiers or stabilizing ingredients is also known, for example:
  • Reference 1 discloses a product LAFR- ⁇ obtained by fermentation using rice as a raw material, and studies the surface tension and interfacial tension of LAFR- ⁇ , and studies the emulsification behavior exhibited by LAFR- ⁇ and contains LAFR- ⁇ The oxidation resistance of the suspension system.
  • Reference 2 discloses a lotion containing fermented rice bran, which contains 0.01-10% by mass of fermented rice bran, and the lotion has a low viscosity of 1000 mPa ⁇ s or less.
  • Reference 3 discloses an emulsifying aid, which is mainly composed of rice fermented by lactic acid bacteria obtained by fermentation of rice with lactic acid bacteria. Fermented rice obtained by fermenting rice with lactic acid bacteria has good emulsifying ability, emulsification stabilizing effect and even protective colloid-like effect. At the same time, since it comes from rice, it has low toxicity, little irritation to the skin, and safety to organisms High, it can be used as a basic raw material for emulsifiers or emulsion stabilizers for cosmetics. In addition, it has been unexpectedly found that the fermented rice shows significant whitening, skin beautifying and hair quality improving effects, and can also be used as a cosmetic effect Compounding agent.
  • fermented cereal products are also found in Reference 4, which relates to a fermented product of cereals and ginseng stems and leaves and its application in skin cleansing products.
  • the method first heat sterilizes the culture medium containing grains or ginseng stems and leaves, and then inserts microorganisms, fermentes, and sterilizes to obtain a fermentation product containing cells, fermentation filtrate, and solid particles.
  • the fermentation product is used in cleaning products. It has a good effect of removing oil from the skin surface, smoothing the skin, anti-inflammatory, acne and so on. And it has the characteristics of nourishing the skin, gently exfoliating the skin, low irritation, safe and gentle.
  • oil-in-water composition in order to obtain a stable form of the oil-in-water composition, for example, to enable oily droplets to be suspended in the system stably for a longer time, it is necessary to give the oil-in-water composition system a certain viscosity or consistency Therefore, under normal circumstances, it is necessary to add a certain amount of thickener to obtain the stability effect.
  • thickeners are synthetic polymers or chemically modified natural polymers.
  • Reference 5 discloses an oil-in-water emulsified skin external preparation.
  • This emulsion preparation is obtained by using hydroxylated phospholipids and lactic acid bacteria fermentation materials of grains and alkyl-modified acrylic-based polymers and / or their salts as essential ingredients.
  • the grain fermentation product is used as an emulsifier
  • the alkyl-modified acrylic polymer and / or its salt is used as a thickener
  • the hydroxylated phospholipid is used as a stabilizer.
  • Reference 5 verifies that the combined use of the above three components is a necessary condition to obtain a stable emulsion system (that is, the phenomenon of water phase separation and oil phase separation does not occur). The desired effect.
  • the present invention mainly relates to the synergistic use of cereal fermentation products and additives in existing skin external preparation compositions.
  • the present invention provides a skin external preparation composition having a synergistic viscosity-increasing effect.
  • a grain fermentation product generally used only as an emulsifier and a polyacrylic acid and its derivative thickener are more
  • carbohydrate thickeners were used simultaneously, it was unexpectedly observed that the simultaneous use of both can significantly increase the viscosity of the system, produce a synergistic thickening effect, and obtain a stable system compared to the case of using the thickener alone.
  • the molecular side chain structure of the polyacrylic acid and its derivative thickener contains the structure of the following formula (1):
  • R 1 is an alkylene group having 2-6 carbon atoms
  • R 2 is an alkyl group having 1-50 carbon atoms
  • n represents an integer of 0-100
  • L is a single bond or a divalent linking group.
  • the present invention first provides a composition for external use of skin, wherein the composition includes:
  • the (B) thickener is selected from polyacrylic acid and its derivative thickener or polysaccharide thickener,
  • the molecular side chain structure of the polyacrylic acid and its derivative thickener contains the structure of the following formula (1):
  • R 1 is a linear or branched alkylene group having 2 to 6 carbon atoms
  • R 2 is a linear or branched alkyl group having 1 to 50 carbon atoms
  • n represents 0 to 100 Integer
  • L represents a single bond or a divalent linking group.
  • composition according to [2] wherein the cereal is selected from one or more of rice, glutinous rice, millet, black rice, corn, and sorghum.
  • composition according to [1] or [2], wherein the fermentation is performed in the presence of lactic acid bacteria is performed in the presence of lactic acid bacteria.
  • composition according to any one of [1] to [3], wherein the composition has a viscosity of 1200 mPa ⁇ s or more.
  • the present invention also provides a cosmetic, wherein the cosmetic includes the skin external agent composition according to any one of the above.
  • fermented grains especially rice fermented materials and thickeners
  • the cosmetics containing the skin external preparation composition of the present invention can give the user a refreshing, non-sticky, and smooth feeling of use when used.
  • FIG. 1 Viscosity changes when different amounts of PEMULEN are used in conjunction with grain fermentation
  • the active ingredient of the fermented product obtained after the fermentation of cereals can be used as an emulsifier or a nutritional ingredient.
  • the present invention unexpectedly discovered that when such a fermented grain is used together with the thickener defined by the present invention, it can produce a synergistic thickening effect with the thickener defined by the present invention.
  • the cereal in the present invention may be one or more selected from rice, glutinous rice, millet, black rice, corn, and sorghum.
  • rice or glutinous rice is preferred, and rice is further preferred.
  • the grains in the present invention may be grains with or without processing, for example, may be any one or more of brown rice, polished rice, processed rice, etc., which are not particularly limited, and in some preferred embodiments of the present invention In order to facilitate the fermentation or the purity of the obtained fermentation product, processed grains, such as polished rice or processed rice, are generally used.
  • the method of fermentation is not particularly limited, and microorganisms can be used to ferment grains, preferably using lactic acid bacteria.
  • these lactic acid bacteria that can be used for grain fermentation include Lactobacillus plantarum, L. brevis, L. casei, and L. cellobiosus. , L. vaccinostercus, Streptococcus faecalis, Bacillus coagulans, etc.
  • Lactobacillus plantarum is preferably used from the viewpoint of emulsifying ability of the obtained fermented rice of lactic acid bacteria.
