CN1326511C - Foam cosmetic composition for cleaning or dress taking off - Google Patents
Foam cosmetic composition for cleaning or dress taking off Download PDFInfo
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- CN1326511C CN1326511C CNB031286119A CN03128611A CN1326511C CN 1326511 C CN1326511 C CN 1326511C CN B031286119 A CNB031286119 A CN B031286119A CN 03128611 A CN03128611 A CN 03128611A CN 1326511 C CN1326511 C CN 1326511C
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/14—Preparations for removing make-up
-
- 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
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- 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
- A61K2800/596—Mixtures of surface active compounds
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Abstract
本发明涉及一种局部应用的泡沫组合物，包括特定的由至少一种部分或全部中和的脂肪酸、非甜菜碱两性辅助表面活性剂和磺基琥珀酸型阴离子辅助表面活性剂组成的表面活性剂系统，还涉及该组合物在化妆或皮肤病领域方面的应用，特别是作为人角质层物质，尤其是皮肤的清洗和/或卸妆产品。本发明的通常制成乳膏剂，并包装于软管中的泡沫组合物显示出良好的延展性能，可很快形成浓稠的乳状泡沫，并能很快地清洗去除掉。在不同温度变化及传送条件下其具有良好的稳定性。The present invention relates to a foam composition for topical application comprising a specific surfactant consisting of at least one partially or fully neutralized fatty acid, a non-betaine amphoteric cosurfactant and an anionic cosurfactant of the sulfosuccinate type It also relates to the application of the composition in the field of cosmetics or dermatology, especially as a cleansing and/or cleansing product for human stratum corneum substances, especially skin. The foam composition of the present invention, which is usually formulated as a cream and packaged in a tube, exhibits good spreading properties, can quickly form a thick milky foam, and can be washed off quickly. It has good stability under different temperature changes and transmission conditions.
Description
Technical field
The present invention relates to a kind of foam compositions of topical application, comprise the specific surfactant system of forming by at least a part or all of neutral fatty acid, non-beet alkali ampholytic cosurfactant and sulfosuccinic acid type anion cosurfactant, also relate to the application of said composition aspect cosmetic or dermatosis field, particularly as the cleaning of people's horny layer material, especially skin and/or the product of removing ornaments and formal dress.
It is extremely important for facial-care to clean skin.Because residual fat such as too much sebum, residual daily cosmetics and unload particularly waterproof product of cosmetics can accumulate in and block skin pore in the wrinkle of skin, cause that skin produces speckled appearance.
Background technology
The skin clean product of several main types is known: the foam lotion and the gel of aqueous, anhydrous oil capable of washing and gel and whipped cream.
Flushable anhydrous oil and gel have cleaning active because of wherein containing oil.These oil can dissolve remaining oils and fats and disperse the cosmetic pigment.These products effectively and easily are accepted.Their shortcoming is that weight is bigger, does not form foam, and does not in use have refrigerant impression, and these angles from cosmetics see it is shortcoming.
And foaming-detergent aqueous emulsion and gel have cleaning action because of the surfactant that it contains can suspend remaining oils and fats and cosmetic pigment.They are effectively and because of it can spume and be easy to remove by glad to use.Yet the lotion flowability is strong excessively, and is meticulousr during use, and when keeping good bubbling character, difficultly forms thickening and forms gel.
Obtain having the dense condensed compositions of good frothing capacity, require to prepare whipped cream.
Here, the implication of " whipped cream " is viscosity, opaque compositions, often be packaged in the flexible pipe, usually by an aqueous medium, and other additive such as polymer, polyhydric alcohol and filler, wherein aqueous medium comprises the mixture of surfactant such as soap (soap class) or anion, nonionic or amphoteric synthetic surfactant.
These Emulsions that are used in particular for cleaning skin mix the generation foam with water.They can use by dual mode:
The first is applied to Emulsion waterborne, is applied on face or the health, then directly rubs at face or whole body in the presence of water, produces foam;
It two is earlier to form foam in the centre of the palm, then is applied to face or whole body again.
The formed foam of this dual mode all will clean removal.
In commercial now whipped cream product, the frothing capacity of some products is also unsatisfactory, especially in quick foaming, and foamability and foamy emulsifiability (density) aspect.
Some other whipped cream is stable inadequately, is subjected to the influence of variation of variations in temperature and transportation and storage condition bigger: these variations can cause that preparation is very fast macroscopic layering to occur, and it is biphase to cause system to be divided at least.
Yet it is very necessary preserving several months for the clean type whipped cream under different temperatures and different traffic condition.Really, in the shelf-life of product, product can be placed under the temperature that changes because of different weather conditions, storage or traffic condition.Product also can be in transit by jolting.The problem that needs these whipped creams to have the ability in hot country, to use equally and do not have transportation and store.
Also need these cleaning foam Emulsions in above unlisted under the unfavorable conditions under different temperatures and the traffic condition, can storing.
Summary of the invention
The discovery that the applicant is surprised, finish above-described target, it is possible obtaining a kind of foam compositions with Emulsion form of good stability, said composition is by using a specific surfactant system to realize its performance, and this system is made up of at least a part or all of neutral fatty acid, non-beet alkali ampholytic cosurfactant and sulfosuccinic acid type anion cosurfactant.
Therefore can obtain a kind of opaque compositions, good cosmetic properties (soft, sliding soft) is arranged, the coating performance of good hose packing is arranged, it is very fast to produce foam, and foam is dense thick like cream, can rinse out very soon.Resulting composition can be preserved the long period under different temperatures and traffic condition.
