CA2173120A1 - Skin-cleansing agents, methods of preparing them and their use - Google Patents
Skin-cleansing agents, methods of preparing them and their useInfo
- Publication number
- CA2173120A1 CA2173120A1 CA002173120A CA2173120A CA2173120A1 CA 2173120 A1 CA2173120 A1 CA 2173120A1 CA 002173120 A CA002173120 A CA 002173120A CA 2173120 A CA2173120 A CA 2173120A CA 2173120 A1 CA2173120 A1 CA 2173120A1
- Authority
- CA
- Canada
- Prior art keywords
- skin
- skin cleaning
- cleaning agents
- paste
- water
- 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.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- 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
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
- A61K8/9783—Angiosperms [Magnoliophyta]
- A61K8/9789—Magnoliopsida [dicotyledons]
-
- 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
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
Abstract
The invention concerns water-containing skin-cleansing agents in liquid, paste or cream form designed to remove strongly adhering dirt, the agents containing anionic and/or amphoteric and/or non-ionic surfactants as wash-active substances, thickeners, at least one abrasive plus, optionally, auxiliaries for regulating the appearance consistency, odour and stability such as pigments, fragrances, stabilizers and preservatives. The agents are characterized in that the only solvent they contain is di-n-butyl and/or diisopropyl adipate. The agents are prepared by thorough mixing of the ingredients, the mixture optionally being heated. If a C8-C16 fatty alcohol is added as a consistency regulator, heating of the mixture becomes unnecessary.
Furthermore, the addition of a fatty alcohol enhances the cleansing action.
The invention also concerns the use of such skin-cleansing agents, the agent first being spread on to the skin without the addition of water or with the addition of a small quantity of water, and the cleansing process continued and completed by rinsing with water.
Furthermore, the addition of a fatty alcohol enhances the cleansing action.
The invention also concerns the use of such skin-cleansing agents, the agent first being spread on to the skin without the addition of water or with the addition of a small quantity of water, and the cleansing process continued and completed by rinsing with water.
Description
~ ; 2i7~1 20 Skin Cleaning Agents, a Process for their Production and their Use The present invention relates to skin cleaning agents having an improved cleaning action and a gentle behavior to the skin. The present invention further relates to a process for their production and to the use of the agents as flowable hand cleaning agents and heavy-duty hand cleaning agents.
Hand cleaning agents, in particular for the removal of strongly ad-hering dirt, have already been used in the industrial sector for some time. Patent application No. W0 91/14 420 describes clean-ing agents which, in addition to anionic and/or non-ionogenic sur-factants, comprise conventional abrasives, organic solvents in the form of carboxylic acid esters, in particular certain acetates, such as preferably n-butoxy-2-ethoxy-ethyl-acetate and fatty alkanolam-ides, fatty polyalkanolamides, the ethylene oxide and/or propylene oxide addition products thereof, as well as fatty acid monoglycer-ides as re-greasing agents. Another preferred, additionally used solvent in these hand cleansing agents is limonene, which is known to have a dermal incompatibility involving a sensitization risk. In order to produce the agents according to W0 91/14 420 in an efficient manner, it is necessary to heat the mixture to tem-peratures above 50C after mixing the raw materials, requiring additional heating energy and involving longer production periods.
Furthermore, hand cleaning agents are known which comprise as solvent component natural oils, such as olive oil, jojoba oil, maca-damia-nuts-oil, and grape-seed oil. These cleaning agents have lim-ited detergent properties due to the interaction between the oil portions and the detergent portions and because of the low soil-removing capacity of the natural oil.
Hand cleaning agents, in particular for the removal of strongly ad-hering dirt, have already been used in the industrial sector for some time. Patent application No. W0 91/14 420 describes clean-ing agents which, in addition to anionic and/or non-ionogenic sur-factants, comprise conventional abrasives, organic solvents in the form of carboxylic acid esters, in particular certain acetates, such as preferably n-butoxy-2-ethoxy-ethyl-acetate and fatty alkanolam-ides, fatty polyalkanolamides, the ethylene oxide and/or propylene oxide addition products thereof, as well as fatty acid monoglycer-ides as re-greasing agents. Another preferred, additionally used solvent in these hand cleansing agents is limonene, which is known to have a dermal incompatibility involving a sensitization risk. In order to produce the agents according to W0 91/14 420 in an efficient manner, it is necessary to heat the mixture to tem-peratures above 50C after mixing the raw materials, requiring additional heating energy and involving longer production periods.
Furthermore, hand cleaning agents are known which comprise as solvent component natural oils, such as olive oil, jojoba oil, maca-damia-nuts-oil, and grape-seed oil. These cleaning agents have lim-ited detergent properties due to the interaction between the oil portions and the detergent portions and because of the low soil-removing capacity of the natural oil.
2 2~73120 In cosmetics the use of special esters of the adipic acid is known.
For instance, owing to its slightly greasing character, di-n-butyl adipate is used in day creams and liquid emulsions as well as in hair sprays and setting lotions as softening component or agent to achieve a superfatted state.
Patent No. GB 1,106,945 describes aqueous shampoo prepara-tions for hair cleaning purposes; they comprise as solvents for fats alkyl esters of the dibasic carboxylic acids, phthalic acid or adipic acid. In hair cleaning and hair conditioning, particularly good re-sults are obtained with dimethyl phthalate, however, there is no reference with respect to skin cleaning, in particular to the clean-ing of skin heavily soiled by foreign substances.
