US3666690A - Skin cleansing composition - Google Patents
Skin cleansing composition Download PDFInfo
- Publication number
- US3666690A US3666690A US89065A US3666690DA US3666690A US 3666690 A US3666690 A US 3666690A US 89065 A US89065 A US 89065A US 3666690D A US3666690D A US 3666690DA US 3666690 A US3666690 A US 3666690A
- Authority
- US
- United States
- Prior art keywords
- percent
- parts
- skin
- mineral oil
- lanolin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002480 mineral oil Substances 0.000 claims abstract description 16
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004166 Lanolin Substances 0.000 claims abstract description 14
- 235000011187 glycerol Nutrition 0.000 claims abstract description 14
- 229940039717 lanolin Drugs 0.000 claims abstract description 14
- 235000019388 lanolin Nutrition 0.000 claims abstract description 14
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 13
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 13
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 13
- -1 alkali metal sulfite Chemical class 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 9
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 16
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 abstract description 8
- 229940107698 malachite green Drugs 0.000 abstract description 8
- 125000002091 cationic group Chemical group 0.000 abstract description 6
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 4
- 239000006071 cream Substances 0.000 description 6
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 5
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 description 5
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- NNKSAZWMTWKXLD-UHFFFAOYSA-N n-methyloctadecan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH2+]C NNKSAZWMTWKXLD-UHFFFAOYSA-N 0.000 description 3
- 229940093625 propylene glycol monostearate Drugs 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 101100264195 Caenorhabditis elegans app-1 gene Proteins 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000008269 hand cream Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/23—Sulfur; Selenium; Tellurium; Compounds 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
- A61K8/31—Hydrocarbons
-
- 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
- A61K8/34—Alcohols
-
- 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
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
-
- 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
- A61K8/731—Cellulose; Quaternized cellulose derivatives
-
- 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
- A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- 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
- A61K2800/54—Polymers characterized by specific structures/properties
- A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
- A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic
Definitions
- ABSTRACT A skin-cleansing composition for the removal of dye stains caused by basic triphcnylmethane dyes, such as malachite green, comprising, in defined proportions, (l) a cationic surface-active quaternary ammonium salt containing a longchain alkyl substituent, (2) mineral oil, (3) lanolin, (4) glycerine, (5) an alkali metal sulfite, (6) sodium carboxymethyl cellulose and (7) water.
- This invention relates to a skin cleansing composition. More particularly, this invention relates to a hand cream for removing dye stains from the skin.
- Dye stains are difficult to remove from the skin. Probably the most difficultly removable dye stains are those from basic triphenylmethane dyes such as malachite green and methyl violet. These are intensely colored materials of great tinctorial strength. The stains produced on the skin by these dyes are resistant to removal and cannot be washed off with ordinary soaps and detergents. Special hand cleaners available on the market are of little or no help. Many of these cleaners contain abrasives and are designed for the use of mechanics and others to remove grease and related stains. It has been a customary practice in many dye laboratories and manufacturing plants to remove the dye stains by application of strong bleaches, such as sodium hypochlorite and potassium permanganate.
- strong bleaches such as sodium hypochlorite and potassium permanganate.
- the object of this invention is to provide an effective skin cleansing agent for removal of dye stains caused by basic triphenylmethane dyes.
- compositions which will remove from the skin stains caused by basic triphenylmethane dyes, particularly malachite green, fuchsine and methyl violet stains, and will not damage the skin.
- the components of the composition are a cationic surface active agent, a mineral oil, an alkali metal sulfite, lanolin, glycerine, water and a thickening agent.
- Optional components include a nonionic surface active agent and a buffering agent to maintain near neutral conditions.
- the cationic surface active agents of use in this invention are quaternary ammonium salts containing a long-chain alkyl group of from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, such as, for example, cetyl dimethyl ethyl ammonium bromide or stearyl dimethyl benzyl ammonium chloride.