Therefore, the application's purpose is the foam compositions that obtains topical application, and said composition contains at least a surfactant system in the acceptable aqueous medium of making up, and this system comprises:
(a) partly or entirely by the mixture of neutral at least a fatty acid of organic or inorganic alkali or fatty acid;
(b) at least a non-beet alkali ampholytic surface active agent;
(c) anion surfactant of at least a sulfosuccinate type, the weight ratio of the surfactant of the amphoteric surfactant of non-betanin and sulfosuccinate type is less than 2.
Another object of the present invention is the cosmetic use of above-described compositions, is cleaning and/or the makeup removing product that is used for the horny layer material.
Another object of the present invention is to clean the cosmetic method of people's horny layer material residual dirt, it is characterized in that using compositions of the present invention on the horny layer material, and in the presence of water, by rubbing the formation foam, remaining dirt is removed in the flushing of reuse water.
The specific embodiment of the present invention
In description, " people's horny layer material " is interpreted as skin (as health or comprise eyelid and the face of scalp) and body surface growth-gen such as hair, eyelashes and eyebrow.
Fatty acid of the present invention normally comprises saturated or undersaturated, contains the fatty acid that 6-30 is preferably the straight or branched alkyl of 12-22 carbon atom.
The fatty acid of being mentioned is lauric acid, myristic acid, Palmic acid, stearic acid and their mixture particularly, especially preferably lauric acid, myristic acid, Palmic acid and stearic mixture.
The alkali of these carboxylic acids of being used for partly or entirely neutralizing can be, for example, inorganic base is as being selected from the hydroxide (magnesium hydroxide) or the ammonia of alkali-metal hydroxide (sodium hydroxide and potassium hydroxide), alkaline-earth metal, or organic base such as triethanolamine, monoethanolamine, single isopropyl alcohol peace, N-methylglucamine, lysine and arginine.Potassium hydroxide is particularly preferred.
The mixture of fatty acid or fatty acid is introduced in the compositions with free form usually, adds alkali then, and neutralization reaction takes place on the spot.
The content of fatty acid of the present invention preferably weight accounts for the 2-50% of composition total weight, and preferably 5-45% is more preferably 10-40%.
The preferred specific embodiments according to the present invention, the degree of neutralization of the mixture of fatty acid or fatty acid are 50-90mol%, more preferably 55-75mol%.
Sulfosuccinic acid type anion surfactant is preferably selected from the material of following general formula (I):
Z-CO-CH-(SO
3X)-CH
2-COOY (I)
Wherein X is derived from alkali metal or contains the alkali of organic amine or the ion of ammonium ion;
Y represents X or R;
R represents straight or branched or cyclic C
6-C
30The alkyl or alkenyl chain;
Z represents group OR, R (OCH
2CH
2O)
nO or RCONHW, wherein W representative (CH
2CH
2O)
n, or (CH
2CH (CH
3)-O)
n", n, n ' and n " be the integer of 1-10.
Here the sulfosuccinic acid type surfactant of being mentioned for example can be, oxyethylation (3 EO) lauryl alcohol list sulfosuccinate (C
12/ C
1470/30), Witco company is with commercial name SETACIN 103SPECIAL, and REWOPOL SB-FA 30 K 4 are commercially available; C
12-C
14Alcohol half disodium sulfosuccinate, Zschimmer Schwarz company is commercially available with commercial name SETACIN F SPECIAL PASTE; Oxyethylation (2 EO) oleamide disodium sulfosuccinate, Henkel company is commercially available with commercial name STANDAPOL SH 135; Oxyethylation (5 EO) lauramide list sulfosuccinate, Sanyo company is commercially available with commercial name LEBONA-5000; Oxyethylation (10 EO) lauryl citric acid disodium sulfosuccinate, Witco company is commercially available with commercial name REWOPOL SB CS 50; And single ricinoleic acid list sulfosuccinate, Witco company is commercially available with commercial name REWODERM S 1333.
Preferred oxyethylation (2 EO) the oleamide disodium sulfosuccinate that uses.
The preferred weight content of sulfosuccinic acid type surfactant of the present invention accounts for the 0.2-20% of composition total weight, more preferably 1-15%.
Preferred non-beet alkali ampholytic surface active agent is selected from the imidazoline type material of following general formula (II):
Wherein:
-R
1Represent saturated or unsaturated, the C of straight or branched
6-C
30Hydrocarbyl group;
-R
2Represent hydrogen atom or group-(CH
2)
q-COOY ';
-X ' and Y ' represent hydrogen atom or univalent cation, particularly metal cation, especially preferably alkali metal cation such as sodium respectively or simultaneously;
-p and q are 1 or 2 integers, can be identical or different.
It is at least a that the preferable range of the amphoteric surfactant of general formula of the present invention (II) expression is that those have, and the material of the feature of preferred several the following stated: p is identical with q; X ' is identical with Y ', preferably represents univalent cation, especially preferably sodium ion; R
1Representative is generally C
5-C
20Hydrocarbyl group, C preferably
7, C
9, C
11, C
13Or C
17Hydrocarbyl group, undersaturated C
17Group, or be present in natural oil, as the R of Oleum Cocois, Cortex cocois radicis fatty oil, Semen Lini oil, wheat germ oil or animal oil
1The hydrocarbyl group of-COOH acid.