EP 229 616 A2 describes bath additives comprising diisopropyl adipate as oil component which deposits on the skin.
EP 513 832 A1 describes pharmaceutical products comprising di-butyl adipate or a combination of dibutyl adipate and isopropyl myristate to improve or to control the skin penetration of a thera-peutic agent.
Diisopropyl adipate is additionally used as lubricant in alcoholic lotions, as softener in hair aerosols and as fat factor in hair tonics and as solubilizer for perfumes.
PCT-application No. W0 92/09 265 describes a solvent-containing hand cleaning paste containing as solvent DBE 2, dimethyl adi-pate, dimethyl glutarate and dimethyl succinate, in an amount up to 54 parts per 100 parts of cleaning agent, as well as isooctyl stearate as additionally required re-greasing agent and bleached kernel or shell flour as mild abrasive.
'3 217312~
.
In EP No. 0166522 A2 a cosmetic preparation for the removal of nail varnish is described, which has also skin cleaning properties and comprises as solvent for the nail enamel esters of dicarboxylic acids, preferably diesters or esters of diols, preferably dioldiesters.
The diethyl esters of dicarboxylic acids having up to 6 C-atoms are preferred as dicarboxylic acid esters, and the diacetates of diols having 2 to 6-C-atoms are preferred as diol esters. Additionally, the preparations contain lanolin or other re-greasing components and no abradant.
For this reason, the use of the known solvents in skin cleaning agents has made it necessary until today to compensate their in-tense effect on the skin by the action of re-greasing agents. How-ever, the detergent action of the surfactants is slightly affected by the re-greasing components.
Accordingly, there was the object to provide skin cleaning agents and a process for their production, whose solvents have a compa-rable or improved cleaning action and thus an action which in-tensifies the cleaning effect, as well as an improved dermatologic compatibility. Additionally, there was the object to find a process for the manufacture of skin cleaning agents, in which heating of the raw material mixture may be omitted.
These objects have been achieved by skin cleaning agents which comprise as exclusive solvents di-n-butyl adipate and/or diisopro-pyl adipate and which, parallel to this, comprise as major compo-nents washing-active substances, components for the improve-ment of consistency, appearance, odor and storage stability, as well as at least one abrasive and water, and the production of which may be effected by using certain fatty alcohols in order to improve the cleaning action and the production conditions.
4 217312~
The subject matter of the present invention are hydrous, liquid, paste- or cream-like skin cleaning agents for the removal of strongly adhering dirt, which comprise anionic and/or amphoteric and/or non-ionogenic surfactants as washing-active substances, thickeners, at least one abrasive and, optionally, adjuvants for the regulation of consistency, appearance, odor, and stability, such as pigments, fragrances, stabilizers, and preservatives, and which are characterized in that they comprise di-n-butyl adipate and/or diiso-propyl adipate as exclusive solvents.
Known detergents are used as washing-active substances, in par-ticular anionic and/or amphoteric and/or non-ionogenic surfac-tants, e.g., alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, and fatty alcohol polyglycol sulfosuccinates, which are predominantly used in the form of their sodium salts, as well as the known non-ionogenic surfactants based on addition products of alkylene ox-ides to alkanols, alkanoic acids, which may also be capped at the end, and preferably alkyl polyglycosides.
Preferred surfactants include Na-lauryl ether sulfate, castor oil sul-fonate, di-Na-lauryl polyglycol ether sulfosuccinate, cocoamido-propyl betaine, and alkyl polyglycosides having an alkyl residue of Cg-C1 6~ preferably C8 to C10 and an oligoglycoside residue hav-ing an oligomerization degree of 1.1-1.7, preferably 1.2-1.3.
The portion of the active detergents amounts to 5-40%-wt., pref-erably 10 - 30%-wt., relative to the skin cleaning agent according to the present invention.
The portion of the esters di-n-butyl adipate and/or diisopropyl adi-pate in the agents according to the present invention amounts to 1 - 25%-wt., preferably 5 to 20%-wt., and particularly preferred 10 - 20%-wt.
21 7312~
Abrasives to be used with preference are the bleached kernel/shell flours according to WO 92/09265, in particular bleached walnut shell flour or olive kernel flour. The portion of the abrasive in the agent according to the present invention amounts to 1 - 30%-wt., preferably 10- 20%-wt.
The agents according to the present invention further comprise viscosity forming agents, such as organophilic and/or hydrophilic phyllosilicates, such as bentonites, polysaccharides, such as cel-lulose and guar flour, as well as modified polysaccharides, such as the cellulose ethers, carboxymethylcellulose, and hydroxyethyl-cellulose and xanthan gum, and inorganic electrolytes, such as NaCI or MgS04. They further comprise chromatophoric pigments, such as TiO2, stabilizers, such as propylene carbonate, pH-regula-tors, fragrances, and preservatives. The water content of the skin cleaning agents amounts to 1 0-50%-wt., preferably 20-40%-wt.
Re-greasing components may be omitted in the production of the skin cleansing agents according to the present invention.
Preferably, the skin cleaning agents are obtained as liquid or creamy agents or as flowable viscous pastes.