- the salt may also contain one or two polyethoxylated groups, i.e., -(CH CH,0),,H in which n is an integer of from about 5 to about 15, such as, for example, di(polyethoxylated) stearyl methyl ammonium chloride and di(polyethoxylated) coco methyl ammonium chloride (coco" being a mixed long-chain (C -C, )-alkyl).
- the quaternary ammonium salts suitable for the composition of the invention will conform to the formula:
- R is methyl, ethyl or -(CH CH,O),,H in which n is an integer of from 5 to l5; R is lower (C,-C )alkyl, benzyl or (CH Cl-l 0bnl-l; and X is chloride or bromide.
- the mineral oil of use in this invention is of the light mineral oil type and includes kerosene.
- a preferred white mineral oil has an SVS viscosity of 70-74 at 100F., a specific gravity at 60F. of 0.8575 and a pour point of +10"F.
- the alkali metal sulfites of use include sodium sulfite, sodium bisulfite, potassium sulfite, and potassium bisulfite.
- Sodium bisulfite is preferred for economic reasons.
- nonionic surface active agents enhance the detergency of the cleaning composition.
- Representative types of nonionic surface active agents which may be used include the polyethoxylated long-chain alkylphenols, such as the reaction products of nonylphenol with from 4 to 30 moles of ethylene oxide per mole of nonylphenol, and glycol monoesters of longchain fatty acids of from 12 to 22 carbon atoms, such as propylene glycol monostearate.
- the preferred nonionic surface active agent is the condensation product of nonylphenol and about 9.5 moles of ethylene oxide.
- the thickening agent provides a stabilized product that is a cream and is easily applied to the skin. Without the thickening agent, the product of this invention is a liquid emulsion.
- Suitable thickening agents include sodium carboxymethylcellulose.
- the buffering agent neutralizes any residual acidity of the components of the cleanser. Obviously, the presence of strong acid in the cleansing composition is undesirable.
- Alkali metal salts of lower fatty acids as represented by sodium acetate or potassium acetate, are suitable buffering agents.
- the cleansing composition should contain between 3 and 12 percent, preferably between 6 and 10 percent, of the cationic surface active agent; between 5 and 20 percent, preferably between 7 and 10 percent, of the mineral oil; between 3 and 25 percent, preferably between 5 and 20 percent, of alkali metal sulfite; between 2 and 6 percent, preferably between 3 and 5 percent, of lanolin; between 5 and 18 percent, preferably between 10 and 15 percent, of glycerine; and between 30 and 50 percent, preferably between 35 and 45 percent, of water.
- the thickening agent should be used in an amount to provide the desired gel or cream. in the case of sodium carboxymethylcellulose, the amount is between 2 and 12 percent, normally between 5 and 8 percent.
- the amount of nonionic surface active agent is between 0 and I5 percent, preferably between 7 and 12 percent.
- the amount of bufi'ering agent, if used, is sufi'lcient to neutralize any strong acidity. For sodium acetate, the amount is between 0 and 2.5 percent, normally between 0.5 and 1 percent.
- the composition contains about 8.3 percent of cetyl dimethyl ethyl ammonium bromide, about 8.6 percent of mineral oil, about 4.1 percent of lanolin, about 13 percent of glycerine, about 10.9 percent of the condensation product of nonylphenol and 9.5 moles of ethylene oxide, about 41 percent water, about 0.6 percent of sodium acetate, about 6.2 percent of sodium bisulfite and 6.8 percent of sodium carboxymethylcellulose.
- the components of the cleansing composition can be combined in several different orders or sequences.
- the cationic surface active agent, mineral oil and lanolin are melted together and to the mixture with good stirring are added the glycerine and nonionic surface active agent.
- the solution of the alkali metal sulfite and buffering compound in warm water is added followed by the thickening agent. The stirring is continued briefly and the mixture is then cooled.
- the cleansing composition of this invention is a stable, soft cream which is easily applied to the skin.