As the example of the extractum product of imidazoline type amphoteric surfactant, be meant especially those RhodiaChimie companies with trade name MIRANOL
Commercially available and those have the material (CTFA dictionary, the 4th edition, 1991) of following CTFA name:
Caproic acid both sexes sodium acetate, caproic acid both sexes sodium propionate, sad both sexes sodium acetate, sad both sexes sodium propionate, Cortex cocois radicis both sexes sodium acetate, Cortex cocois radicis both sexes sodium propionate, isostearic acid both sexes sodium acetate, isostearic acid both sexes sodium propionate, lauric acid both sexes sodium acetate, lauric acid both sexes sodium propionate, oleic acid both sexes sodium acetate, oleic acid both sexes sodium propionate, stearic acid both sexes sodium acetate, stearic acid both sexes sodium propionate, animal oil both sexes sodium acetate and Fructus Hordei Germinatus both sexes sodium acetate, caproic acid both sexes oxalic acid disodium, caproic acid both sexes disodium beclomethasone, sad both sexes oxalic acid disodium, sad both sexes disodium beclomethasone, Cortex cocois radicis both sexes oxalic acid disodium, Cortex cocois radicis both sexes disodium beclomethasone, isostearic acid both sexes oxalic acid disodium, isostearic acid both sexes disodium beclomethasone, lauric acid both sexes oxalic acid disodium, lauric acid both sexes disodium beclomethasone, oleic acid both sexes disodium beclomethasone, stearic acid both sexes oxalic acid disodium, animal oil both sexes oxalic acid disodium and Fructus Hordei Germinatus both sexes oxalic acid disodium.
Cortex cocois radicis both sexes sodium acetate, for example more preferably use the commercially available prod of the commercialization of Rhodia Chimie company MIRANOL ULTRAC32 by name.
The preferred weight content of non-beet alkali ampholytic surface active agent of the present invention accounts for the 0.2-30% of composition total weight, is preferably 1-20%.
The weight ratio of non-beet alkali surface activator and sulfosuccinic acid type surfactant is 0.25-1.5, preferably is less than or equal to 1.2.
Compositions of the present invention can contain other surfactant in addition, and it is selected from the anion surfactant except the sulfosuccinic acid type, beet alkali ampholytic surface active agent, and non-ionic surface active agent, and their mixture.
Additional anion surfactant among the present invention can be a salt, especially preferably alkali metal salt such as sodium salt, ammonium salt, organic amine salt, amino alkoxide or alkali salt such as magnesium salt, described salt are following form: alkyl sulfate, alkyl ether sulfate, alkyl acyl ammonia ether sulfate, alkyl aryl polyether sulfate, monoglyceride sulfate; Alkylsulfonate, alkylamide sulfonate, alkylaryl sulfonates, alpha-alkene sulfonate, paraffin sulfonate; Alkyl sulfoacetate; Acyl sarcosinates; Acyl glutamate, the alkyl of described material and carboxyl groups comprise 6-24 carbon atom, preferred phenyl of aromatic yl group or benzyl group.Can also use C
6-C
24Ester and polysaccharide glycosides carboxylate such as alkyl androstanediol citrate, the APG tartrate; Alkyl sulfosuccinic carboxylic acid amide esters, acyl-hydroxyethyl sulfonate and N-acyl taurine salt, the alkyl of described material and carboxyl groups comprise 12-20 carbon atom.In these anion surfactants, acyl-lactate can also be arranged, described acyl group contains 8-20 carbon atom.
In addition, can also be alkyl D-galactoside alduronic acid and its salt, i.e. polyoxy alkylene (C
6-C
24) alkyl ether carboxylic acid, polyoxy alkylene (C
6-C
24) alkyl (C
6-C
24) the aryl ether carboxylic acid, polyoxy alkylene (C
6-C
24) alkyl amido ether carboxylic acid and their salt, wherein especially those comprise the ethylene oxide group of 2-50, and composition thereof.
Beet alkali ampholytic surface active agent can be (C
8-C
20) alkyl betaine, sulfobetaines, (C
8-C
20) alkyl amido (C
6-C
8) alkyl betaine, or (C
8-C
20) alkyl amido (C
6-C
8) the alkyl sulfobetaines; And their mixture.
Suitable non-ionic surface active agent of the present invention is that those known substances are (special in M.R.PORTER " surfactant handbook ", Blackie﹠amp; Son (Glasgow and London) publishes, and 1991, pp.116-178).Particularly preferably be alcohols, salmefamol, (C
1-C
20) alkylphenol or polyethoxylated, poly-propoxylation or bound to polyglycerol fatty acid, described aliphatic chain comprises for example 8-18 carbon atom, and its ethylene oxide or propylene oxide group quantity are preferably 2-50, and glycerol group preferred amount is 2-30.Can also be the copolymer of ethylene oxide and propylene oxide, the polymer of ethylene oxide and propylene oxide and aliphatic alcohol; The polyethoxylated fatty acid amide preferably contains the 2-30mol ethylene oxide, and polyglycereol fat amide contains average 1-5 glycerol group, especially preferably 1.5-4; The ethoxylated fatty acid ester of anhydro sorbitol that contains the ethylene oxide of 2-30mol; Sucrose fatty acid ester, cithrol, (C
6-C
24) alkyl poly glucoside, N-(C
6-C
24) the alkylated glucamine derivant, amine oxide is as (C
10-C
14) alkyl amine oxide or N-(C
10-C
14) acyl amino propyl group morpholine oxide and their mixture.
The weight content of additional surfactant preferably accounts for the 0.1-20% of composition total weight, is more preferably 0.2-10%.
Compositions of the present invention is normally used with dense or rare Emulsion form.Its viscosity is at 25 ℃, with the Rh é omat RM180 (from Rheometric Scientific) that has No. 4 rotors (set TV), measuring system 75, velocity gradient 200s
-1, under 10 minutes the situation of rotational time, measured value is 1-20Pa.s, preferably 2-10Pa.s.
The acceptable aqueous medium of the cosmetic of foam compositions of the present invention can comprise one or more solvents outside dewatering, and described solvent is selected from the lower alcohol that contains 1-6 carbon atom, as ethanol; Polyhydric alcohol is as glycerol; Ethylene glycol is as butanediol, isoprenediol, propylene glycol, Polyethylene Glycol such as PEG-8; Sorbitol; Sugar is as glucose, fructose, maltose, lactose, sucrose; And their mixture.Solvent in the present composition accounts for the 0.5-30% of composition total weight, is preferably 5-20%.
