EP0919611A1 - Barre de nettoyage ayant des niveaux élevés en liquides et en silice particulaire - Google Patents

Barre de nettoyage ayant des niveaux élevés en liquides et en silice particulaire Download PDF

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Publication number
EP0919611A1
EP0919611A1 EP98120910A EP98120910A EP0919611A1 EP 0919611 A1 EP0919611 A1 EP 0919611A1 EP 98120910 A EP98120910 A EP 98120910A EP 98120910 A EP98120910 A EP 98120910A EP 0919611 A1 EP0919611 A1 EP 0919611A1
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EP
European Patent Office
Prior art keywords
composition
cleansing
liquid phase
silica
fumed silica
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.)
Withdrawn
Application number
EP98120910A
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German (de)
English (en)
Inventor
Jose E. Ramirez
Mohan Vishnupad
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Imaginative Research Associates Inc
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Imaginative Research Associates Inc
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Filing date
Publication date
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Publication of EP0919611A1 publication Critical patent/EP0919611A1/fr
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/002Surface-active compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/006Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0094High foaming compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2065Polyhydric alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/18Water-insoluble compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/24Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/26Organic compounds, e.g. vitamins containing oxygen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/26Organic compounds, e.g. vitamins containing oxygen
    • C11D9/265Organic compounds, e.g. vitamins containing oxygen containing glycerol