  • the grains are also pre-treated before fermentation, and the pre-treatment includes screening or washing.
  • the grains are processed, and suitable pretreatment methods such as washing are applied to remove possible impurities or other bacteria that hinder the fermentation of lactic acid bacteria, to obtain grains with relatively pure ingredients, such as clean refined rice.
  • the above-mentioned refined rice is placed in a fermentation container, which is airtight, so that the subsequent fermentation process can be performed under anaerobic conditions.
  • water, lactic acid bacteria, and fermentation auxiliary components are introduced into the fermentation vessel.
  • the water is preferably distilled water or purified water, and the amount thereof is not particularly limited, and can generally be less than 10 times the mass of the grains (finished rice) after processing and pretreatment.
  • the fermentation auxiliary component can be selected from various carbohydrates, and glucose, fructose, galactose, sucrose, etc. can be used, among which fructose is most preferably used.
  • the container is closed so that the fermentation can be performed under anaerobic conditions.
  • the temperature and time of the fermentation are not particularly limited, and the usual fermentation method can be followed.
  • fermentation may be performed under room temperature conditions or under heating conditions, and the fermentation time may be several days or weeks.
  • the lactic acid bacteria-containing fermentation liquid obtained by the above fermentation step can be used as an active ingredient as it is.
  • the obtained fermentation liquid may also be purified or concentrated.
  • the means of purification is not particularly limited, and filtration may be performed under normal pressure or under reduced pressure.
  • the concentration method can be carried out using distillation or the like.
  • a concentration step can be carried out after purification.
  • (B) thickeners in the present invention can impart a certain viscosity to the composition for external use on skin, and in some preferred embodiments, impart a certain viscosity to the aqueous composition.
  • the (B) thickener of the present invention is selected from polyacrylic acid and its derivative thickeners or polysaccharide thickeners.
  • the polyacrylic acid and its derivative thickener of the present invention may be a polymer or its derivative obtained by copolymerizing acrylic acid and acrylate.
  • the molecular side chain structure of the polyacrylic acid and its derivative thickener contains the structure of the following formula (1):
  • R 1 is a linear or branched alkylene group having 2 to 6 carbon atoms, preferably a linear or branched alkylene group having 2 to 4 carbon atoms
  • R 2 is a carbon atom having A linear or branched alkyl group of 1-50, preferably a linear or branched alkyl group having 6 to 30 carbon atoms, and more preferably a linear or branched alkyl group of 10-25, where n represents An integer of 0-100, preferably an integer of 1-100, further preferably an integer of 6-50, even more preferably an integer of 10-30, L represents a single bond or a divalent linking group, preferably an alkylene group group.
  • the thickener of the present invention can be regarded as copolymerized with acrylic acid and alkyl acrylate.
  • polyacrylic acid and its derivative thickener may have the following molecular structure:
  • R and R ' may be alkyl groups having 10 to 30 carbon atoms.
  • Thickeners with such a structure can be obtained commercially, for example TR-1, TR-2.
  • n in the side chain of the thickener of polyacrylic acid and its derivatives is 1-30, that is, there is a polyoxyalkylene structure in the side chain, which may be cited,
  • the polyoxyalkylene group may have a polyoxyethylene or polyoxypropylene structure.
  • it may have an ester structure, for example, it may be an ester formed by acrylic acid and an alcohol having 1-6 carbon atoms, Typically, it has the following structure:
  • R may be H or an alkyl group having 1 to 4 carbon atoms.
  • thickeners with such structures are commercially available, for example, ACULYN TM series thickeners under the name of DOW Chemicals.
  • the polyacrylic acid and its derivative thickener used in some embodiments of the present invention may have an amide and sulfonate (salt) group in its side chain .
  • the structures that can be enumerated are:
  • Thickeners with such a structure can be obtained commercially, for example HMB series thickener, etc.
  • the molecule may have a certain cross-linked structure, for example, physical cross-links formed by hydrogen bonds or cross-links formed by ionic bonds.
  • starch and cellulose thickeners can be used, and preferably, the cellulose thickener is used in the present invention.
  • alkyl and / or polyalkoxy segments are used for etherification modification in the molecule.
  • modified cellulose obtained by modifying cellulose, which is obtained by alkylating (etherifying) the hydroxyl group on one unit ring of the fiber is optional. That is, the modified cellulose has the following structure:
  • R may be H, an alkyl group having 1-4 carbon atoms,-(R a O) m -R b or -R c OR d , where R a represents an alkylene group having 1-4 carbon atoms , R b represents H or an alkyl group having 1 to 4 carbon atoms, R c represents an alkylene group having 1 to 4 carbon atoms, and is optionally substituted with a hydroxyl group, and R d represents 10 to 30 carbon atoms Alkyl, m is an integer of 1-100.
  • the thickeners having the above structure can be listed under the name of DAIDO Products, etc.
  • the form when these thickeners are used is not particularly limited, and for example, they can be used in the form of an aqueous solution or another solution.
  • the above-mentioned thickener may be used in the form of an emulsion, especially an oil-in-water emulsion.
  • such a solution may also contain other auxiliary stabilizing ingredients, such as acids, alkalis or salts as stabilizing ingredients.
  • the present invention found that even in the absence of other viscosity-increasing ingredients, when the thickener is used synergistically with the fermented grain, the viscosity will be higher than that of the system using only or having the thickener Substantial growth.
  • the amount of the thickener is such that the viscosity obtained due to the above-mentioned synergistic effect is 1.2 times or more the viscosity of the system using only or having the thickener, preferably 2 times, 4 times, 4.1 times , 4.5 times, 6 times or 10 times or more, more preferably 20 times, 30 times, 50 times or 70 times.
  • the viscosity of the following system X is determined and set to ⁇ , the system X contains:
  • the balance is water.
  • the balance is water.
  • the necessary stability ingredients mentioned above are preservatives and / or pH adjusters.
  • the skin external preparation composition of the present invention is a functional composition suitable for use on the surface of human skin. Usually such compositions have multiple functional ingredients. Common skin external preparation compositions can be used in the form of liquids, gels, and semi-solids. In the present invention, the preferred external skin preparation composition is used in the form of an aqueous composition or an oil-in-water composition.
  • the skin external preparation composition of the present invention is formed with the above components (A) and (B) as essential components.