Can also in compositions, add one or more thickening agents, polymer preferably, its concentration preferably accounts for the 0.05-2% of composition total weight.
The example of described thickening agent has:
-polysaccharide biopolymer material is as xanthan gum, guar gum, alginate, modified cellulose;
-synthetic polymer is as the commercially available prod of the CARBOPOL by name 980 of polyacrylate such as GOODRICH company, the commercially available prod of the HYPAN SS201 by name of acrylic acid/acrylonitrile copolymer such as KINGSTON company;
-inorganic thickening agent, as terre verte, the commercially available prod of the Strese Hofmann's hectorite. of modification or unmodified such as the BENTONE by name of RHEOX company, the commercially available prod of the LAPONITE by name of SOUTHERN CLAY PRODUCTS company, the commercially available prod of the VEEGUM HS by name of R.TVANDERBILT company;
-and their mixture.
Compositions of the present invention can also comprise the adjuvant in conventional foam cleaning agent field, as bringing the polyammonium type cationic polymer of soft and cunning sensation to whipped cream.The preferably following polymer of these cationic polymers:
Polyammonium 5 is as the commercially available prod of the MERQUAT by name 5 of CALGON company;
Polyammonium 6, as the commercially available prod of the SALCARE SC 30 by name of CIBA company, and the commercially available prod of the MERQUAT 100 of CALGON company;
Polyammonium 7, as the MERQUAT S by name of CALGON company, the commercially available prod of MERQUAT 2200 and MERQUAT 550, and the commercially available prod of the SALCARE SC 10 by name of CIBA company;
Polyammonium 10 is as the commercially available prod of the polymer JR 400 by name of AMERCHOL company;
Polyammonium 11 is as the GAFQUAT by name 755 of ISP company, the commercially available prod of GAFQUAT 755N and GAFQUAT734;
Polyammonium 15 is as the commercially available prod of the ROHAGITKF 720F by name of ROHM company;
Polyammonium 16 is as the LUVIQUAT FC905 by name of BASF AG, LUVIQUAT FC370, the commercially available prod of LUVIQUAT HM552 and LUVIQUAT FC550;
Polyammonium 22 is as the commercially available prod of the MERQUAT by name 280 of CALGON company;
Polyammonium 28 is as the commercially available prod of the STYLEZE CC10 by name of ISP company;
Polyammonium 39 is as the commercially available prod of the MERQUAT PLUS 3330 by name of CALGON company;
Polyammonium 44 is as the commercially available prod of the LUVIQUAT CARE by name of BASF AG;
Polyammonium 46 is as the commercially available prod of the LUVIQUAT HOLD by name of BASF AG;
Polyammonium 47 is as the commercially available prod of the MERQUAT by name 2001 of CALGON company.
Equally also can use the commercially available prod of the JAGUAR by name of cationic glue class such as RHODIA company to make cationic polymer.
In addition, compositions of the present invention can contain the adjuvant that is generally used for cosmetic field, and described adjuvant is selected from oil, active agent, spice, antiseptic, chelating agen (EDTA), pigment, pearling agent, inorganic or organic filler such as Pulvis Talci, Kaolin, silicon dioxide or polyethylene powder, soluble colorant.The content of these adjuvant all is the habitual amount in affiliated field, for example accounts for the 0.01-20% of composition total weight.These adjuvant and content thereof must not change the performance that compositions of the present invention requires.
For example oily, can be vegetable oil (Jojoba oil, American Avocado Tree oil, Oleum sesami, Oleum helianthi, Semen Maydis oil, soybean oil, safflower oil, Oleum Vitis viniferae), mineral oil (vaseline, optional hydrogenation isoparaffin), artificial oil (isopropyl myristate, cetyl caprylate, polyisobutylene, ethylhexyl cetylate, alkyl benzoate), volatilization or nonvolatile silicone oil such as polydimethylsiloxane (PDMS) and ring dimethyl siloxane or cyclomethicone, with the silicone oil that replaces with fluorine processing or fluorine, and their mixture.The amount of being refueled can not change the performance that the present composition requires: its content maximum accounts for 15% of composition total weight, is more preferably and accounts for 10%, preferably accounts for 0.1-5%, more preferably is to account for 0.1-3%.
As active component, can be sunscreen for example; Anti-dandruff dose; Wetting agent; Depigmenting agent; Propigmentingagent; 'alpha '-hydroxy acids; Antibacterial; Antifree radical agent, antistain agent; Antiinflammatory; The retinoid material; Algae, fungus, plant, yeast and bacterial extract; Hydrolysis, protein partial hydrolysis or unhydrolyzed; Enzyme, hormone, vitamin and derivant thereof, flavone and isoflavone, and their mixture.
Another object of the present invention comprises the cosmetic use of the above compositions, be as people's horny layer material particularly skin clean and/or the makeup removing product.
Another object of the present invention comprises cleans the particularly cosmetic method of skin residual dirt of people's horny layer material, it is characterized in that using compositions of the present invention in the presence of the water on the horny layer material, by rubbing the formation foam, remaining dirt is removed in the flushing of reuse water.