According to another preferred embodiment, the skin cleaning agents according to the present invention additionally comprise at least one fatty alcohol of the general formula R-OH wherein R rep-resents an alkyl residue having C8 to C1 6, preferably Cg-C12. The amount of the fatty alcohol in the agent amounts to 0.1-10.0%-wt., preferably 0.1-5.0%-wt.
The mentioned raw material components may usually also be em-ployed by using combinations of one type of raw material, i.e., as mixtures of different surfactants, viscosity formers, abrasives, and stabilizers, etc.
- 6 21733 ~0 The flowable skin cleansing agents are manufactured by means of known devices according to the batch or continuous method.
Suitable devices are heatable vessels including an agitator, mixer and extruder, e.g., described in "Surfactants in Consumer Prod-ucts", J. Falbe, Springer Verlag, 1987, page 399 ff.
The present invention further relates to a process for the produc-tion of the skin cleaning agents, in which the components are combined under stirring as usual, optionally using partial amounts of the raw materials, wherein the adipic ester solvents are pref-erably prepared first, and the pigment, viscosity forming agents/
thickeners, and a partial amount of the surfactant are added then;
this mixture is heated and preferably adjusted to a temperature of up to 70C, preferably 40-60C, whereupon the remaining raw material amounts, in particular surfactants amounts, the inorganic electrolyte, the pH-regulator and fragrance, the preservative, and the abrasive are added. The homogeneous mixture is then cooled and filled into conventional vessels, such as cans, pump vessels, such as dispensers, jars, and tubes.
According to a special production method according to the present invention, fatty alcohols are added as consistency regulators to produce the agents. Most surprisingly, it was found that the addition of the fatty alcohol allows the mixing the raw materials, e.g., in the succession as mentioned above, to form homogeneous products at room temperature, i.e., at 5 to 30C, without having to heat the raw material mixture. The fact that the heating phase is omitted and the involved saving of energy and time offer advan-tages with respect to process technology.
_ ` 7 217312~
Moreover, the addition of the fatty alcohol has a positive effect on the use of the skin cleansing agents since, for example, the deter-gent effect is increased.
The skin cleaning agents according to the present invention are particularly suitable for the removal of rough dirt strongly adhering to the skin, e.g., fats, oils and other lubricants, dyes, varnishes, tar, graphite, soot, coloring pigments, and similar substances oc-curring in industry and public utilities, in the craftsmen's trade, or in agriculture and in the household.
The use of the skin cleaning agents according to the present in-vention is preferably effected by first distributing the cleaning agent on the skin without water or with a small amount of water, continuing the cleaning with water and finishing by rinsing with water. The small amount of water results by wetting or moistening the soiled skin areas with water or aqueous liquids. For instance, in the case of dirty hands, this quantity may amount to about 1 to
For instance, owing to its slightly greasing character, di-n-butyl adipate is used in day creams and liquid emulsions as well as in hair sprays and setting lotions as softening component or agent to achieve a superfatted state.
Patent No. GB 1,106,945 describes aqueous shampoo prepara-tions for hair cleaning purposes; they comprise as solvents for fats alkyl esters of the dibasic carboxylic acids, phthalic acid or adipic acid. In hair cleaning and hair conditioning, particularly good re-sults are obtained with dimethyl phthalate, however, there is no reference with respect to skin cleaning, in particular to the clean-ing of skin heavily soiled by foreign substances.
EP 229 616 A2 describes bath additives comprising diisopropyl adipate as oil component which deposits on the skin.
EP 513 832 A1 describes pharmaceutical products comprising di-butyl adipate or a combination of dibutyl adipate and isopropyl myristate to improve or to control the skin penetration of a thera-peutic agent.
Diisopropyl adipate is additionally used as lubricant in alcoholic lotions, as softener in hair aerosols and as fat factor in hair tonics and as solubilizer for perfumes.
PCT-application No. W0 92/09 265 describes a solvent-containing hand cleaning paste containing as solvent DBE 2, dimethyl adi-pate, dimethyl glutarate and dimethyl succinate, in an amount up to 54 parts per 100 parts of cleaning agent, as well as isooctyl stearate as additionally required re-greasing agent and bleached kernel or shell flour as mild abrasive.
'3 217312~
.
In EP No. 0166522 A2 a cosmetic preparation for the removal of nail varnish is described, which has also skin cleaning properties and comprises as solvent for the nail enamel esters of dicarboxylic acids, preferably diesters or esters of diols, preferably dioldiesters.
The diethyl esters of dicarboxylic acids having up to 6 C-atoms are preferred as dicarboxylic acid esters, and the diacetates of diols having 2 to 6-C-atoms are preferred as diol esters. Additionally, the preparations contain lanolin or other re-greasing components and no abradant.
For this reason, the use of the known solvents in skin cleaning agents has made it necessary until today to compensate their in-tense effect on the skin by the action of re-greasing agents. How-ever, the detergent action of the surfactants is slightly affected by the re-greasing components.
Accordingly, there was the object to provide skin cleaning agents and a process for their production, whose solvents have a compa-rable or improved cleaning action and thus an action which in-tensifies the cleaning effect, as well as an improved dermatologic compatibility. Additionally, there was the object to find a process for the manufacture of skin cleaning agents, in which heating of the raw material mixture may be omitted.