  • the skin external agent composition is an aqueous composition, which can be obtained by dissolving or suspending various components in water as a matrix.
  • the composition may be a homogeneous solution system or an aqueous system containing insolubles.
  • the external skin composition is an oil-in-water composition.
  • oil-in-water composition means that the oil phase as the dispersed phase is dispersed in the water phase as the continuous phase by means of dispersion aids to form an emulsified composition.
  • the oil phase as the dispersed phase exists in the form of particles. It should be noted that in some embodiments, the “particles” used in the present invention may exist in the form of beads or approximately beads.
  • the composition is mainly water or an aqueous substance, preferably deionized water or distilled water.
  • the mixing amount of water in the composition is not particularly limited, and it is blended in a sufficient amount to make the whole 100%. However, it is usually 50 to 99% by mass relative to the total mass of the composition, preferably 60 to 98% by mass, and more preferably 70 to 95% by mass.
  • a dispersed phase may also be present in the composition of the present invention, and various oils may be used. It can be selected from substances used in general cosmetics within a range that does not impair stability. Examples of preferred oil components include hydrocarbon oil, silicone oil, ester oil, and other liquid fats and oils.
  • hydrocarbon oil liquid paraffin, squalane, squalene, paraffin, isoparaffin, ozokerite, petrolatum, hydrogenated polydecene and the like can be used.
  • silicone oils include chain organic silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; octamethylcyclotetrasiloxane, decamethyl Cyclic silicones such as cyclopentasiloxane and dodecylcyclohexasiloxane; silicone resins and silicone rubbers with a three-dimensional network structure.
  • liquid fats there are: palm oil, palm kernel oil, linseed oil, camellia oil, macadamia oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil , Sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, triglyceride, glyceryl tricaprylate, glyceryl triisopalmitate, etc.
  • ester oil there are: cetyl caprylate, hexyl laurate, isopropyl myristate, octyl palmitate, isocetyl stearate, isopropyl isostearate, octyl isopalmitate, oleic acid Isodecyl ester, cetyl ethylhexanoate, triglyceride of 2-ethylhexanoic acid, pentaerythritol tetra-2-ethylhexanoate, 2-ethylhexyl succinate, diethyl sebacate and the like.
  • the composition of the present invention is not particularly limited, and the blending amount of the oil phase component is preferably about 20% by mass or less.
  • the oil phase component refers to a component that is mixed as an oil phase and dispersed and emulsified in the water phase when producing an oil-in-water composition; specifically, it contains an oil-soluble preservative and oil-soluble ultraviolet rays in addition to the aforementioned oil component Absorbent, oil-soluble agent, oily antioxidant, oily fragrance, etc. If the oil phase component is more than 20% by mass, it becomes oily and feels sticky, which is not preferable.
  • the external composition for skin of the present invention may contain the usual ingredients used in an external composition for skin, such as cosmetics, in an amount that does not substantially impair the effects of the present invention based on the above-mentioned essential ingredients.
  • the usual components include surfactants, moisturizers, powders, alcohols, water-soluble polymers, oil-soluble polymers, film-forming agents, resins, ultraviolet absorbers, and antiseptics other than the above.
  • Agents antibacterial agents, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skincare ingredients (whitening agents, cell activators, skin roughness improvers, blood circulation enhancers, skin astringents Agents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, etc.
  • the skin external preparation composition obtained by the present invention has a viscosity of 200,000 mPa ⁇ s or 150,000 mPa ⁇ s or 100,000 mPa ⁇ s or 50,000 mPa ⁇ s or 10,000 mPa ⁇ s (30 ° C) or less and 1200 mPa ⁇ s or 1500mPa ⁇ s or 2000mPa ⁇ s or 3000mPa ⁇ s (30 °C) or more, to maintain a good sense of use, will not produce a sticky feeling, and bring consumers a refreshing skin feel. It is further preferred to have a viscosity of 4000-9000 mPa ⁇ s (30 ° C). If the viscosity is too low, it may affect the effect of the product when it is used, and if the viscosity is too high, there will be concerns that it is not conducive to coating and affects the sense of use.
  • the preparation method of the external preparation for skin of the present invention can be obtained by using a general method of mixing the composition.
  • the skin external preparation composition of the present invention is manufactured in the form of an aqueous composition or an oil-in-water composition.
  • the aqueous composition or the oil-in-water composition can be produced by a method for producing a commonly used composition.
  • the water phase component and the oil phase component may be mixed at the same temperature, and the oil phase may be added to the water phase while stirring to disperse and emulsify the mixture, which is suitable for cooling. .
  • the method of forming the oil-in-water composition in the present invention is not particularly limited, and mechanical mixing may be used to provide the necessary mixing shear, or ultrasonic treatment may be used to mix the oil phase component and the water phase component. Get a stable emulsion.
  • the device for preparing the external preparation for skin of the present invention is not particularly limited as long as it can satisfy the above requirements.
  • the external preparation for skin of the present invention may be in the form of a solution, an emulsion, or the like, and may be in a translucent or opaque form.
  • Grain ferment
  • PEMULEN TM (purchased from Lubrizol Corporation)
  • Aristoflex TM (purchased from Clariant)
  • Test temperature 30 °C.
  • a composition was formed according to the following composition, and its viscosity was measured. For data, see Table 1.
  • composition was formed according to the following composition, and its viscosity was measured. For data, see Table 2.
  • composition was formed according to the following composition, and its viscosity was measured. For data, see Table 3.
  • composition was formed according to the following composition, and its viscosity was measured. See Table 4 for data.
  • composition was formed according to the following composition, and its viscosity was measured. For data, see Table 5.
  • composition was formed according to the following composition, and its viscosity was measured. For data, see Table 6.
  • Example 1-1 Comparing Example 1-1 and Comparative Example 1-1, the viscosity of Example 1-1 is about 4.06 times the viscosity of Comparative Example 1-1, comparing Example 1-2 with Comparative Example 1-2, Example 1 The viscosity of -2 is about 6.57 times that of Comparative Example 1-2.
  • composition was formed according to the following composition, and its viscosity was measured. For data, see Table 7 and FIG. 1, where FIG. 1 is based on the data in Table 7.
  • the amount of PEMULEN in the present invention is preferably 0.06-0.2% by mass.