Following listed examples is to be used for explanation, but does not limit the present invention.Wherein said content all is weight percentages unless stated otherwise, represents with %.The name of material is called chemical name or CTFA name (seeing international cosmetic composition dictionary and handbook), indivedual except.
| Compositions | The comparative example 1 | The comparative example 2 | Embodiment 3 (the present invention) | Embodiment 4 (the present invention) |
| Palmic acid | 10.20g | 10.20g | 10.20g | 10.20g |
| Myristic acid | 10.15g | 10.15g | 10.15g | 10.15g |
| Lauric acid | 2.50g | 2.50g | 2.50g | 2.50g |
| Stearic acid | 2.65g | 2.65g | 2.65g | 2.65g |
| Potassium hydroxide | 3.66g | 3.66g | 3.66g | 3.66g |
| Oleamide PGE-2 disodium sulfosuccinate | - | 2.00g | 3.00g | 4.00g |
| Cortex cocois radicis both sexes sodium acetate | 6.00g | 4.00g | 3.00g | 2.00g |
| Cortex cocois radicis PGE-7 glyceride | 2.00g | 2.00g | 2.00g | 2.00g |
| Glycerol | 1.00g | 1.00g | 1.00g | 1.00g |
| 16/octodecyl alcohol polyoxyethylene (60) ether myristic acid glycol ester | 0.50g | 0.50g | 0.50g | 0.50g |
| Electrolyte | In right amount | In right amount | In right amount | In right amount |
| Antiseptic | In right amount | In right amount | In right amount | In right amount |
| Chelating agen | In right amount | In right amount | In right amount | In right amount |
| Antioxidant | In right amount | In right amount | In right amount | In right amount |
| Spice | In right amount | In right amount | In right amount | In right amount |
| Water | Add to 100g | Add to 100g | Add to 100g | Add to 100g |
The Emulsion of embodiment 1-4 prepares by following process:
In a retort, add entry, fatty acid (Palmic acid, lauric acid, stearic acid and myristic acid), glycerol, Cortex cocois radicis PEG-7 glyceride, 16/octodecyl alcohol polyoxyethylene (60) ether myristic acid glycol ester, antiseptic, chelating agen and antioxidant, stir in the retort, be heated to 75 ℃ (existing biphase).Under 75 ℃, add oleamide PGE-2 disodium sulfosuccinate and Cortex cocois radicis both sexes sodium acetate, note ventilating: stir 10 minutes (form smooth Emulsion and have only a phase) 75 ℃ of following middling speeds.
Mixture cools off under 55 ℃ of vacuum conditions, adds spice, still stirs under vacuum condition.
Under 50 ℃, add potassium hydroxide (add total amount 95%); Mixture stirred 30 minutes under vacuum condition.Be cooled to 25 ℃, keep vacuum condition to stir to avoid product to be exposed in the air down.
The viscosity of product is at 25 ℃, with the Rh é omat RM180 (from Rheometric Scientific company) that has No. 4 rotors (set TV), measuring system 75, velocity gradient 200s
-1, measure under 10 minutes the situation of rotational time.
Carry out stability test with Certomat:
Here use the Certomat of B.Braun Biotech Internafional
HR type instrument is measured.
Get the 50g sample in the every kind of preparation that needs to measure and place 100ml glass plate container.Each dull and stereotyped container places 30 ℃ of water-baths.They are placed on the pallet, with the jolting of 150rpm speed.This jolting is the transportation of imitation product.
This mode can be observed the unstability that is separated: liquid phase more or less produces clear but matt and glossiness intermediate phase at container bottom; The then rare gloss in surface.
The observation of this outward appearance or phenomenon of phase separation is after 30 days.
Experimental observation result such as following table:
| Compositions | The comparative example 1 | The comparative example 2 | Embodiment 3 (the present invention) | Embodiment 4 (the present invention) |
| 25 ℃ viscosity Pas | 9.0 | 5.7 | 4.5 | 5.7 |
| The stability of measuring with Certomat after 30 days | Instability is observed after 24 hours and is separated, and still keeps after 30 days | Instability is observed after 24 hours and is separated, and still keeps after 30 days | Stable | Stable |
Stability test is the result show: the embodiment of the invention 3,4 comprise Cortex cocois radicis both sexes sodium acetate/bonded cosurfactant of oleamide PEG-2 disodium sulfosuccinate, and the two weight ratio is still stable after 30 days less than the compositions of 2: 1 (as 1: 1 and 2: 4), the compositions of this and comparative example's 1 (non-part of the present invention) the cosurfactant that only comprises Cortex cocois radicis both sexes sodium acetate and comparative example's 2 (non-part of the present invention) the oleamide PEG-2 disodium sulfosuccinate/Cortex cocois radicis both sexes sodium acetate weight ratio that comprises is that 2: 1 the compositions of bonded cosurfactant is different, this compositions instability.
Embodiment 5-7
| Compositions | Embodiment 5 | Embodiment 6 | The comparative example 7 |
| Palmic acid | 10.64g | 10.20g | 9.76g |
| Myristic acid | 7.68g | 10.15g | 10.12g |
| Lauric acid | 5.00g | 2.50g | 2.5g |
| Stearic acid | 3.18g | 2.65g | 2.12g |
| Potassium hydroxide | 3.96g | 3.66g | 3.66g |
| Oleamide PGE-2 disodium sulfosuccinate | 2.00g | 2.00g | 3.40g |
| Cortex cocois radicis both sexes sodium acetate | 2.00g | 2.00g | |
| Cortex cocois radicis PGE-7 glyceride | 2.00g | 2.00g | 2.00g |
| Glycerol | 1.00g | 1.00g | 1.00g |
| 16/octodecyl alcohol polyoxyethylene (60) ether myristic acid glycol ester | 0.50g | 0.50g | 0.50g |
| Electrolyte | In right amount | In right amount | |
| Antiseptic | In right amount | In right amount | In right amount |
| Chelating agen | In right amount | In right amount | In right amount |
| Antioxidant | In right amount | In right amount | In right amount |
| Spice | In right amount | In right amount | In right amount |
| Water | Add to 100g | Add to 100g | Add to 100g |
| The viscosity Pas of 25C | 4.0 | 6.6 | 6.9 |
The Emulsion of embodiment 5-7 is to prepare according to the identical preparation process of embodiment 1-4.Its viscosity is at 25 ℃, with the Rh é omat RM180 (from Rheometric Scientific company) that has No. 4 rotors (set TV), measuring system 75, velocity gradient 200s
-1, measure under 10 minutes the situation of rotational time.