- the cleansing cream is applied to the hands and the cream is worked into the skin until the stains are removed. When the stains have been removed, the excess cream can be wiped off or it can be flushed off with water.
- EXAMPLE 1 A mixture of 400 parts of cetyl dimethyl ethyl ammonium bromide, 415 parts of mineral oil and 200 parts of lanolin is melted, and to the melt with good stirring there are added 630 parts of glycerine and 525 parts of the condensation product of 1 mole of nonylphenol with about 9.5 moles of ethylene oxide. With vigorous stirring, 2,000 parts of warm water, 30 parts of sodium acetate, 300 parts of sodium bisulfite and 325 parts of sodium carboxymethylcellulose are added. The mixture is stirred for about 30 minutes and is then cooled. The product removes stains of malachite green, fuchsine and methyl violet from the skin and leaves the skin soft.
- EXAMPLE 2 A mixture of 50 parts of propylene glycol monostearate and 200 parts of cetyl dimethyl ethyl ammonium bromide is melted, and 210 parts of mineral oil, parts of lanolin, 315
- the product removes stains of methyl violet, fuchsine and malachite green from the skin and leaves the skin soft.
- EXAMPLE 3 A mixture of 100 parts of propylene glycol monostearate and 100 parts of di(polyethoxylated) stearyl methyl ammonium chloride (containing a total of 15 ethylene oxide units per molecule) and 415 parts of mineral oil is melted, and while the mixture is vigorously stirred, a solution of 500 parts of sodium bisulfite in 1,000 parts of water is slowly added. The thin solution is then thickened by addition of 200 parts of sodium carboxymethylcellulose. A solution of 90 parts of lanolin in 200 parts of glycerine is then added.
- the product removes stains of malachite green, fuchsine and methyl violet from the skin and leaves the skin soft.
- EXAMPLE 4 To a stirred mixture of 100 parts of di(polyethoxylated) stearyl methyl ammonium chloride (containing a total of 15 ethylene oxide units per molecule) and 415 parts of mineral oil, there is added a solution of 500 parts of sodium bisulfite in 1,000 parts of water. The resulting solution is heated to 90C. and stirred with cooling. Sodium carboxymethylcellulose (200 parts) is added, followed by a solution of 90 parts of lanolin in 250 parts of glycerine.
- the product removes stains of malachite green, fuchsine and methyl violet from the skin and leaves the skin soft.
- a hand cleansing composition consisting essentially of:
- R is methyl, ethyl or -(CH CH O),,H in which n is an integer of from 5 to 15; R is lower alkyl, benzyl or (CH CH O),,H; and X is chloride or bromide;
- a composition according to Claim 1 containing up to about 15 percent of a non-ionic surface active agent selected from (a) a condensation product of 1 mole proportion of nonylphenol with from 4 to 30 mole proportions of ethylene oxide and (b) a glycol monoester of a long-chain fatty acid.
- a non-ionic surface active agent selected from (a) a condensation product of 1 mole proportion of nonylphenol with from 4 to 30 mole proportions of ethylene oxide and (b) a glycol monoester of a long-chain fatty acid.
- a composition according to Claim 2 containing up to about 2.5 percent of an alkali metal acetate as buffering agent.
- composition according to claim 1 containing:
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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- Epidemiology (AREA)
- Birds (AREA)
- Emergency Medicine (AREA)
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- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Cosmetics (AREA)
Abstract
A skin-cleansing composition for the removal of dye stains caused by basic triphenylmethane dyes, such as malachite green, comprising, in defined proportions, (1) a cationic surface-active quaternary ammonium salt containing a long-chain alkyl substituent, (2) mineral oil, (3) lanolin, (4) glycerine, (5) an alkali metal sulfite, (6) sodium carboxymethyl cellulose and (7) water.
Description
United States Patent Bann [54] SKIN CLEANSING COMPOSITION [72] Inventor: Robert Francis Bann, Bn'dgewater Township, Somerset County, Nd,
[73] Assignee: American Cyanamid Company, Stamford,
Conn.