  • composition of the present invention can be used as a thickening system in aqueous cosmetic compositions.

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Abstract

一种皮肤外用剂组合物，所述组合物包括：(A)谷物经过发酵而得到的谷物发酵物有效成分，(B)增稠剂，所述(B)增稠剂选自聚丙烯酸及其衍生物增稠剂或者多糖类增稠剂，其中，所述聚丙烯酸及其衍生物增稠剂的分子侧链结构中包括如下式(1)结构： -C(O)-O-L-(R 1O) n-R 2………(1) 其中，R 1为碳原子数为2～6的直链或支化的亚烷基，R 2为碳原子数为1～50的直链或支化的烷基，n表示0～100的整数，L为单键或者二价连接基团。所述组合物具有明显的协同增粘效应，可以在减少增稠剂的使用的情况下，通过谷物发酵物的使用而达到所需的粘度。

Description

皮肤外用剂组合物 技术领域
本发明属于护肤品技术领域，涉及一种具有协同增粘效应的组合物体系，更具体而言，涉及一种皮肤外用剂组合物。
背景技术
皮肤外用剂组合物被广泛地应用于化妆品产品中，这样的组合物通常包括了水性体系和油性体系。
水性体系，尤其是水包油组合物被广泛地应用于化妆品产品中，在起到特定功能的同时，也能够给人带来清爽的感觉。水包油组合物中，水或水性物质作为连续相，油性成分作为分散相，形成液态或半固态等体系。
通常的水包油组合物中，含有各种活性成分，以实现保湿、补充营养、防护或者修复等效果。同时，为了将上述各种活性成分长久稳定地保存于该组合物中，可以加入各种添加剂，例如各种乳化剂、稳定剂、增稠剂、防腐剂等成分。
一方面，为了使化妆品能够实现各种所期望的功能而存在尝试将各种活性成分进行复合使用的需要。这样的情况下，对于包含多种活性成分的水包油组合物，其体系的稳定性是重要的。例如，由于多种活性成分的同时存在，容易在生产、运输、保存或者使用过程中出现体系内部的相分离等状况，导致化妆品外部观感的恶化。或者例如，多种活性成分的存在，使得形成稳定的油相液滴以期望的形式悬浮或分散于水性连续相中时，存在操作困难。另一方面，更多活性成分的引入，往往导致更多种或更多量的添加剂的使用。因此，产品的安全性也是关注的重点。例如，通常情况下，为了使用的安全性、生产的环保性以及更好的人体亲和性，人们更倾向于更多地使用源自于天然物质的化妆品成分，例如以往，在关于化妆料的乳化方面，主要使用聚氧乙烯烷基醚、脱水山梨糖醇脂肪酸部分酯等非离子型表面活性剂。但是，那些表面活性剂不可避免地对皮肤有程度不同的刺激作用，为此尽可能减少表面活性剂的用量，而且有时尝试不使用这些表面活性剂进行乳化，但在乳 化物的均匀性、稳定性等方面容易产生问题，未必能够得到满足要求的乳化物。
进一步，讨论了使用源自天然物质而得到的乳化剂，目前，使用谷物发酵物作为乳化剂或者稳定性成分也已经是已知的，例如：
参考文献1公开了一种使用大米为原料，经发酵得到的产品LAFR-ɑ，并研究了LAFR-ɑ的表面张力和界面张力，并研究了LAFR-ɑ表现出的乳化行为以及包含LAFR-ɑ的悬浮体系的抗氧化性。
参考文献2公开了一种含米糠发酵物的化妆水，其含有以质量百分比计的0.01-10％的米糠发酵物，其化妆水具有1000mPa·s以下的低粘度。
参考文献3公开了一种乳化助剂，它主要是由米经乳酸菌发酵得到的乳酸菌发酵米构成的。米经乳酸菌发酵得到的发酵米具有良好的乳化能力和乳化稳定化作用乃至保护胶体样作用，同时，由于来自于米，故为低毒性，且对皮肤的刺激性小，对生物体的安全性高，可以作为化妆料用乳化剂或乳化稳定剂等基础原料，此外还意外地发现，该发酵米表现出显著的美白·美肤作用和发质改善作用，也可以作为用于产生美容效果的配合剂。
对于谷物发酵产物的利用也见于参考文献4，涉及一种谷物和人参茎叶发酵物及其在皮肤清洁产品中的应用。该方法首先对含有谷物或人参茎叶的培养基加热灭菌，后接入微生物，发酵，灭菌，得包含菌体、发酵滤液及固体颗粒的发酵产物。所述发酵产物用于清洁产品中。其具有良好的去除皮肤表面油脂、平滑肌肤、抗炎症、痤疮等作用。并且具有营养肌肤，温和去除皮肤角质，低刺激性，安全温和的特点。
可见现有技术对于使用源自于天然成分的大米发酵物等作为乳化剂或其他活性成分而替代现有人工合成乳化剂或功能性成分已经有了一定的探索。
此外，通常为了使水包油组合物能够获得稳定的形态，例如，能够使得油性液滴在更长的时间内稳定地悬浮于体系中，需要赋予水包油组合物体系一定的粘度或稠度，因此，通常情况下，需要加入一定量的增稠剂以获得稳定性效果。通常这样的增稠剂为人工合成的高分子或者化学改性的天然高分子。
参考文献5公开了一种水包油型乳化皮肤外用制剂。该乳液制剂采用由羟基化磷脂和谷物的乳酸菌发酵物质以及烷基改性的丙烯酸基聚合物和/或其盐作为必要成分而得到。其中谷物发酵产物作为乳化剂，烷基改性的丙烯酸基聚合物和/或其盐作为增稠剂，同时以羟基化磷脂作为稳定剂。进一步，参考文献5验证了上述三种成分的配合使用是得到稳定的乳液体系(即不发生水相分离和油相分离现象)的必要条件，对其中任意成分替换为其它种类物质均无法获得所期望的效果。
可见，本领域中对于作为乳化剂的谷物发酵产物的应用已经取得了一定的进展，但由于其本身的天然物质的属性，因此，也存在这进一步拓展其使用范围的需求。同时，对于将谷物发酵产物与其他化妆品用添加剂的协同使用的研究还有进一步探讨的余地。
参考文献：