Sensory property
The frothing capacity of the compositions of embodiment 5,6,7 is to be assessed by the evaluation group that 7 people form according to following described scheme:
Before using the assessment product, the group member all will wash one's hands with soap and suitably rinse well.
Then implement following steps:
-with 38 ℃ of flow velocitys of water temperature moistening both hands of circulating water that are 81/min,
-the 2g product is placed the centre of the palm recess of a hands,
The above-mentioned same water of-Jia 3ml 15 seconds on product,
-by testing standard assessment quality, froth,
-wash both hands with same circulating water.
The grade of the following and labelling 0-10 of evaluation criteria.
The initial foaming: bubble more early, score is high more.
Foam number: foamability; Product is in that foam number is big more on hand, and score is high more.
The cream impression: the impression of cream is strong more, and score is high more.
During the average perceptual result of each standard is listed in the table below:
| Foam quality | Embodiment 5 | Embodiment 6 | The comparative example 7 |
| The initial foaming | 6.1 | 5.8 | 4.5 |
| Foam volume (foamability) | 7.5 | 6.7 | 5.0 |
| Cream is experienced (density) | 9.0 | 8.5 | 7.3 |
Experiencing the testing experiment result shows: the embodiment of the invention 5 and 6 the compositions that comprises oleamide PEG-2 disodium sulfosuccinate/bonded cosurfactant of Cortex cocois radicis both sexes sodium acetate, its quality, froth is better than the compositions that only comprises oleamide PEG-2 disodium sulfosuccinate cosurfactant of comparative example 7 (non-part of the present invention).
Embodiment 8 and 9
Embodiment 8 and 9 Emulsion are according to the identical preparation process preparation of embodiment 1-4.Its viscosity is at 25 ℃, with the Rh é omat RM180 (from Rheometric Scientific company) that has No. 4 rotors (set TV), measuring system 75, velocity gradient 200s
-1, measure under 10 minutes the situation of rotational time.
| Compositions | Embodiment 8 | Embodiment 9 |
| Palmic acid | 10.64g | 10.64g |
| Myristic acid | 7.68g | 7.68g |
| Stearic acid | 3.18g | 3.18g |
| Lauric acid | 5.00g | 5.00g |
| Potassium hydroxide | 3.96g | 3.96g |
| Oleamide PGE-2 disodium sulfosuccinate | 4.00g | 3.00g |
| Cortex cocois radicis both sexes sodium acetate | 2.00g | 2.00g |
| Cortex cocois radicis PGE-7 glyceride | 2.00g | 2.00g |
| Glycerol | 1.00g | 1.00g |
| 16/octodecyl alcohol polyoxyethylene (60) ether myristic acid glycol ester | 0.50g | 0.50g |
| Electrolyte | In right amount | In right amount |
| Antiseptic | In right amount | In right amount |
| Chelating agen | In right amount | In right amount |
| Antioxidant | In right amount | In right amount |
| Spice | In right amount | In right amount |
| Water | Add to 100g | Add to 100g |
| 25 ℃ viscosity Pas | 4.0 | 4.0 |
Claims (37)
1. be used for the foam compositions that skin cleans or removes ornaments and formal dress, it contains at least a surfactant system in the acceptable aqueous medium of making up, and this system comprises:
(a) part is by the mixture of neutral at least a fatty acid of organic or inorganic alkali or fatty acid, and the degree of neutralization of the mixture of described fatty acid or fatty acid is 50-90mol%;
(b) at least a non-beet alkali ampholytic surface active agent, this non-beet alkali ampholytic surface active agent has following general formula (II):
Wherein:
-R
1Represent saturated or unsaturated, the C of straight or branched
6-C
30Hydrocarbyl group;
-R
2Represent hydrogen atom or group-(CH
2)
q-COOY ';
-X ' and Y ' represent hydrogen atom or univalent cation respectively or simultaneously;
-p and q are 1 or 2 integers, can be identical or different;
(c) anion surfactant of at least a sulfosuccinate type, this sulfosuccinic acid type anion surfactant has following general formula (I):
Z-CO-CH-(SO
3X)-CH
2-COOY (I)
Wherein X is derived from alkali metal or contains the alkali of organic amine or the ion of ammonium ion; Y represents X or R; R represents straight or branched or ring-type C
6-C
30The alkyl or alkenyl chain; Z represents group OR, R (OCH
2CH
2O)
nO or RCONHW, wherein W representative (CH
2CH
2O)
n' or (CH
2CH (CH
3)-O)
n", n, n ' and n " be the integer of 1-10,
The weight ratio of the surfactant of the amphoteric surfactant of non-betanin and sulfosuccinate type is less than 2.
2. compositions as claimed in claim 1 is characterized in that described fatty acid is to comprise saturatedly or undersaturated, contains the carboxylic acid of the straight or branched alkyl of 6-30 carbon atom.
3. compositions as claimed in claim 2 is characterized in that described fatty acid is selected from lauric acid, myristic acid, Palmic acid, stearic acid and their mixture.
4. compositions as claimed in claim 3 is characterized in that said composition comprises fatty acid mixt, and described fatty acid mixt is made up of lauric acid, myristic acid, Palmic acid and stearic acid.
5. compositions as claimed in claim 1, wherein inorganic base is selected from the hydroxide or the ammonium hydroxide of alkali-metal hydroxide, alkaline-earth metal.