[22] Filed: Nov. 12, 1970 [21] App1.No.: 89,065
2,948,686 8/1960 Gianladis ..252/ 153 [451 May 30, 1972 3,178,371 4/1965 Friedenberg ..252/153 3,207,694 9/ 1965 Gogek ..252/105 3,400,079 9/1968 Clifford et a] ..252/105 X Primary Examiner-Richard D. Lovering Attorney-John L. Sullivan [5 7] ABSTRACT A skin-cleansing composition for the removal of dye stains caused by basic triphcnylmethane dyes, such as malachite green, comprising, in defined proportions, (l) a cationic surface-active quaternary ammonium salt containing a longchain alkyl substituent, (2) mineral oil, (3) lanolin, (4) glycerine, (5) an alkali metal sulfite, (6) sodium carboxymethyl cellulose and (7) water.
4 Claims, No Drawings SKIN CLEANSING COMPOSITION This invention relates to a skin cleansing composition. More particularly, this invention relates to a hand cream for removing dye stains from the skin.
Dye stains are difficult to remove from the skin. Probably the most difficultly removable dye stains are those from basic triphenylmethane dyes such as malachite green and methyl violet. These are intensely colored materials of great tinctorial strength. The stains produced on the skin by these dyes are resistant to removal and cannot be washed off with ordinary soaps and detergents. Special hand cleaners available on the market are of little or no help. Many of these cleaners contain abrasives and are designed for the use of mechanics and others to remove grease and related stains. It has been a customary practice in many dye laboratories and manufacturing plants to remove the dye stains by application of strong bleaches, such as sodium hypochlorite and potassium permanganate. The latter requires the subsequent use of a reducing agent to remove the brown stain left by the permanganate. Strong bleaching compounds are detrimental to the skin. Therefore, a completely satisfactory cleaner has not been available for removing stains caused by basic triphenylmethane dyes from the skin without damage to the skin.
The object of this invention is to provide an effective skin cleansing agent for removal of dye stains caused by basic triphenylmethane dyes.
It is a further object of this invention to provide a cleaner which not only removes the dye stains, but does so without damage to the skin.
A stable composition has now been discovered which will remove from the skin stains caused by basic triphenylmethane dyes, particularly malachite green, fuchsine and methyl violet stains, and will not damage the skin. The components of the composition are a cationic surface active agent, a mineral oil, an alkali metal sulfite, lanolin, glycerine, water and a thickening agent. Optional components include a nonionic surface active agent and a buffering agent to maintain near neutral conditions. I
The cationic surface active agents of use in this invention are quaternary ammonium salts containing a long-chain alkyl group of from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, such as, for example, cetyl dimethyl ethyl ammonium bromide or stearyl dimethyl benzyl ammonium chloride. The salt may also contain one or two polyethoxylated groups, i.e., -(CH CH,0),,H in which n is an integer of from about 5 to about 15, such as, for example, di(polyethoxylated) stearyl methyl ammonium chloride and di(polyethoxylated) coco methyl ammonium chloride (coco" being a mixed long-chain (C -C, )-alkyl). The quaternary ammonium salts suitable for the composition of the invention will conform to the formula:
wherein R is methyl, ethyl or -(CH CH,O),,H in which n is an integer of from 5 to l5; R is lower (C,-C )alkyl, benzyl or (CH Cl-l 0bnl-l; and X is chloride or bromide.
The mineral oil of use in this invention is of the light mineral oil type and includes kerosene. A preferred white mineral oil has an SVS viscosity of 70-74 at 100F., a specific gravity at 60F. of 0.8575 and a pour point of +10"F.
The alkali metal sulfites of use include sodium sulfite, sodium bisulfite, potassium sulfite, and potassium bisulfite. Sodium bisulfite is preferred for economic reasons.