参考文献1：IFSCC Paris 2014 poster communications,1910-1917
参考文献2：CN103565724A
参考文献3：CN 1256938C
参考文献4：CN106176357A
参考文献5：JP特许第5010372号
发明内容
发明要解决的问题
本发明主要涉及谷物发酵产物与现有的皮肤外用剂组合物中的添加剂的协同使用。特别的，本发明提供了一种具有协同增粘效应的皮肤外用剂组合物，所述组合物中将通常仅作为乳化剂而使用的谷物发酵产物与聚丙烯酸及其衍生物增稠剂或多糖类增稠剂同时使用时，意外地观察到，相对于单独使用增稠剂的情况，二者的同时使用能够显著增加体系的粘度，产生协同增粘效应，并且能够得到稳定的体系。
其中，所述聚丙烯酸及其衍生物增稠剂的分子侧链结构中含有如下式(1)结构：
-C(O)-O-L-(R 1O) n-R 2   ………….(1)
其中，R 1为碳原子数为2-6的亚烷基，R 2为碳原子数为1-50的烷基，n表示0-100的整数，L为单键或者二价连接基团。
用于解决问题的方案
本发明通过以下技术手段以解决上述技术问题：
[1].本发明首先提供了一种皮肤外用剂组合物，其中，所述组合物包括：
(A)谷物经过发酵而得到的谷物发酵物有效成分，
(B)增稠剂，
所述(B)增稠剂选自聚丙烯酸及其衍生物增稠剂或者多糖类增稠剂，
其中，所述聚丙烯酸及其衍生物增稠剂的分子侧链结构中含有如下式(1)结构：
-C(O)-O-L-(R 1O) n-R 2   ………(1)
其中，R 1为碳原子数为2-6的直链或支化的亚烷基，R 2为碳原子数为1-50的直链或支化的的烷基，n表示0-100的整数，L表示单键或者二价连接基团。
[2].根据[1]所述的组合物，其中，所述谷物选自大米、糯米、小米、黑米、玉米、高粱中的一种或多种。
[3].根据[1]或[2]所述的组合物，其中，所述发酵是在乳酸菌的存在下进行的。
[4].根据[1]-[3]任一项所述的组合物，其中，所述组合物具有1200mPa·s以上的粘度。
[5].根据[1]-[4]任一项所述的组合物，其中，所述聚丙烯酸及其衍生物增稠剂中，R 1的碳原子数为2-4，R 2的碳原子数为3-50，n为1-100。
[6].根据[1]-[4]任一项所述的组合物，其中，所述聚丙烯酸及其衍生物增稠剂中，n为0，且所述组合物中不包含磷酯类物质。
[7].根据[1]-[6]任一项所述的组合物，其中，所述多糖类增稠剂选自纤维素类增稠剂。
[8].进一步，本发明还提供了一种化妆品，其中，所述化妆品包括根据以上任一项所述的皮肤外用剂组合物。
发明的效果
通过采用以上的技术手段，本发明所能够获得的技术效果如下：
(1)将谷物发酵物，尤其是将大米发酵物与增稠剂协同使用，能够相对于单独使用增稠剂的情况，使得体系粘度显著地升高，拓宽了谷物发酵物的使用场景；
(2)协同增粘作用的出现，使得在实现所需体系粘度时能够更少地使用源自于合成或化学改性得到的增稠剂，并允许源自于天然物质的发酵成分更多使用。
(3)通过协同增粘效果，可以在更少使用其他稳定性添加剂的情况下实现体系的稳定效果。
(4)通过谷物发酵物的应用，使得包含本发明的皮肤外用剂组合物的化妆品在使用时，能够给使用者带来清爽、不黏腻、柔滑的使用感。
附图说明
图1：不同含量的PEMULEN与谷物发酵物协同使用时的粘度变化
具体实施方式
以下将对本发明的具体实施方式进行描述，如无特殊声明，本发明所使用的单位均为国际标准单位，并且本发明中出现的数值，数值范围，均应当理解为包含了工业生产中所不可避免的系统性误差。
<(A)谷物经过发酵而得到的谷物发酵物有效成分>
通常在现有技术中认为谷物发酵后得到的发酵物有效成分可以作为乳化剂或者营养成分来使用。但本发明意外地发现了将这种谷物发酵物与本发明所限定的增稠剂共同使用时，其能够与本发明所限定的增稠剂产生协同增粘作用。
本发明中的谷物，可以为选自大米、糯米、小米、黑米、玉米、高粱中的一种或多种。在本发明的一些优选的实施方案中，优选为大米或糯米，进一步优选为大米。
另外，本发明中的谷物可以是经过或未经过加工处理的谷物，例如，可以是糙米、精米、加工米等任一种或多种，没有特别的限制，在本发明一些优选的实施方案中，出于有利于发酵或者得到的发酵产物纯度的考虑，一般 使用经过加工处理的谷物，例如精米或加工米。
本发明中对于发酵的方法没有特别的限定，可以使用微生物对于谷物进行发酵，优选使用乳酸菌进行发酵。作为这些用于谷物发酵时可以使用的乳酸菌，例如有胚芽乳杆菌(Lactobacillus plantarum)、短乳杆菌(L.brevis)、干酪乳杆菌(L.casei)、纤维二糖乳杆菌(L.cellobiosus)、牛痘乳杆菌(L.vaccinostercus)、粪链球菌(Streptococcus faecalis)、凝固芽孢杆菌(Bacillus coagulans)等。在本发明一些优选的实施方案中，从所得到的乳酸菌发酵米的乳化能力等方面考虑，优选使用胚芽乳杆菌(Lactobacillusplantarum)。
在本发明的另一些优选的实施方案中，谷物在发酵前还进行了预处理，所述的预处理包括筛选或清洗等手段。
对于发酵方法，例如可按以下步骤进行：
首先，对谷物进行加工处理，并施行清洗等适宜预处理手段，以除去可能存在的杂质成分或者有碍乳酸菌发酵的杂菌，获得成分较纯的谷物，例如干净的精加工米。
接着，将上述精加工米放置于发酵容器中，所述发酵容器具有密闭性，可以使得后续的发酵过程可以在厌氧的条件下进行。进一步，向发酵容器中导入水和乳酸菌以及发酵辅助成分。所述水优选为蒸馏水或纯净水，其用量没有特别的限制，一般可以为上述经过加工处理和预处理后的谷物(精加工米)的质量的10倍以下。所述的发酵辅助成分可以选择各种糖类物质，可以使用葡萄糖、果糖、半乳糖、蔗糖等，其中最优选使用果糖。对于各种物质的添加方式，没有特别的限定，可以遵循本领域通常的添加方式。