6. compositions as claimed in claim 1, wherein organic base is selected from triethanolamine, monoethanolamine, monoisopropanolamine, N-methylglucamine, lysine and arginine.
7. compositions as claimed in claim 1, wherein said alkali is potassium hydroxide.
8. compositions as claimed in claim 1, wherein the weight content of fatty acid is the 2-50% that accounts for composition total weight.
9. compositions as claimed in claim 1, wherein the degree of neutralization of the mixture of fatty acid or fatty acid is 55-75mol%.
10. compositions as claimed in claim 1, wherein X ' and Y ' represent metal cation respectively or simultaneously.
11. compositions as claimed in claim 1, wherein X ' and Y ' represent alkali metal cation respectively or simultaneously.
12. compositions as claimed in claim 1, wherein X ' and Y ' difference or represent sodium simultaneously.
13. compositions as claimed in claim 1, wherein sulfosuccinic acid type surfactant is selected from
-oxyethylation lauryl alcohol list sulfosuccinate
-C
12-C
14Alcohol half disodium sulfosuccinate
-oxyethylation oleamide disodium sulfosuccinate
-oxyethylation lauramide list sulfosuccinate
-oxyethylation lauryl citric acid list disodium sulfosuccinate
-single ricinoleic acid list sulfosuccinate.
14. compositions as claimed in claim 1, wherein sulfosuccinic acid type surfactant is an oxyethylation oleamide disodium sulfosuccinate.
15. compositions as claimed in claim 1, wherein the weight content of sulfosuccinic acid type surfactant accounts for the 0.2-20% of composition total weight.
16. compositions as claimed in claim 15, wherein the weight content of sulfosuccinic acid type surfactant accounts for the 1-15% of composition total weight.
17. compositions as claimed in claim 1, the amphoteric surfactant of its formula of (II) expression is selected from:
Caproic acid both sexes sodium acetate, caproic acid both sexes sodium propionate, sad both sexes sodium acetate, sad both sexes sodium propionate, Cortex cocois radicis both sexes sodium acetate, Cortex cocois radicis both sexes sodium propionate, isostearic acid both sexes sodium acetate, isostearic acid both sexes sodium propionate, lauric acid both sexes sodium acetate, lauric acid both sexes sodium propionate, oleic acid both sexes sodium acetate, oleic acid both sexes sodium propionate, stearic acid both sexes sodium acetate, stearic acid both sexes sodium propionate, animal oil both sexes sodium acetate and Fructus Hordei Germinatus both sexes sodium acetate, caproic acid both sexes oxalic acid disodium, caproic acid both sexes disodium beclomethasone, sad both sexes oxalic acid disodium, sad both sexes disodium beclomethasone, Cortex cocois radicis both sexes oxalic acid disodium, Cortex cocois radicis both sexes disodium beclomethasone, isostearic acid both sexes oxalic acid disodium, isostearic acid both sexes disodium beclomethasone, lauric acid both sexes oxalic acid disodium, lauric acid both sexes disodium beclomethasone, oleic acid both sexes disodium beclomethasone, stearic acid both sexes oxalic acid disodium, animal oil both sexes oxalic acid disodium and Fructus Hordei Germinatus both sexes oxalic acid disodium.
18. compositions as claimed in claim 17, the amphoteric surfactant of its formula of (II) are Cortex cocois radicis both sexes sodium acetates.
19. as the described arbitrary compositions of claim 1-18, wherein the weight content of non-beet alkali ampholytic surface active agent accounts for the 0.2-30% of composition total weight.
20. compositions as claimed in claim 19, wherein the weight content of non-beet alkali ampholytic surface active agent accounts for the 1-20% of composition total weight.
21. as the described arbitrary compositions of claim 1-18, the weight ratio of wherein non-beet alkali surface activator and sulfosuccinic acid type surfactant is 0.25-1.5.
22. compositions as claimed in claim 21, the weight ratio of wherein non-beet alkali surface activator and sulfosuccinic acid type surfactant is less than or equal to 1.2.
23. as the described arbitrary compositions of claim 1-18, wherein also contain at least a additional surfactant, it is selected from the anion surfactant except the sulfosuccinic acid type, beet alkali ampholytic surface active agent, and non-ionic surface active agent, and their mixture.
24. as the described arbitrary compositions of claim 1-18, wherein the weight content of additional surfactant accounts for the 0.1-20% of composition total weight.
25. compositions as claimed in claim 24, wherein the weight content of additional surfactant accounts for the 0.2-10% of composition total weight.
26., it is characterized in that it provides with the Emulsion form as the described arbitrary compositions of claim 1-18.
27. as the described arbitrary compositions of claim 1-18, it is characterized in that its viscosity, with the Rh é omat RM180 that has No. 4 rotors, measuring system 75, velocity gradient 200s at 25 ℃
-1, under 10 minutes the situation of rotational time, measured value is 1-20Pas.
28. as the described arbitrary compositions of claim 1-18, the acceptable aqueous medium that it is characterized in that making up comprises at least a solvent, it is selected from lower alcohol; Polyhydric alcohol; Sugar and their mixture.
29., it is characterized in that also comprising at least a thickening agent as the described arbitrary compositions of claim 1-18.
30., it is characterized in that also comprising at least a polyammonium type cationic polymer as the described arbitrary compositions of claim 1-18.
31. as the described arbitrary compositions of claim 1-18, it is characterized in that also comprising at least a adjuvant, it is selected from oil, active agent, spice, antiseptic, chelating agen, pigment, pearling agent, inorganic or organic filler, soluble colorant.
32. compositions as claimed in claim 31, wherein said filler are Pulvis Talci, Kaolin, silicon dioxide or polyethylene powder.