The nonionic surface active agents enhance the detergency of the cleaning composition. Representative types of nonionic surface active agents which may be used include the polyethoxylated long-chain alkylphenols, such as the reaction products of nonylphenol with from 4 to 30 moles of ethylene oxide per mole of nonylphenol, and glycol monoesters of longchain fatty acids of from 12 to 22 carbon atoms, such as propylene glycol monostearate. The preferred nonionic surface active agent is the condensation product of nonylphenol and about 9.5 moles of ethylene oxide.
The thickening agent provides a stabilized product that is a cream and is easily applied to the skin. Without the thickening agent, the product of this invention is a liquid emulsion. Suitable thickening agents include sodium carboxymethylcellulose.
The buffering agent neutralizes any residual acidity of the components of the cleanser. Obviously, the presence of strong acid in the cleansing composition is undesirable. Alkali metal salts of lower fatty acids, as represented by sodium acetate or potassium acetate, are suitable buffering agents.
The cleansing composition should contain between 3 and 12 percent, preferably between 6 and 10 percent, of the cationic surface active agent; between 5 and 20 percent, preferably between 7 and 10 percent, of the mineral oil; between 3 and 25 percent, preferably between 5 and 20 percent, of alkali metal sulfite; between 2 and 6 percent, preferably between 3 and 5 percent, of lanolin; between 5 and 18 percent, preferably between 10 and 15 percent, of glycerine; and between 30 and 50 percent, preferably between 35 and 45 percent, of water. The thickening agent should be used in an amount to provide the desired gel or cream. in the case of sodium carboxymethylcellulose, the amount is between 2 and 12 percent, normally between 5 and 8 percent. The amount of nonionic surface active agent is between 0 and I5 percent, preferably between 7 and 12 percent. The amount of bufi'ering agent, if used, is sufi'lcient to neutralize any strong acidity. For sodium acetate, the amount is between 0 and 2.5 percent, normally between 0.5 and 1 percent.
In a preferred embodiment of this invention, the composition contains about 8.3 percent of cetyl dimethyl ethyl ammonium bromide, about 8.6 percent of mineral oil, about 4.1 percent of lanolin, about 13 percent of glycerine, about 10.9 percent of the condensation product of nonylphenol and 9.5 moles of ethylene oxide, about 41 percent water, about 0.6 percent of sodium acetate, about 6.2 percent of sodium bisulfite and 6.8 percent of sodium carboxymethylcellulose.
The components of the cleansing composition can be combined in several different orders or sequences. In a particularly convenient procedure, the cationic surface active agent, mineral oil and lanolin, are melted together and to the mixture with good stirring are added the glycerine and nonionic surface active agent. The solution of the alkali metal sulfite and buffering compound in warm water is added followed by the thickening agent. The stirring is continued briefly and the mixture is then cooled.
The cleansing composition of this invention is a stable, soft cream which is easily applied to the skin. The cleansing cream is applied to the hands and the cream is worked into the skin until the stains are removed. When the stains have been removed, the excess cream can be wiped off or it can be flushed off with water.
EXAMPLE 1 A mixture of 400 parts of cetyl dimethyl ethyl ammonium bromide, 415 parts of mineral oil and 200 parts of lanolin is melted, and to the melt with good stirring there are added 630 parts of glycerine and 525 parts of the condensation product of 1 mole of nonylphenol with about 9.5 moles of ethylene oxide. With vigorous stirring, 2,000 parts of warm water, 30 parts of sodium acetate, 300 parts of sodium bisulfite and 325 parts of sodium carboxymethylcellulose are added. The mixture is stirred for about 30 minutes and is then cooled. The product removes stains of malachite green, fuchsine and methyl violet from the skin and leaves the skin soft.
EXAMPLE 2 A mixture of 50 parts of propylene glycol monostearate and 200 parts of cetyl dimethyl ethyl ammonium bromide is melted, and 210 parts of mineral oil, parts of lanolin, 315
parts of glycerine, 1,000 parts of water, 500 parts of sodium bisulfite, 50 parts of sodium acetate and 95 parts of sodium carboxymethylcellulose are added in the stated order with good stirring.