接着，封闭容器，使得发酵能够在厌氧的条件下进行，发酵的温度和时间没有特别的限定，可以遵循通常的发酵方法。例如，可以在室温条件下进行发酵，也可以在加热的条件下进行发酵，发酵时间可以为数天或数周。
由上述发酵工序得到的含有乳酸菌发酵液体，可以直接作为有效成分而使用。在本发明一些优选的实施方案中，还可以对得到的发酵液体进行纯化或浓缩处理。对于纯化的手段没有特别限制，可使用常压或在减压的条件下进行过滤。另外，对于浓缩的方法，可以使用蒸馏等方式进行。在本发明优选的实施方案中，可以在纯化后进行浓缩的步骤。
<(B)增稠剂>
本发明中使用(B)增稠剂能够赋予皮肤外用剂组合物一定的粘度，在一些优选的实施方案中，赋予水性组合物一定的粘度。
本发明所述(B)增稠剂选自聚丙烯酸及其衍生物增稠剂或者多糖类增稠剂。
对于本发明的聚丙烯酸及其衍生物增稠剂，可以是通过对丙烯酸与丙烯酸酯进行共聚得到的聚合物或其衍生物。
其中，所述聚丙烯酸及其衍生物增稠剂的分子侧链结构中含有如下式(1)结构：
-C(O)-O-L-(R 1O) n-R 2   ………(1)
其中，R 1为碳原子数为2-6的直链或支化的亚烷基，优选为碳原子数为2-4的直链或支化的亚烷基，R 2为碳原子数为1-50的直链或支化的烷基，优选为碳原子数为6-30的直链或支化的烷基，进一步优选为10-25的直链或支链的烷基，n表示0-100的整数，优选为1-100的整数，进一步优选为6-50的整数，更进一步优选为10-30的整数，L表示单键或者二价连接基团，优选为亚烷基基团。
在本发明一些实施方案中，所述聚丙烯酸及其衍生物增稠剂的侧链中n＝0，即侧链中不存在聚氧亚烷基的结构。在这种情况下，本发明的增稠剂可以视为丙烯酸与丙烯酸烷基酯共聚得到。例如，一些实施方案中，聚丙烯酸及其衍生物增稠剂可以具有如下分子结构：
Figure PCTCN2019105171-appb-000001
其中R和R’可以为碳原子数为10-30的烷基。具有这样结构的增稠剂可以通过市售而得到，例如
Figure PCTCN2019105171-appb-000002
TR-1，
Figure PCTCN2019105171-appb-000003
TR-2。
在本发明的另一些实施方案中，所述聚丙烯酸及其衍生物增稠剂的侧链中n为1-30，即在所述侧链中存在聚氧亚烷基结构，可以列举的，聚氧亚烷 基可以为聚氧乙烯或者聚氧丙烯结构。在一些情况下，除了具有这样的聚氧烷基结构的侧链以外，在另外一些侧链中，可以具有酯的结构，例如可以为丙烯酸与碳原子数为1-6的醇形成的酯，典型的，具有如下结构：
Figure PCTCN2019105171-appb-000004
其中，R可以为H或者碳原子数为1-4的烷基。同样，具有这样结构的增稠剂可以通过市售而得到，例如DOW化学名下的ACULYN TM系列增稠剂等。
另外，在除了上述所说明的侧链的结构情况以外，在本发明一些实施方案中使用的聚丙烯酸及其衍生物增稠剂，其侧链还可以具有酰胺以及磺酸酯(盐)基团。可以列举的结构为：
Figure PCTCN2019105171-appb-000005
具有这样结构的增稠剂可以通过市售而得到，例如
Figure PCTCN2019105171-appb-000006
HMB系列增稠剂等。
对于上述增稠剂，从提高增稠效果的观点来看，其分子内部可以具有一定交联结构，例如通过氢键而形成的物理交联或者通过离子键而形成的交联。
对于本发明的多糖类增稠剂，可以使用淀粉、纤维素类增稠剂，优选的，本发明中使用纤维素类增稠剂。对于本发明的多糖类增稠剂，在一些优选的实施方案中，其分子中使用烷基和/或聚烷氧基链段进行醚化改性。例如，本发明中可选的是通过对纤维素进行改性而得到的改性纤维素，所述改性为在对纤维的一个单元环上的羟基进行烷基化(醚化)而得到。即，所述改性纤维素具有如下结构：
Figure PCTCN2019105171-appb-000007
其中：R可以为H、碳原子数为1-4的烷基、-(R aO) m-R b或-R cOR d，其中R a表示碳原子数为1-4的亚烷基、R b表示H或碳原子数为1-4的烷基，R c表示碳原子数为1-4的亚烷基，并且任选的被羟基取代，R d为碳原子数为10-30的烷基，m为1-100的整数。
可以列举的具有上述结构的增稠剂可以为DAIDO名下的
Figure PCTCN2019105171-appb-000008
产品等。
另外，对于这些增稠剂使用时的形态没有特别的限定，例如可以以水溶液或其他溶液的形式使用。优选的，在本发明的一些实施方案中，可以将上述增稠剂以乳液，尤其是水包油的乳液形式来使用。同时，这样的溶液中也可以含有其他辅助性稳定成分，例如作为稳定性成分的酸、碱或盐等物质。
对于增稠剂的用量，本发明发现，即使在没有其他增粘性成分的存在下，当增稠剂与谷物发酵物协同使用时，相对于仅使用或存在增稠剂的体系，其粘度也会大幅增长。本发明中，所述增稠剂的用量为能够实现由于上述协同作用而获得的粘度为仅使用或存在增稠剂的体系粘度的1.2倍以上的量，优选为2倍、4倍、4.1倍、4.5倍、6倍或10倍以上，更有选为20倍以上、30倍以上、50倍以上或70倍以上。
需要说明的是，本发明上述倍数通过如下方法确定：
测定如下体系X的粘度，设为ɑ，所述体系X含有：
(B)增稠剂；
必要的稳定性成分；
余量为水。