33. as the compositions of claim 30, wherein active agent is selected from sunscreen; Anti-dandruff dose; Wetting agent; Depigmenting agent; Propigmenting agent; 'alpha '-hydroxy acids; Antibacterial; Antifree radical agent, antistain agent; Antiinflammatory; The retinoid material; Algae, fungus, plant; Hydrolysis, protein partial hydrolysis or unhydrolyzed; Enzyme, hormone, vitamin, flavone and isoflavone, and their mixture.
34. the cosmetic use of the described compositions of claim 1-33, it is as the cosmetic product that cleans and/or remove people's horny layer material.
35. purposes as claimed in claim 34 is cleaning and/or the makeup removing product as skin.
36. clean the cosmetic method of people's horny layer material residual dirt, it is characterized in that using as the described compositions of claim 1-33 on the horny layer material, in the presence of water, by rubbing the formation foam, remaining dirt is removed in the flushing of reuse water.
37. method as claimed in claim 36 is the residual dirt that is used to clean skin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0203929A FR2837697B1 (en) | 2002-03-28 | 2002-03-28 | FOAMING COSMETIC COMPOSITION; USES FOR CLEANING OR CLEANING |
| FR02/03929 | 2002-03-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1449735A CN1449735A (en) | 2003-10-22 |
| CN1326511C true CN1326511C (en) | 2007-07-18 |
Family
ID=27839292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031286119A Expired - Lifetime CN1326511C (en) | 2002-03-28 | 2003-03-27 | Foam cosmetic composition for cleaning or dress taking off |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100540616B1 (en) |
| CN (1) | CN1326511C (en) |
| FR (1) | FR2837697B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI694840B (en) * | 2015-03-05 | 2020-06-01 | 南韓商愛茉莉太平洋股份有限公司 | Cosmetic composition of mousse form comprising the scoria |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005028622A1 (en) * | 2005-06-20 | 2007-01-04 | Henkel Kgaa | Hair care products |
| US8110533B1 (en) * | 2010-09-28 | 2012-02-07 | Conopco, Inc. | Liquid soap compositions |
| PH12014500163A1 (en) * | 2011-07-20 | 2014-02-24 | Colgate Palmolive Co | Cleansing composition with whipped texture |
| WO2013042274A1 (en) * | 2011-09-22 | 2013-03-28 | L'oreal | Cosmetic cleansing composition |
| FR3064471B1 (en) | 2017-03-31 | 2020-11-06 | Oreal | BIPHASE COSMETIC COMPOSITION AND COSMETIC TREATMENT OF KERATINIC MATERIALS |
| CN109589273A (en) * | 2017-09-30 | 2019-04-09 | 株式会社Lg生活健康 | Low irritant body cleanser composition |
| WO2020164087A1 (en) * | 2019-02-15 | 2020-08-20 | Beiersdorf Daily Chemical (Wuhan) Co. Ltd. | A cleansing composition releasable as a shapeable foam |
| JP2023503362A (en) * | 2019-11-28 | 2023-01-27 | セヴァ サンテ アニマレ | Veterinary composition for shampoo |
| US20240307281A1 (en) * | 2020-12-22 | 2024-09-19 | L V M H Recherche | Stable fatty acid soap-type cosmetic composition |
| KR102515905B1 (en) | 2022-10-20 | 2023-03-31 | 주식회사 제이피에스코스메틱 | Low irritant gel type cleasing cosmetic and Manufacturing method thereof |
| KR102515900B1 (en) | 2022-10-31 | 2023-03-31 | 주식회사 제이피에스코스메틱 | Gel type face cleasing cosmetic and Manufacturing method thereof |
| CN115813789B (en) * | 2023-01-03 | 2024-10-08 | 上海家化联合股份有限公司 | Foam composition with improved foam durability |
| WO2025222366A1 (en) * | 2024-04-23 | 2025-10-30 | L'oreal | Composition for cleansing and/or removing makeups from keratin materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04117321A (en) * | 1990-09-07 | 1992-04-17 | Kao Corp | Detergent composition |
| US6077816A (en) * | 1995-08-07 | 2000-06-20 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Liquid cleansing composition comprising soluble, lamellar phase inducing structurant |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753657B2 (en) * | 1986-12-03 | 1995-06-07 | ライオン株式会社 | Skin cleanser |
| JPH07309742A (en) * | 1994-05-16 | 1995-11-28 | Lion Corp | Creamy skin cleanser |
| US6071541A (en) * | 1998-07-31 | 2000-06-06 | Murad; Howard | Pharmaceutical compositions and methods for managing skin conditions |
| GB9928820D0 (en) * | 1999-12-06 | 2000-02-02 | Unilever Plc | Stable high glycerol liquids comprising sulfosuccinic acid monoesters |
-
2002
- 2002-03-28 FR FR0203929A patent/FR2837697B1/en not_active Expired - Lifetime
-
2003
- 2003-03-27 CN CNB031286119A patent/CN1326511C/en not_active Expired - Lifetime
- 2003-03-28 KR KR1020030019540A patent/KR100540616B1/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04117321A (en) * | 1990-09-07 | 1992-04-17 | Kao Corp | Detergent composition |
| US6077816A (en) * | 1995-08-07 | 2000-06-20 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Liquid cleansing composition comprising soluble, lamellar phase inducing structurant |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI694840B (en) * | 2015-03-05 | 2020-06-01 | 南韓商愛茉莉太平洋股份有限公司 | Cosmetic composition of mousse form comprising the scoria |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2837697B1 (en) | 2005-01-28 |
| KR20030078767A (en) | 2003-10-08 |
| KR100540616B1 (en) | 2006-01-11 |
| CN1449735A (en) | 2003-10-22 |
| FR2837697A1 (en) | 2003-10-03 |
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