These objects have been achieved by skin cleaning agents which comprise as exclusive solvents di-n-butyl adipate and/or diisopro-pyl adipate and which, parallel to this, comprise as major compo-nents washing-active substances, components for the improve-ment of consistency, appearance, odor and storage stability, as well as at least one abrasive and water, and the production of which may be effected by using certain fatty alcohols in order to improve the cleaning action and the production conditions.
4 217312~
The subject matter of the present invention are hydrous, liquid, paste- or cream-like skin cleaning agents for the removal of strongly adhering dirt, which comprise anionic and/or amphoteric and/or non-ionogenic surfactants as washing-active substances, thickeners, at least one abrasive and, optionally, adjuvants for the regulation of consistency, appearance, odor, and stability, such as pigments, fragrances, stabilizers, and preservatives, and which are characterized in that they comprise di-n-butyl adipate and/or diiso-propyl adipate as exclusive solvents.
Known detergents are used as washing-active substances, in par-ticular anionic and/or amphoteric and/or non-ionogenic surfac-tants, e.g., alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, and fatty alcohol polyglycol sulfosuccinates, which are predominantly used in the form of their sodium salts, as well as the known non-ionogenic surfactants based on addition products of alkylene ox-ides to alkanols, alkanoic acids, which may also be capped at the end, and preferably alkyl polyglycosides.
Preferred surfactants include Na-lauryl ether sulfate, castor oil sul-fonate, di-Na-lauryl polyglycol ether sulfosuccinate, cocoamido-propyl betaine, and alkyl polyglycosides having an alkyl residue of Cg-C1 6~ preferably C8 to C10 and an oligoglycoside residue hav-ing an oligomerization degree of 1.1-1.7, preferably 1.2-1.3.
The portion of the active detergents amounts to 5-40%-wt., pref-erably 10 - 30%-wt., relative to the skin cleaning agent according to the present invention.
The portion of the esters di-n-butyl adipate and/or diisopropyl adi-pate in the agents according to the present invention amounts to 1 - 25%-wt., preferably 5 to 20%-wt., and particularly preferred 10 - 20%-wt.
21 7312~
Abrasives to be used with preference are the bleached kernel/shell flours according to WO 92/09265, in particular bleached walnut shell flour or olive kernel flour. The portion of the abrasive in the agent according to the present invention amounts to 1 - 30%-wt., preferably 10- 20%-wt.
The agents according to the present invention further comprise viscosity forming agents, such as organophilic and/or hydrophilic phyllosilicates, such as bentonites, polysaccharides, such as cel-lulose and guar flour, as well as modified polysaccharides, such as the cellulose ethers, carboxymethylcellulose, and hydroxyethyl-cellulose and xanthan gum, and inorganic electrolytes, such as NaCI or MgS04. They further comprise chromatophoric pigments, such as TiO2, stabilizers, such as propylene carbonate, pH-regula-tors, fragrances, and preservatives. The water content of the skin cleaning agents amounts to 1 0-50%-wt., preferably 20-40%-wt.
Re-greasing components may be omitted in the production of the skin cleansing agents according to the present invention.
Preferably, the skin cleaning agents are obtained as liquid or creamy agents or as flowable viscous pastes.
According to another preferred embodiment, the skin cleaning agents according to the present invention additionally comprise at least one fatty alcohol of the general formula R-OH wherein R rep-resents an alkyl residue having C8 to C1 6, preferably Cg-C12. The amount of the fatty alcohol in the agent amounts to 0.1-10.0%-wt., preferably 0.1-5.0%-wt.
The mentioned raw material components may usually also be em-ployed by using combinations of one type of raw material, i.e., as mixtures of different surfactants, viscosity formers, abrasives, and stabilizers, etc.
- 6 21733 ~0 The flowable skin cleansing agents are manufactured by means of known devices according to the batch or continuous method.
Suitable devices are heatable vessels including an agitator, mixer and extruder, e.g., described in "Surfactants in Consumer Prod-ucts", J. Falbe, Springer Verlag, 1987, page 399 ff.
The present invention further relates to a process for the produc-tion of the skin cleaning agents, in which the components are combined under stirring as usual, optionally using partial amounts of the raw materials, wherein the adipic ester solvents are pref-erably prepared first, and the pigment, viscosity forming agents/
thickeners, and a partial amount of the surfactant are added then;
this mixture is heated and preferably adjusted to a temperature of up to 70C, preferably 40-60C, whereupon the remaining raw material amounts, in particular surfactants amounts, the inorganic electrolyte, the pH-regulator and fragrance, the preservative, and the abrasive are added. The homogeneous mixture is then cooled and filled into conventional vessels, such as cans, pump vessels, such as dispensers, jars, and tubes.
According to a special production method according to the present invention, fatty alcohols are added as consistency regulators to produce the agents. Most surprisingly, it was found that the addition of the fatty alcohol allows the mixing the raw materials, e.g., in the succession as mentioned above, to form homogeneous products at room temperature, i.e., at 5 to 30C, without having to heat the raw material mixture. The fact that the heating phase is omitted and the involved saving of energy and time offer advan-tages with respect to process technology.
_ ` 7 217312~
Moreover, the addition of the fatty alcohol has a positive effect on the use of the skin cleansing agents since, for example, the deter-gent effect is increased.