测定如下体系Y的粘度，设为β，所述体系Y含有：
(A)谷物经过发酵而得到的谷物发酵物有效成分，
(B)增稠剂，含量与体系X中含量相同，
必要的稳定性成分，
余量为水。
上述必要的稳定性成分为防腐剂和/或pH值调节剂。
以β/ɑ表示上述倍数。
需要说明的是，在上述粘度测试的条件下，如果以本发明所定义的增稠剂的某一个含量值(质量％，以组合物总重量为基准)作为定值，以粘度和谷物发酵产物含量(质量％，以组合物总重量为基准)为两个变量进行考察，如果在上述增稠剂含量定值的情况下，能够出现由于上述协同增粘作用导致的粘度为单独使用增稠剂的粘度的1.2倍以上的情况，则增稠剂的该含量值就在本发明保护的范围以内。
<皮肤外用剂组合物>
本发明的皮肤外用剂组合物，为适用于人体皮肤表面使用的功能性组合物。通常这样的组合物具有多种功能性成分。常用的皮肤外用剂组合物可以以液体、凝胶、半固体的形式使用。本发明中，优选的皮肤外用剂组合物以水性组合物或者水包油组合物等形式使用。
本发明的皮肤外用剂组合物，以上述组分(A)和(B)作为必要组分而形成。
在本发明的一些优选的实施方案中，所述皮肤外用剂组合物为水性组合物，可以使多种成分溶解或者悬浮于作为基体的水中而得到。在这样的体系中，组合物可以是均相溶液体系，也可以是含有不溶物的水性体系。
在另外一些优选的实施方案中，所述皮肤外用剂组合物为水包油型组合物。所述“水包油型组合物”即通过分散辅助手段，将作为分散相的油相分散于作为连续相的水相中，形成乳化组合物。其中作为分散相的油相以颗粒的形式存在。需要说明的是本发明所使用的“颗粒”在一些实施方案中，可以以珠状或近似珠状的形式存在。
本发明的组合物中，其组成中主要是水或水性物质，优选为去离子水或蒸馏水。组合物中水的混合量没有特别限制，以使整体为100％的充分量进行配合。但通常是相对于组合物的总质量，为50～99质量％，优选60～98质量％，更优选70～95质量％。
本发明组合物中还可以存在分散相，可以使用各种油分。可以从通常化妆品中使用的物质中在不有损稳定性的范围内进行选择。作为优选的油分，可列举出：烃油、硅油、酯油、其它液体油脂等。
作为烃油，可以使用液体石蜡、角鲨烷、角鲨烯、石蜡、异链烷烃、地蜡、凡士林、氢化聚癸烯等。
作为硅油，可例示出例如：二甲基聚硅氧烷、甲基苯基聚硅氧烷、甲基氢聚硅氧烷等链状有机硅；八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷等环状有机硅；形成有三维网络结构的有机硅树脂、硅橡胶等。
作为液体油脂，有：棕榈油、棕榈仁油、亚麻仁油、山茶油、澳洲坚果油、玉米油、貂油、橄榄油、鳄梨油、山茶花油、蓖麻油、红花油、霍霍巴油、向日葵油、杏仁油、菜籽油、芝麻油、大豆油、花生油、二缩三甘油、三辛酸甘油酯、三异棕榈酸甘油酯等。
作为酯油，有：辛酸鲸蜡酯、月桂酸己酯、肉豆蔻酸异丙酯、棕榈酸辛酯、硬脂酸异鲸蜡酯、异硬脂酸异丙酯、异棕榈酸辛酯、油酸异癸酯、乙基己酸鲸蜡基、三2-乙基己酸甘油酯、四2-乙基己酸季戊四醇酯、琥珀酸2-乙基己酯、癸二酸二乙酯等。
对于本发明的组合物，没有特别的限制，优选将油相成分的配合量设为约20质量％以下。此处，油相成分是指在制造水包油型组合物时作为油相混合而在水相中分散乳化的成分；具体而言，除了前述油分之外，包含油溶性防腐剂、油溶性紫外线吸收剂、油溶性药剂、油性抗氧化剂、油性香料等。如果油相成分多于20质量％，则在使用感方面变油、也产生黏腻而不优选。
另外，本发明的皮肤外用组合物可以在上述的必需成分基础上，以本质上不有损本发明的效果的量的范围内配合化妆品等皮肤外用组合物中应用的通常的成分。作为该通常的成分，可列示出例如：除了上述以外的表面活性剂、保湿剂、粉体、醇类、水溶性高分子、油溶性高分子、膜形成剂、树脂、紫外线吸收剂、防腐剂、抗菌剂、香料、盐类、抗氧化剂、pH调节剂、螯合剂、清凉剂、抗炎剂、美肌用成分(美白剂、细胞活化剂、皮肤粗糙改善剂、血液循环促进剂、皮肤收敛剂、抑皮脂分泌剂(antiseborrheic)等)、维生素类、氨基酸类、核酸、荷尔蒙、包接化合物等。
出于生产和使用上的考虑，本发明所得到的皮肤外用剂组合物具有的粘度为200000mPa·s或150000mPa·s或100000mPa·s或50000mPa·s或10000mPa·s(30℃)以下且1200mPa·s或1500mPa·s或2000mPa·s或3000mPa·s(30℃)以上，以保持良好的使用感，不会产生黏腻的感觉，给消费者带来清爽的肤感。进一步优选具有4000-9000mPa·s(30℃)的粘度。粘度过低，则可能影响产品使用时的效果，而粘度过高，则会有不利于涂覆、影响使用感的担忧。
＜皮肤外用剂组合物的制造方法＞
本发明的皮肤外用剂组合物的制备方法可以使用通常的组合物的混合方法而得到。在一些本发明优选的实施方案中，本发明的皮肤外用剂组合物以水性组合物或者水包油型组合物形式进行制造。
水性组合物或者水包油型组合物能够通过通常使用的组合物的制造方法而制造。例如，在水包油型组合物的制备方法中，可以通过将水相成分和油相成分分别在相同温度下混合，边搅拌边向水相中添加油相使之分散乳化，适宜冷却而制造。
进一步，本发明中的水包油型组合物形成方法没有特殊的限制，可以使用机械搅拌的方式提供必要的混合剪切力，或者使用超声波的处理方式将油相成分与水相成分进行混合而得到稳定的乳液。
同样，对于制备本发明的皮肤外用剂组合物的装置也没有特别的限定，只要能够满足以上需要即可。
对于本发明的皮肤外用剂组合物可以是溶液状、乳液状等，并且可以为半透明或不透明的形态。
实施例：