The product removes stains of methyl violet, fuchsine and malachite green from the skin and leaves the skin soft.
EXAMPLE 3 A mixture of 100 parts of propylene glycol monostearate and 100 parts of di(polyethoxylated) stearyl methyl ammonium chloride (containing a total of 15 ethylene oxide units per molecule) and 415 parts of mineral oil is melted, and while the mixture is vigorously stirred, a solution of 500 parts of sodium bisulfite in 1,000 parts of water is slowly added. The thin solution is then thickened by addition of 200 parts of sodium carboxymethylcellulose. A solution of 90 parts of lanolin in 200 parts of glycerine is then added.
The product removes stains of malachite green, fuchsine and methyl violet from the skin and leaves the skin soft.
EXAMPLE 4 To a stirred mixture of 100 parts of di(polyethoxylated) stearyl methyl ammonium chloride (containing a total of 15 ethylene oxide units per molecule) and 415 parts of mineral oil, there is added a solution of 500 parts of sodium bisulfite in 1,000 parts of water. The resulting solution is heated to 90C. and stirred with cooling. Sodium carboxymethylcellulose (200 parts) is added, followed by a solution of 90 parts of lanolin in 250 parts of glycerine.
The product removes stains of malachite green, fuchsine and methyl violet from the skin and leaves the skin soft.
I claim:
1. A hand cleansing composition consisting essentially of:
1. from about 3 to about 12 percent of a cationic quaternary ammonium salt of the formula:
wherein R is methyl, ethyl or -(CH CH O),,H in which n is an integer of from 5 to 15; R is lower alkyl, benzyl or (CH CH O),,H; and X is chloride or bromide;
2. from about 5 to about 20 percent of mineral oil;
3. from about 2 to about 6 percent of lanolin;
4. from about 5 to about 18 percent of glycerine;
5. from about 3 to about 25 percent of an alkali metal sulfite;
6. from about 2 to about 12 percent of sodium carboxymethylcellulose; and
7. from about 30 to about 50 percent of water.
2. A composition according to Claim 1 containing up to about 15 percent of a non-ionic surface active agent selected from (a) a condensation product of 1 mole proportion of nonylphenol with from 4 to 30 mole proportions of ethylene oxide and (b) a glycol monoester of a long-chain fatty acid.
3. A composition according to Claim 2 containing up to about 2.5 percent of an alkali metal acetate as buffering agent.
4. A composition according to claim 1 containing:
1. from 6 to 10 percent of cetyl dimethyl ethyl ammonium bromide;
2. from 7 to 10 percent of mineral oil;
3. from 3 to 5 percent lanolin;
4. from 10-15 percent glycerine; V
5. from 10 to 15 percent sodium bisulfite;
6. from 5 to 8 percent sodium carboxymethylcellulose;
7. from 35-45 percent of water;
8. from 7-12 percent of the condensation product of 1 mole proportion of nonylphenol and 9.5 mole proportions of ethylene oxide; and
9. from 0.5 to 1 percent of sodium acetate.
Claims (17)
- 2. from 7 to 10 percent of mineral oil;
- 2. from about 5 to about 20 percent of mineral oil;
- 2. A composition according to Claim 1 containing up to about 15 percent of a non-ionic surface active agent selected from (a) a condensation product of 1 mole proportion of nonylphenol with from 4 to 30 mole proportions of ethylene oxide and (b) a glycol monoester of a long-chain fatty acid.
- 3. A composition according to Claim 2 containing up to about 2.5 percent of an alkali metal acetate as buffering agent.