The skin cleaning agents according to the present invention are particularly suitable for the removal of rough dirt strongly adhering to the skin, e.g., fats, oils and other lubricants, dyes, varnishes, tar, graphite, soot, coloring pigments, and similar substances oc-curring in industry and public utilities, in the craftsmen's trade, or in agriculture and in the household.
The use of the skin cleaning agents according to the present in-vention is preferably effected by first distributing the cleaning agent on the skin without water or with a small amount of water, continuing the cleaning with water and finishing by rinsing with water. The small amount of water results by wetting or moistening the soiled skin areas with water or aqueous liquids. For instance, in the case of dirty hands, this quantity may amount to about 1 to
3 ml of water per palm.
The agents according to the present invention can easily be dis-tributed on the skin during washing. They have a good foaming power and - compared to conventional products - a better deter-gent action, with the dirt being easily removed from the skin with water. In addition to the good soil removing capacity, the agents according to the present invention have an improved dermatologi-cal compatibility.
Owing to the use of suitable raw materials the agents are biode-gradable and, for this reason, are characterized by a good ecologi-cal compatibility.
The invention will be illustrated by the following examples:
~ 1 7312 ~
Formulation I
Di-n-butyl adipate 10.00%-wt.
Titanium dioxide 1.00%-wt.
Organophilic bentonite 2.10%-wt.
Carboxymethylcellulose 1.20%-wt.
Sulfated castor oil (70%) 10.53%-wt.
Propylene carbonate 0.50%-wt.
Sodium fatty alcohol ether sulfate (C12-C1s) 28% 47.00%-wt.
Water 0.19%-wt.
Di-sodium-lauryl polyglycol ether sulfosuccinate (32-35%)10.00%-wt.
Common salt 2.00%-wt.
Citric acid 0.20%-wt.
Fragrance 0.20%-wt.
Preservative 0.08%-wt.
Walnut shell flour, bleached15.00%-wt.
100.00%-wt.
Formulation ll Di-isopropyl adipate 10.00%-wt.
Titanium dioxide 1.00%-wt.
Organophilic bentonite 2.00%-wt.
Hydrophilic bentonite 3.00%-wt.
Alkyl polyglycoside (Cg-C10), 55%20.00%-wt.
Municipal water 1.89%-wt.
Citric acid 0.23%-wt.
Preservative 0.08%-wt.
Boiled salt 2.50%-wt.
9 21~73120 Sodium fatty alcohol ether sulfate (C1 2-C1 5), 28% 44.00%-wt.
Walnut shell flour, bleached 1 5.00%-wt.
Fragrance 0.30%-wt.
1 00.00%-wt.
Formulation lll Solvent a to 9*) 10.00%-wt.
Titanium dioxide 1.00%-wt.
Hydrophilic bentonite 1.00%-wt.
Organophilic bentonite 4.00%-wt.
Alkyl polyglycoside (C8-C10)~ 55%20.00%-wt.
Fatty alcohol (C8-C 1 2) 1 . 50%-wt.
Municipal water 2.47 %-wt.
Preservative 0.08%-wt.
Fragrance 0.30%-wt.
Citric acid 0.1 5 %-wt.
Common salt 2. 50%-wt.
Sodium fatty alcohol ether sulfate (C1 2-C1 5), 28% 44.00%-wt.
Walnut shell flour, bleached 1 3.00%-wt.
1 00. 00 %-wt.
Illa: di-n-butyl adipate Illb: without solvent Illc: n-paraffin Illd: grape-seed oil Ille: DBE 2 Illf: di-isopropyl adipate lllg: di-n-butyl adipate, without fatty alcohol (Cg-C12) ~ 7312 0 --' 10 Formulation IV
Di-n-butyl adipate 10.00%-wt.
Titanium dioxide 1.00%-wt.
Hydrophilic bentonite 1.00%-wt.
Organophilic bentonite 3.00%-wt.
Alkyl polyglycoside (C8-C10)r 55% 20.00%-wt.
Fatty alcohol (C8-C12) 4.00%-wt.
Municipal water 0.97%-wt.
Preservative 0.08%-wt.
Fragrance 0.30%-wt.
Citric acid 0.15%-wt.
Common salt 2.50%-wt.
Sodium fatty alcohol ether sulfate (C12-C1s), 28% 44.00%-wt.
Walnut shell flour, bleached 13.00%-wt.
100.00%-wt.
Formulation V
Di-n-butyl adipate 7.00%-wt.
Titanium dioxide 1.00%-wt.
Hydrophilic bentonite 1.00%-wt.
Organophilic bentonite 2.50%-wt.
Alkyl polyglycoside (Cg-C10), 55% 20.00%-wt.
Fatty alcohol (C8-C 12) 8.00%-wt.
Municipal water 0.47%-wt.
Preservative ~ 0.08%-wt.
Fragrance 0.30%-wt.
Citric acid 0.15%-wt.
Common salt 0.50%-wt.
Sodium fatty alcohol ether sulfate (C12-C1s), 28% 44.00%-wt.
alnut shell flour, bleached 1 5.00%-wt.
1 00.00%-wt.
The cleaning efficiency of the formulations was tested in the hand washing test according to the method described in DE 27 36 970 A1. It was found that the agents show a considerably improved cleaning action with respect to model soil mainly consisting of oil, wax, vaseline, graphite, lampblack, and iron oxide, and with re-spect to model varnish consisting of synthetic resin, fish oil, and a paint pigment.