Definitions

  • This disclosure relates generally to personal cleansing bars with lathering detergents and/or soaps.
  • the bars have a high liquid content in combination with lathering additives ad particulate silica to give the bars a desirable consistency.
  • a superior processable mild personal cleansing bar formulation with good mildness, good smear, good lather potential and good rinsability is difficult to formulate, but would be highly desirable.
  • particulate silica in certain ratios with emollients like oils, waxes, petrolatum, esters and/or humectants like polyols, e.g., glycerine, propylene glycol, polyethylene glycol, sorbitol, etc. and/or water in combination with detergent and/or soap additives can be formulated into cleansing bars of good hardness and acceptable processing characteristics.
  • emollients like oils, waxes, petrolatum, esters and/or humectants like polyols, e.g., glycerine, propylene glycol, polyethylene glycol, sorbitol, etc. and/or water in combination with detergent and/or soap additives
  • emollients like oils, waxes, petrolatum, esters and/or humectants like polyols, e.glycerine, propylene glycol, polyethylene glycol, sorbitol, etc. and/or water
  • a novel finding of these compositions is the effect of particulate silica having a high surface area on detergents from the groups consisting of sodium acyl isethionate, sodium alpha olefin sulfonates, disodium alkyl sulfosuccinate, soap base, tallow and coco sodium salts, and mixtures thereof, which produces a hard processable cleansing bar.
  • the hardening effect desirable for processing is observed at silica contents of a minimum of 1 part silica to 10 parts of liquid on a w/w basis, varying according to the particular liquids and waxes employed.
  • Particularly useful embodiments of the present cleansing bar compositions contain: a liquid phase consisting of either mineral, vegetable oils or polyols with or without the addition of waxes; amorphous silica; and soap, detergent or a mixture thereof.
  • the composition is capable of foaming when combined with water during use.
  • the present compositions provide formulations of a flowable phase of liquids, or of oils or of oils and waxes and silica which, upon combination with soap and/or detergents can be processed and stamped into a cleansing bar.
  • This disclosure relates generally to formulations of cleansing bars having high liquid and particulate silica content and containing levels of a suitable hardening agent or agents in combination with soap and/or detergents and additives that give the bars a desirable consistency. More particularly, this disclosure is concerned with the discovery that cleansing bars with soap and/or detergents and high levels of oils or high levels of polyols or water can be formulated properly and. fabricated using well-established equipment and procedures. In contrast, most synthetic detergents and detergent-filler combinations that are presently available do not become plastic and modifications have to be made to the manufacturing equipment and fatty acids and soap-like ingredients have to be added for suitable manufacturing.
  • oils, polyols, water and other materials like petrolatum, paraffin and waxes is well known in the fabrication of bars.
  • oils and waxes because of their foam suppressing and softening properties, the use of oils and waxes is limited to low levels in cleansing bars.
  • the use of oils, waxes and polyols in synthetic detergent bars softens the product, making it very difficult to prepare a suitable commercial bar.
  • a novel finding of the compositions described herein is that silica when used in certain ratios in the liquid phase, allows the preparation of cleansing bars that can be processed using established manufacturing methods while aiding with the foaming characteristics of the bars.
  • the first component of the compositions described herein is a liquid phase which contains oils, and/or polyols and optionally waxes.
  • the oils can be mineral oils which are a purified mixture of liquid hydrocarbons obtained from petroleum. Normally, mineral oils are a mixture of oils of the methane series having the general formula C n H 2n+2 .
  • the oils can be of vegetable origin, that is extracted from the seeds, fruits or leaves of plants and generally considered to be mixtures of mixed glycerides (e.g., sesame, avocado, olive, cottonseed, etc.). Mixtures of vegetable and mineral oils can also be used in the oil phase.
  • the oils can be modified by the addition of paraffinic and microcrystalline waxes.
  • a particularly useful oil phase is petrolatum.
  • Petrolatum is a combination of mineral oils and wax which forms a white to faintly yellow unctuous mass of well recognized pharmaceutical properties.
  • the preferred white petrolatum USP has a density of from about 0.82 to about 0.865, a melting point of from about 38E to 54EC and a refractive index of from about 1.460 to 1.474.
  • the polyols can be glycerine, corn syrup, propylene glycol, dibutylene glycol, dipropylene glycol or other liquid polyfunctional alcohols. As exemplified hereinafter, in certain embodiments, the liquid phase contains no added water.
  • the liquid phase constitutes from about 15 to about 45 percent by weight of the final composition.
  • the liquid phase is from about 20 to about 40 weight percent of the final composition.
  • the second component of the present compositions is an effective amount of silica.
  • Silica gives the liquid phase an appropriate degree of solid characteristic so that the resulting mixture can be processed with soaps, detergents or mixtures thereof.
  • Any particulate silica having a surface area greater than about 75 m 2 /g is suitable.
  • the particulate silica is amorphous and has a surface area of greater than 100 m 2 /gm.
  • a particularly useful amorphous silica is fumed silica.
  • Fumed silica is fumed silicon oxide, SiO 2 , a material which is produced by the hydrolysis of silicon tetrachloride vapor in a flame of hydrogen and oxygen.
  • molten spheres of silica are formed with extremely small particle size and enormous surface area.
  • the resulting fumed silica is a fluffy white powder of very low bulk density, from 2.5 to 5 lbs./ft 3 and a surface area from 10 to 380 m 2 /gm.
  • Other silicas having the desired surface area are also suitable; such as, for example precipitated silicas or silica fume.
  • the particulate silica should be present in the composition in an amount sufficient to harden the composition.
  • the hardness of the composition is conveniently ascertained by measuring penetration value as described more fully hereinafter.
  • the ratio of liquid phase to silica is preferably greater than about 2:1 more preferably in the range of about 4:1 to about 10:1.
  • the effective amount of particulate silica will range from about 3 percent by weight of the final composition to about 20 percent by weight of the final composition. Preferably, from about 3 to about 15 weight percent silica is present.
  • the third component of the present composition is a cleansing agent, e.g., a soap, a detergent or a mixture thereof.
  • a composition is produced that can be processed and stamped into a cleansing bar and when combined with water exhibits foaming behavior.
  • a particularly useful soap base suitable for personal care is a blend of tallow and coco sodium salts (80/20).
  • Representative classes of detergents which have been found to be useful are the sodium acyl isethionates, the sodium alpha olefin sulfonates and disodium alkyl sulfosuccinates. However, this disclosure is not limited to these detergents.
  • the amount of cleansing agent included in the composition will vary depending on the exact detergent chosen, the identity of other components employed, and the desired physical and performance characteristics to be achieved. Normally, however, the amount of cleansing agent in particularly useful embodiments will range from about 25 to about 85 percent by weight of the final composition. Preferably, the cleansing agent is present in an amount from about 40 to about 75 percent by weight of the final composition.
  • the detergent chosen should be mild to the skin and relatively unaffected by ions which might be present in hard water.
  • An unusual finding in connection with the compositions of this disclosure is that when adding silica to oils or oils and waxes (preferably molten), and/or polyols and processing the resulting composition through a blade blender and a screw mixer, the resulting mass can be compacted into a solid that has similar hardness characteristics as compacted soaps, detergents or mixtures thereof. This allows the blend of oils or oils and waxes and/or polyols and silica to be added to the soap, detergent or mixtures thereof without the resulting softening characteristics of adding oils by themselves.