- 3. from about 2 to about 6 percent of lanolin;
- 3. from 3 to 5 percent lanolin;
- 4. from 10-15 percent glycerine;
- 4. from about 5 to about 18 percent of glycerine;
- 4. A composition according to claim 1 containing:
- 5. from about 3 to about 25 percent of an alkali metal sulfite;
- 5. ''from 10 to 15 percent sodium bisulfite;
- 6. from 5 to 8 percent sodium carboxymethylcellulose;
- 6. from about 2 to about 12 percent of sodium carboxymethylcellulose; and
- 7. from about 30 to about 50 PERCENT of water.
- 7. from 35-45 percent of water;
- 8. from 7-12 percent of the condensation product of 1 mole proportion of nonylphenol and 9.5 mole proportions of ethylene oxide; and
- 9. from 0.5 to 1 percent of sodium acetate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8906570A | 1970-11-12 | 1970-11-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3666690A true US3666690A (en) | 1972-05-30 |
Family
ID=22215488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US89065A Expired - Lifetime US3666690A (en) | 1970-11-12 | 1970-11-12 | Skin cleansing composition |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3666690A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4295985A (en) * | 1979-10-25 | 1981-10-20 | Petrow Henry G | Method of removal of chlorine retained by human skin and hair after exposure to chlorinated water, and soap and shampoo compositions adapted to effect said removal |
| US4476044A (en) * | 1982-05-13 | 1984-10-09 | Henkel Corporation | Surfactant product |
| US4707189A (en) * | 1984-11-07 | 1987-11-17 | Hercules Incorporated | Biostable compositions and the aqueous solutions thereof as thickeners for aqueous-based systems |
| US4708813A (en) * | 1985-08-14 | 1987-11-24 | The Procter & Gamble Company | Nonlathering cleansing mousse with skin conditioning benefits |
| US4798682A (en) * | 1985-06-18 | 1989-01-17 | Henkel Kommanditgesellschaft Auf Aktien | Oil-in-water emulsions with increased viscosity under shear stress |
| US4806262A (en) * | 1985-08-14 | 1989-02-21 | The Procter & Gamble Company | Nonlathering cleansing mousse with skin conditioning benefits |
| EP0318279A3 (en) * | 1987-11-26 | 1990-04-04 | Unilever Plc | Machine dishwashing compositions |
| US4950475A (en) * | 1988-07-19 | 1990-08-21 | Imaginative Research Associates, Inc. | Novel film-forming gels with high concentrations of humectants and emollients |
| WO1994028715A1 (en) * | 1993-06-09 | 1994-12-22 | Lonza Inc. | Quaternary ammonium and waterproofing/preservative compositions |
| US5855817A (en) * | 1993-06-09 | 1999-01-05 | Lonza, Inc. | Waterproofing and preservative compositions and preparation thereof |
| US6136775A (en) * | 1998-12-18 | 2000-10-24 | Kimberly-Clark Worldwide, Inc. | Wet wipe with non-aqueous, oil-based solvent for industrial cleaning |
| US20040231070A1 (en) * | 2003-05-19 | 2004-11-25 | The Procter & Gamble Company | Cosmetic compositions comprising a polymer and a colorant |
| US20050116198A1 (en) * | 2001-11-08 | 2005-06-02 | Douglas Ryan | Stabilisation of particulate material using wool grease |
| RU2322435C1 (en) * | 2007-01-19 | 2008-04-20 | Институт органической и физической химии им. А.Е. Арбузова Казанского научного центра РАН (ИОФХ им. А.Е. Арбузова КазНЦ РАН) | N-[alkylphenoxypoly(ethyleneoxy)carbonylmethyl]-morpholinium chlorides possessing property of inhibitors of asphalt-resin-paraffin deposits, method for their preparing |
| WO2008058717A3 (en) * | 2006-11-17 | 2009-05-22 | Beiersdorf Ag | Cosmetic preparations having a high glycerol content |