The skin compatibility was tested in the Duhring chamber test [Frosch, P.J., Kligman, A.M.: The Duhring chamber and improved technique for epicutaneous testing of irritant and allergic reactions.
Contact Derm. 5, 73-81 (1979); Frosch P.J., Kligman, A.M.: The soap chamber test, a new method of assessing the irritancy of soaps. J. Am. Acad. Derm. 1, 35-41 (1979)]. The results show that the dermal compatibility of the agents according to the pres-ent invention, as compared to commercially known products, is also improved.
Hand washing test Test Formulation p~.r~r)n 1 Illn 1 Ulf~ I Ille 11 Ul~ 11 Illrl . Il 111.-1.01.50.00.50.50.00.00.51.01.01.00.0 2 0.50.50.50.50.50.50.01.50.01.01.50.5 3 0.50.50.51.01.00.50.51.50.51.51.00.5
The agents according to the present invention can easily be dis-tributed on the skin during washing. They have a good foaming power and - compared to conventional products - a better deter-gent action, with the dirt being easily removed from the skin with water. In addition to the good soil removing capacity, the agents according to the present invention have an improved dermatologi-cal compatibility.
Owing to the use of suitable raw materials the agents are biode-gradable and, for this reason, are characterized by a good ecologi-cal compatibility.
The invention will be illustrated by the following examples:
~ 1 7312 ~
Formulation I
Di-n-butyl adipate 10.00%-wt.
Titanium dioxide 1.00%-wt.
Organophilic bentonite 2.10%-wt.
Carboxymethylcellulose 1.20%-wt.
Sulfated castor oil (70%) 10.53%-wt.
Propylene carbonate 0.50%-wt.
Sodium fatty alcohol ether sulfate (C12-C1s) 28% 47.00%-wt.
Water 0.19%-wt.
Di-sodium-lauryl polyglycol ether sulfosuccinate (32-35%)10.00%-wt.
Common salt 2.00%-wt.
Citric acid 0.20%-wt.
Fragrance 0.20%-wt.
Preservative 0.08%-wt.
Walnut shell flour, bleached15.00%-wt.
100.00%-wt.
Formulation ll Di-isopropyl adipate 10.00%-wt.
Titanium dioxide 1.00%-wt.
Organophilic bentonite 2.00%-wt.
Hydrophilic bentonite 3.00%-wt.
Alkyl polyglycoside (Cg-C10), 55%20.00%-wt.
Municipal water 1.89%-wt.
Citric acid 0.23%-wt.
Preservative 0.08%-wt.
Boiled salt 2.50%-wt.
9 21~73120 Sodium fatty alcohol ether sulfate (C1 2-C1 5), 28% 44.00%-wt.
Walnut shell flour, bleached 1 5.00%-wt.
Fragrance 0.30%-wt.
1 00.00%-wt.
Formulation lll Solvent a to 9*) 10.00%-wt.
Titanium dioxide 1.00%-wt.
Hydrophilic bentonite 1.00%-wt.
Organophilic bentonite 4.00%-wt.
Alkyl polyglycoside (C8-C10)~ 55%20.00%-wt.
Fatty alcohol (C8-C 1 2) 1 . 50%-wt.
Municipal water 2.47 %-wt.
Preservative 0.08%-wt.
Fragrance 0.30%-wt.
Citric acid 0.1 5 %-wt.
Common salt 2. 50%-wt.
Sodium fatty alcohol ether sulfate (C1 2-C1 5), 28% 44.00%-wt.
Walnut shell flour, bleached 1 3.00%-wt.
1 00. 00 %-wt.
Illa: di-n-butyl adipate Illb: without solvent Illc: n-paraffin Illd: grape-seed oil Ille: DBE 2 Illf: di-isopropyl adipate lllg: di-n-butyl adipate, without fatty alcohol (Cg-C12) ~ 7312 0 --' 10 Formulation IV
Di-n-butyl adipate 10.00%-wt.
Titanium dioxide 1.00%-wt.
Hydrophilic bentonite 1.00%-wt.
Organophilic bentonite 3.00%-wt.
Alkyl polyglycoside (C8-C10)r 55% 20.00%-wt.
Fatty alcohol (C8-C12) 4.00%-wt.
Municipal water 0.97%-wt.
Preservative 0.08%-wt.
Fragrance 0.30%-wt.
Citric acid 0.15%-wt.
Common salt 2.50%-wt.
Sodium fatty alcohol ether sulfate (C12-C1s), 28% 44.00%-wt.
Walnut shell flour, bleached 13.00%-wt.
100.00%-wt.
Formulation V
Di-n-butyl adipate 7.00%-wt.
Titanium dioxide 1.00%-wt.
Hydrophilic bentonite 1.00%-wt.
Organophilic bentonite 2.50%-wt.
Alkyl polyglycoside (Cg-C10), 55% 20.00%-wt.
Fatty alcohol (C8-C 12) 8.00%-wt.
Municipal water 0.47%-wt.
Preservative ~ 0.08%-wt.
Fragrance 0.30%-wt.
Citric acid 0.15%-wt.
Common salt 0.50%-wt.
Sodium fatty alcohol ether sulfate (C12-C1s), 28% 44.00%-wt.
alnut shell flour, bleached 1 5.00%-wt.
1 00.00%-wt.