  • foam boosters may be incorporated into the present compositions.
  • Suitable foam enhancers include potassium polymetaphosphate, sodium lauryl sulfoacetate, sodium lauryl sulfate, sodium lauryl sarcosinate, acyl glutamate and amides. These materials will enhance the foam produced when the present compositions are exposed to water during use.
  • compositions may also contain conventional additives such as fragrance, color, fillers, preservatives, etc.
  • active ingredients may be incorporated in the present compositions.
  • Such active ingredients include, but are not limited to deodorants, medicaments such as, for example coal-tar, benzoyl peroxide, vitamin A and vitamin E, and antibacterial ingredients such as, for example, triclosan, PVP-iodine, salicylic acid and sunscreens.
  • the amount of active ingredient included in the present compositions should be an "effective amount" by which it is meant an amount sufficient to achieve a desired effect. The precise amount that is effective will depend upon the particular active ingredient and the desired effect to be achieved. Normally, an effective amount will be from about 0.001 to about 10 weight percent, more preferably from about 0.01 to about 5.0 weight percent.
  • compositions described herein are preferably prepared by first mixing the ingredients of the liquid phase. Silica is then added to the liquid phase. Heating and vigorous mixing may be used to aid in providing a homogenous liquid/silica composition. Next, the cleansing agent is added to and mixed with the liquid/silica mixture. At this point, the composition can be pelletized, if desired. Finally, any additives (fragrance, filler, active ingredient, etc.) are added to the composition. In certain particularly useful embodiments, the composition from which the cleansing bar is formed contains less than about 10% by weight of added water. Once prepared, the composition can be formed into a bar using known techniques. One such technique is described, for example, in U.S. Patent No. 4,812,253, the disclosure of which is incorporated herein by this reference.
  • Examples 1-4 present formulations of the compacted mass that is produced when fumed silica and petroleum jelly are mixed and properly processed.
  • compositions of Examples 1 to 4 show the effect that changing the ratios of silica to petrolatum has on the consistency of the compacted mass. Comparative example A has been included to show the consistency of pure petrolatum.
  • the petroleum jelly employed in the Examples was designated White Petrolatum USP, G1951, and is commercially available from Witco, Greenwich, CT.
  • the silica used in the Examples presented herein is a fumed silica sold under the trademark CAB-O-SIL, available from Cabot Corp., Tuscola, III. The results are presented in Table I. Example No.
  • the consistency of the resulting paste or solid is tested using a Penetrometer (Universal Penetrometer, ASTM, (Precision 73510), Catalog No. 33541, Macalaster Bicknell Company of Connecticut, Inc., New Haven, Connecticut) which was equipped with a 300g cone.
  • the amount of penetration of the cone into the sample was displayed by, and read off, the penetrometer in units of mm x 10. A lower penetration value indicates a harder mass.
  • the samples were compacted by adding 20g of mixture to a die punch. The pasty or powdery mixture was then compressed to form discs 12" wide by 5/8" high.
  • the compositions of this invention have penetration values of less than about 50 mm x 10.
  • the compositions preferably have a ratio of silica to oil phase greater than about 0.1.
  • Examples 5-8 present formulations of the compacted mass that is produced when fumed silica and glycerin are mixed and properly processed.
  • compositions of Examples 5-8 show the effect that changing the ratios of silica to glycerin has on the consistency of the compacted mass.
  • Comparative example B has been included to show the consistency of pure glycerin.
  • the glycerin employed in the Examples was designated glycerin USP, 99.5% and is commercially available from Ruger Chemical, 83 Cordier Street, Irvington, N.J.
  • the consistency of the compositions, tested as previously described, are reported in Table II.
  • the glycerine-based compositions in accordance with this disclosure preferably have a silica to glycerine ratio greater than about 0.25.
  • Examples 9 to 20 present the hardness of the compacted mass that is produced when fumed silica, petroleum jelly and soap are mixed and properly processed. The consistency of the resulting paste or solid is tested as previously described, that is by using a Penetrometer and measuring the hardness of the resulting 20g disc. Comparative examples C, D and E have been included to show the consistency of the commercial soap base with petrolatum and no fumed silica. The results are present in Table III. Example No.
  • Examples 21-32 present the hardness of the compacted mass that is produced when fumed silica, glycerin and soap are mixed and properly processed. The consistency of the resulting paste or solid is tested as previously described, that is by using a Penetrometer and measuring the hardness of the resulting 20g disc. Comparative examples F, G, and H have been included to show the consistency of the commercial soap base with glycerin and no filmed silica. The results are presented in Table IV.
  • the resulting mixtures required at least about 1 part of fumed silica for 5 parts of glycerin for the bars with the lower levels of glycerin (20%) to have a penetration of approximately 50 mm x 10 or less.
  • Higher levels of glycerin (40%) require at least about 1 part of fumed silica in 3 parts of glycerin for bars with penetration values lower than 50 mm x 10.
  • the hardness of the soap mass without silica and without glycerin added is approached by all blends of glycerin, silica, and soap, once the ratio Si/Glycerine is 0.5 or higher.
  • Examples 33-44 present the penetration values of the compacted mass that is produced when fumed silica, petroleum jelly and a commercial blend of syndet and soap are mixed and properly processed. The consistency of the paste or solid is tested as previously described. Comparative examples I, J and K have been included to show the consistency of the commercial soap/syndet base with petrolatum and no fumed silica.
  • Example No. I 33 34 35 36 Petroleum Jelly USP 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Fumed Silica 0.0 4.0 5.0 6.67 10.0 Soap/Syndet Base 80.0 76.0 75.0 73.33 70.0 R Si/PJ 0.0 0.2 0.25 0.33 0.5 Penetration Value (mmx10) 90.0 35.0 30.0 23.0 15.0
  • the resulting mixtures require at least about 1.5 parts of fumed silica for 10 parts of petroleum jelly for bars with the lower levels of petroleum jelly (20%) while the higher levels of petroleum jelly (40%) require at least about 1 part of fumed silica to 4 parts of petroleum jelly to increase hardness of the syndet/soap bars to values less than 50mm x 10. It will be pointed out that the hardness of the syndet/soap mass processed without fumed silica and without petroleum jelly is 15mm x 10. This value is approached by all blends of petroleum jelly, silica and syndet/soap, once the ratios of fumed silica to petroleum jelly has a value of 0.5 or higher.
  • Examples 45-56 present the hardness of the compacted mass that is produced when fumed silica, petroleum jelly and a commercial blend of syndet are mixed and properly processed. Comparative examples L, M and N have been included to show the consistency of the commercial syndet base with petroleum and no fumed silica.
  • the consistency of the paste or solid is tested as previously described.
  • the resulting mixtures require at least about 1 part of fumed silica for 5 parts of petroleum jelly for bars with the lower levels of petroleum jelly (20%) while the higher levels of petroleum jelly (40%) require at least about 1 part of fumed silica to 3.5 parts of petroleum jelly to increase hardness of the syndet bars to values of 50mm x 10.
  • the hardness of the syndet mass processed without fumed silica and petroleum jelly is 15mm x 10. This value is approached by all blends of petroleum jelly, silica and syndet, once the ratio of fumed silica to petroleum jelly has a value of 0.5 or higher (that is 1 part of fumed silica to 2 parts of petroleum jelly).
  • compositions in accordance with the present invention are additional specific, non-limiting examples of compositions in accordance with the present invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
EP98120910A 1997-11-07 1998-11-04 Barre de nettoyage ayant des niveaux élevés en liquides et en silice particulaire Withdrawn EP0919611A1 (fr)