以下将对本发明具体的实施方案进行说明，需要强调的是，以下具体实施方案仅是对本发明优选的实施方式的具体列举，并不构成对本发明所有可行的实施方案的限制。
<主要原料>
谷物发酵物：
RICE FERMENT-LP(购自TECHNOLONG公司)
增稠剂：
PEMULEN TM(购自路博润公司)
ACULYN TM(购自陶氏化学公司)
Aristoflex TM(购自科莱恩公司)
SANGELOSE(购自大同化成工业株式会社)
Resinol(购自日光化学株式会社)
<测试仪器和方法>
粘度测试：
采用BROOKFIELD LVDV-II+P或HADV-II+P粘度计进行测试；
测试温度：30℃。
实施例1-1至1-6和比较例1-1至1-3：
按照以下组成形成组合物，并测定其粘度，数据参见表1。
实施例2-1至2-6和比较例2-1至2-3：
按照以下组成形成组合物，并测定其粘度，数据参见表2。
实施例3-1至3-6和比较例3-1至3-3：
按照以下组成形成组合物，并测定其粘度，数据参见表3。
实施例4-1至4-6和比较例4-1至4-3：
按照以下组成形成组合物，并测定其粘度，数据参见表4。
实施例5-1至5-6和比较例5-1至5-3：
按照以下组成形成组合物，并测定其粘度，数据参见表5。
从上述实施例与比较例的比较情况看，当本发明的组合物中同时使用了谷物发酵物以及增稠剂时，相对于仅使用增稠剂的情况，粘度都存在明显的 增长，由于通常并不会认为谷物发酵物的使用会对组合物粘度有明显影响，因此，可以确认谷物发酵物乳化剂的使用与增粘剂产生了协同效应。
参考例对比1：
按照以下组成形成组合物，并测定其粘度，数据参见表6。
其中，参考例1和2中使用了增稠剂PEMULEN，同时，还使用了具有稳定性作用的磷脂类表面活性剂(纯化的氢化大豆磷脂)。并在参考例3和4中额外加入了谷物发酵物，进行如下比较：
将实施例1-1与比较例1-1比较，实施例1-1的粘度为比较例1-1粘度的约4.06倍，将实施例1-2与比较例1-2比较，实施例1-2的粘度为比较例1-2的粘度的约6.57倍。
将参考例1与参考例3比较，参考例3的粘度为参考例1粘度的约4.03倍，将参考例2与参考例4比较，参考例4的粘度为参考例2的3.03倍。
可见，在磷脂类物质的存在下，对于本发明所指出的谷物发酵物与增稠剂的协同增粘效果产生抑制作用。
推测可能的原因是由于磷脂类表面活性剂的存在对谷物发酵物产生了影响，从而对本发明的粘度增加的协同效应有抑制作用。因此，在本发明优选的实施方案中，尤其是在上述式(1)所表示的结构中，当n＝0时，组合物中不存在或不使用磷脂类表面活性剂或磷脂类物质。
参考例对比2：
按照以下组成形成组合物，并测定其粘度，数据参见表7和图1，其中图1基于表7中数据。
从图1数据可以看出，当PEMULEN的用量为0.05时，曲线较为平缓，这可以理解为由于PEMULEN的用量过少而导致了与谷物发酵物产生的协同增粘效果不完全充分。当PEMULEN的用量为0.2时，曲线较为陡峭，这可以理解为由于PEMULEN的用量较多而导致了与谷物发酵物产生的协同增粘效果急剧增加。因此，从协同效果的明显程度和粘度增加的可控性角度考虑，本发明中PEMULEN的用量优选为0.06-0.2质量％。
Figure PCTCN2019105171-appb-000009
Figure PCTCN2019105171-appb-000010
Figure PCTCN2019105171-appb-000011
Figure PCTCN2019105171-appb-000012
Figure PCTCN2019105171-appb-000013
Figure PCTCN2019105171-appb-000014
Figure PCTCN2019105171-appb-000015
产业上的可利用性
本发明的组合物可以作为一种增粘体系而用于化妆品用水性组合物中。

Claims (8)

  1. 一种皮肤外用剂组合物，其特征在于，所述组合物包括：
    (A)谷物经过发酵而得到的谷物发酵物有效成分，
    (B)增稠剂，
    所述(B)增稠剂选自聚丙烯酸及其衍生物增稠剂或者多糖类增稠剂，
    其中，所述聚丙烯酸及其衍生物增稠剂的分子侧链结构中包括如下式(1)结构：
    -C(O)-O-L-(R 1O) n-R 2………(1)
    其中，R 1为碳原子数为2-6的直链或支化的亚烷基，R 2为碳原子数为1-50的直链或支化的烷基，n表示0-100的整数，L为单键或者二价连接基团。
  2. 根据权利要求1所述的组合物，其特征在于，所述谷物选自大米、糯米、小米、黑米、玉米、高粱中的一种或多种。
  3. 根据权利要求1或2所述的组合物，其特征在于，所述发酵是在乳酸菌的存在下进行的。
  4. 根据权利要求1-3任一项的组合物，其特征在于，所述组合物具有1200mPa.s以上的粘度。
  5. 根据权利要求1-4任一项所述的组合物，其特征在于，所述聚丙烯酸及其衍生物增稠剂中，R 1的碳原子数为2-4，R 2的碳原子数为3-50，n为1-100。
  6. 根据权利要求1-4任一项所述的组合物，其特征在于，所述聚丙烯酸及其衍生物增稠剂中，n为0，且所述组合物中不包含磷酯类物质。
  7. 根据权利要求1-5任一项所述的组合物，其特征在于，所述多糖类增稠剂选自纤维素类增稠剂。
  8. 一种化妆品，其特征在于，所述化妆品包括根据权利要求1-7任一项所述的皮肤外用剂组合物。
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