The cleaning efficiency of the formulations was tested in the hand washing test according to the method described in DE 27 36 970 A1. It was found that the agents show a considerably improved cleaning action with respect to model soil mainly consisting of oil, wax, vaseline, graphite, lampblack, and iron oxide, and with re-spect to model varnish consisting of synthetic resin, fish oil, and a paint pigment.
The skin compatibility was tested in the Duhring chamber test [Frosch, P.J., Kligman, A.M.: The Duhring chamber and improved technique for epicutaneous testing of irritant and allergic reactions.
Contact Derm. 5, 73-81 (1979); Frosch P.J., Kligman, A.M.: The soap chamber test, a new method of assessing the irritancy of soaps. J. Am. Acad. Derm. 1, 35-41 (1979)]. The results show that the dermal compatibility of the agents according to the pres-ent invention, as compared to commercially known products, is also improved.
Hand washing test Test Formulation p~.r~r)n 1 Illn 1 Ulf~ I Ille 11 Ul~ 11 Illrl . Il 111.-1.01.50.00.50.50.00.00.51.01.01.00.0 2 0.50.50.50.50.50.50.01.50.01.01.50.5 3 0.50.50.51.01.00.50.51.50.51.51.00.5
4 0.51.01.01.51.00.51.00.51.01.00.51.0 S 1.00.50.00.50.00.51.01.01.01.00.50.5 6 0.51.50.50.50.50.50.50.50.50.50.00.5 Aver- 0.60.90.40.80.60.40.50.90.71.00.80.5 age Test Formulation person Illa Illb Illa Illc ¦ llla Illd Illa Ille Illa Illf Illa lllg Illf Ille Illf Illd 0.50.50.50.0,! o.o 1.50.50.51.02.00.01.50.50.50.51.0 2 0.01.00.50.00.00.50.00.51.01.00.51.00.00.50.50.5 3 0.0200.51.00.01.01.51.00.50.50.51.01.51.01.01.5 4 0.50.50.50.51.00.50.51.00.01.00.51.01.00.50.50.5 0.01.00.52.50.00.51.51.00.50.50.01.02.01.51.52.5 6 0.10.50.52.01.01.02.02.52.01.51.51.50.50.01.01.0 Aver-age 0.30.90.51.00.30.81.01.10.81.10.51.20.90.70.81.2 Illa: Formulation with di-n-butyl adipate Illb: Formulation without solvent Illc: Formulation with n-paraffin Illd: Formulation with grape-seed oil Ille: Formulation with DBE2 illf: Formulation with di-isopropyl adipate lllg: Formulation with di-n-butyl adipate without fatty alcohol (Cg-C12) Amount of test product: 1.2 9 Amount of dirt: 0.5 9 Result Both, formulation I with di-n-butyl adipate and formulation ll with di-isopropyl adipate have a better detergent action than Illc and Illd, but a slightly worse action than Ille.
- ~13 ~1~312G
The washing tests clearly show the superiority of the formulation Illa comprising di-n-butyl adipate and fatty alcohol (Cg-C12), as compared with those without solvent ~Illb), with di-n-butyl adipate (Illg), with n-paraffin (Illc) and grape-seed oil (Illd).
In comparison with the formulations comprising DBE 2 (mixture of dimethyl adipate, dimethyl succinate, dimethyl glutarate), Ille, and di-isopropyl adipate, Illf, Illa has a comparable or better detergent action.
Additionally, the formulation comprising diisopropyl adipate, Illf, has a better cleaning effect than that comprising grape-seed oil, Illd, but a slightly worse one than the formulation with DBE 2, Ille.
Duhring-Chamber-Test Water NaLS Formulation 0.5% 1 ll IV V Illb A-value25.1 4.3 16.1 14.4 14.8 15.3 14.2 Water NaLS Formulation 0.5% Illa Illc Illd Ille Illf lllg A-value25.1 4.3 15.2 5.0 17.1 8.2 14.7 14.5 Illa: Formulation with di-n-butyl adipate Illb: Formulation without solvent Illc: Formulation with n-paraffin Illd: Formulation with grape-seed oil Ille: Formulation with DBE2 Illf: Formulation with di-isopropyl adipate Illg: Formulation with di-n-butyl adipate without fatty alcohol (Cg-c12) Amount of test product: appr. 200 mg Duration of test: 3 weeks Application intervals: 1st day 2 hours 2nd day 4 hours 3rd day 6 hours 4th day 6 hours 5th day about 5 hours Number of test persons: 25 Result:
The Duhring Chamber Test proves the good dermal compatibility of the formulations according to the present invention 1, Il, IV, Illa, Illf, and lllg for this product class. In comparison, the formulations with n-paraffin (Illc) and DBE 2 (Ille) show a considerably worse skin compatibility.
- ~13 ~1~312G
The washing tests clearly show the superiority of the formulation Illa comprising di-n-butyl adipate and fatty alcohol (Cg-C12), as compared with those without solvent ~Illb), with di-n-butyl adipate (Illg), with n-paraffin (Illc) and grape-seed oil (Illd).
In comparison with the formulations comprising DBE 2 (mixture of dimethyl adipate, dimethyl succinate, dimethyl glutarate), Ille, and di-isopropyl adipate, Illf, Illa has a comparable or better detergent action.
Additionally, the formulation comprising diisopropyl adipate, Illf, has a better cleaning effect than that comprising grape-seed oil, Illd, but a slightly worse one than the formulation with DBE 2, Ille.