Applications Claiming Priority (2)

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US96589697A 1997-11-07 1997-11-07
US965896 1997-11-07

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EP (1) EP0919611A1 (fr)
JP (1) JPH11217587A (fr)
KR (1) KR19990045091A (fr)
AU (1) AU747236B2 (fr)
CA (1) CA2253046A1 (fr)

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FR3007641A1 (fr) * 2013-06-27 2015-01-02 Oreal Composition nettoyante stable sous forme de solide souple
US9187722B2 (en) 2012-12-28 2015-11-17 The Dial Corporation Controlling a release of a cleaning agent by sorbing the agent on silica particles
EP3138454A1 (fr) * 2015-09-01 2017-03-08 New Flag GmbH Dispositif de lavage
US10201485B2 (en) 2014-10-30 2019-02-12 Amorepacific Corporation Washing composition

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JP3763567B2 (ja) * 2001-01-19 2006-04-05 株式会社資生堂 化粧料
CN109589279B (zh) * 2019-01-08 2020-03-20 明辉实业(深圳)有限公司 一种固体洗发水及其制备方法

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EP0194126A2 (fr) * 1985-03-05 1986-09-10 The Procter & Gamble Company Compositions détergentes
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US9187722B2 (en) 2012-12-28 2015-11-17 The Dial Corporation Controlling a release of a cleaning agent by sorbing the agent on silica particles
FR3007641A1 (fr) * 2013-06-27 2015-01-02 Oreal Composition nettoyante stable sous forme de solide souple
WO2014207697A3 (fr) * 2013-06-27 2015-05-21 L'oreal Composition cosmetique aqueuse sous forme de solide souple
US10201485B2 (en) 2014-10-30 2019-02-12 Amorepacific Corporation Washing composition
EP3138454A1 (fr) * 2015-09-01 2017-03-08 New Flag GmbH Dispositif de lavage

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KR19990045091A (ko) 1999-06-25
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AU747236B2 (en) 2002-05-09
JPH11217587A (ja) 1999-08-10

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