| WO2010125050A3 (en) * | 2009-04-28 | 2011-01-13 | Pastaclean Gmbh | Cleaning paste |
| CN109953908A (en) * | 2019-03-13 | 2019-07-02 | 广州莱倩化妆品有限公司 | A kind of formula and preparation method thereof of essence cream |
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| US2948686A (en) * | 1955-07-14 | 1960-08-09 | G H Packwood Mfg Company | Thixotropic and fast breaking skin cleaner emulsion and process for producing the same |
| US3178371A (en) * | 1960-10-31 | 1965-04-13 | David L Berman | Lipstick removing methods |
| US3207694A (en) * | 1961-05-26 | 1965-09-21 | Colgate Palmolive Co | Compositions for and processes of removing stains |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4295985A (en) * | 1979-10-25 | 1981-10-20 | Petrow Henry G | Method of removal of chlorine retained by human skin and hair after exposure to chlorinated water, and soap and shampoo compositions adapted to effect said removal |
| US4476044A (en) * | 1982-05-13 | 1984-10-09 | Henkel Corporation | Surfactant product |
| US4707189A (en) * | 1984-11-07 | 1987-11-17 | Hercules Incorporated | Biostable compositions and the aqueous solutions thereof as thickeners for aqueous-based systems |
| US4798682A (en) * | 1985-06-18 | 1989-01-17 | Henkel Kommanditgesellschaft Auf Aktien | Oil-in-water emulsions with increased viscosity under shear stress |
| US4708813A (en) * | 1985-08-14 | 1987-11-24 | The Procter & Gamble Company | Nonlathering cleansing mousse with skin conditioning benefits |
| US4806262A (en) * | 1985-08-14 | 1989-02-21 | The Procter & Gamble Company | Nonlathering cleansing mousse with skin conditioning benefits |
| AU618036B2 (en) * | 1987-11-26 | 1991-12-12 | Unilever Plc | Machine dishwashing compositions |
| EP0318279A3 (en) * | 1987-11-26 | 1990-04-04 | Unilever Plc | Machine dishwashing compositions |
| US4950475A (en) * | 1988-07-19 | 1990-08-21 | Imaginative Research Associates, Inc. | Novel film-forming gels with high concentrations of humectants and emollients |
| WO1994028715A1 (en) * | 1993-06-09 | 1994-12-22 | Lonza Inc. | Quaternary ammonium and waterproofing/preservative compositions |
| US5855817A (en) * | 1993-06-09 | 1999-01-05 | Lonza, Inc. | Waterproofing and preservative compositions and preparation thereof |
| US6136775A (en) * | 1998-12-18 | 2000-10-24 | Kimberly-Clark Worldwide, Inc. | Wet wipe with non-aqueous, oil-based solvent for industrial cleaning |
| US20050116198A1 (en) * | 2001-11-08 | 2005-06-02 | Douglas Ryan | Stabilisation of particulate material using wool grease |
| US20040231070A1 (en) * | 2003-05-19 | 2004-11-25 | The Procter & Gamble Company | Cosmetic compositions comprising a polymer and a colorant |
| US7837742B2 (en) | 2003-05-19 | 2010-11-23 | The Procter & Gamble Company | Cosmetic compositions comprising a polymer and a colorant |
| WO2008058717A3 (en) * | 2006-11-17 | 2009-05-22 | Beiersdorf Ag | Cosmetic preparations having a high glycerol content |
| RU2322435C1 (en) * | 2007-01-19 | 2008-04-20 | Институт органической и физической химии им. А.Е. Арбузова Казанского научного центра РАН (ИОФХ им. А.Е. Арбузова КазНЦ РАН) | N-[alkylphenoxypoly(ethyleneoxy)carbonylmethyl]-morpholinium chlorides possessing property of inhibitors of asphalt-resin-paraffin deposits, method for their preparing |
| WO2010125050A3 (en) * | 2009-04-28 | 2011-01-13 | Pastaclean Gmbh | Cleaning paste |
| CN109953908A (en) * | 2019-03-13 | 2019-07-02 | 广州莱倩化妆品有限公司 | A kind of formula and preparation method thereof of essence cream |
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