Duhring-Chamber-Test Water NaLS Formulation 0.5% 1 ll IV V Illb A-value25.1 4.3 16.1 14.4 14.8 15.3 14.2 Water NaLS Formulation 0.5% Illa Illc Illd Ille Illf lllg A-value25.1 4.3 15.2 5.0 17.1 8.2 14.7 14.5 Illa: Formulation with di-n-butyl adipate Illb: Formulation without solvent Illc: Formulation with n-paraffin Illd: Formulation with grape-seed oil Ille: Formulation with DBE2 Illf: Formulation with di-isopropyl adipate Illg: Formulation with di-n-butyl adipate without fatty alcohol (Cg-c12) Amount of test product: appr. 200 mg Duration of test: 3 weeks Application intervals: 1st day 2 hours 2nd day 4 hours 3rd day 6 hours 4th day 6 hours 5th day about 5 hours Number of test persons: 25 Result:
The Duhring Chamber Test proves the good dermal compatibility of the formulations according to the present invention 1, Il, IV, Illa, Illf, and lllg for this product class. In comparison, the formulations with n-paraffin (Illc) and DBE 2 (Ille) show a considerably worse skin compatibility.
Claims (11)
1. Hydrous, liquid, paste- or cream-like skin cleaning agents for the removal of strongly adhering soil, comprising anionic and/or amphoteric and/or non-ionogenic surfactants as washing-active substances, viscosity formers, at least one abrasive and, option-ally, adjuvants for the regulation of consistency, appearance, odor, and stability, such as pigments, fragrances, stabilizers, and pre-servatives, characterized in that they comprise as exclusive sol-vents di-n-butyl adipate and/or di-isopropyl adipate.
2. The hydrous, liquid, paste- or cream-like skin cleaning agents according to claim 1 characterized in that they comprise at least one fatty alcohol of the general formula R-OH wherein R is an alkyl residue having C8 to C16, preferably C8 to C12.
3. The hydrous, liquid, paste- or cream-like skin cleaning agents according to any one of claims 1 to 2 characterized in that the content of solvent amounts to 1 - 25, preferably 5 - 20%-wt., rel-ative to the skin cleaning agent.
4. The hydrous, liquid, paste- or cream-like skin cleaning agents according to any one of claims 1 to 3 characterized in that the content of fatty alcohol amounts to 0.1 to 10.0%-wt., preferably 0.1 to 5.0%-wt., relative to the skin cleaning agent.
5. The hydrous, liquid, paste- or cream-like skin cleaning agents according to any one of claims 1 to 4 characterized in that they comprise as non-ionogenic surfactants a!kyl polyglycosides having an alkyl residue of C8 to C16, preferably C8 to C10 and an oligo-glycoside residue with an oligomerization degree of 1.1 to 1.7, preferably 1.2 to 1.3, as well as sodium fatty alcohol ether sulfate and bleached walnut shell flour.
6. The hydrous, liquid, paste- or cream-like skin cleaning agents according to any one of claims 1 to 5 characterized in that the content of washing-active substances amounts to 5 - 40, pref-erably 10- 30%-wt., relative to the skin cleaning agent.
7. The hydrous, liquid, paste- or cream-like skin cleaning agents according to any one of claims 1 to 6 characterized in that the content of abrasive amounts to 1 - 30, preferably 10 - 20%-wt.
8. The hydrous, liquid, paste- or cream-like skin cleaning agents according to any one of claims 1 to 7 characterized in that the content of water amounts to 10 - 50, preferably 20 - 40%-wt.
9. A process for the production of the skin cleaning agents as de-fined in any one of claims 1 to 8, characterized in that the solvent is prepared first, pigment, viscosity forming agents/thickeners and a partial amount of the surfactant are added then, the mixture thus obtained is heated to a temperature of up to 70°C, preferably 40 - 60°C, whereupon the remaining amounts of components, in particular amounts of surfactant, the inorganic electrolyte, the pH-regulator, the fragrance, the preservative and the abrasive are added, followed by homogenization and final cooling.
10. The process according to claim 9 characterized in that the mixing of the components and the homogenization is effected without heating if a fatty alcohol is used as component.
11. The use of the skin cleaning agents according to any one of claims 1 to 8, characterized in that during cleansing the cleaning agent is distributed on the skin, preferably without the addition of water or with a small amount of water first, and that the cleaning procedure is finished under rinsing with water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4335933.7 | 1993-10-21 | ||
| DE4335933A DE4335933C2 (en) | 1993-10-21 | 1993-10-21 | Skin cleanser |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2173120A1 true CA2173120A1 (en) | 1995-04-27 |
Family
ID=6500682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002173120A Abandoned CA2173120A1 (en) | 1993-10-21 | 1994-10-20 | Skin-cleansing agents, methods of preparing them and their use |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US5891449A (en) |
| EP (1) | EP0724426B1 (en) |
| JP (2) | JP2946238B2 (en) |
| AT (1) | ATE166226T1 (en) |
| AU (1) | AU684841B2 (en) |
| BR (1) | BR9407861A (en) |
| CA (1) | CA2173120A1 (en) |
| DE (2) | DE4335933C2 (en) |
| DK (1) | DK0724426T3 (en) |
| ES (1) | ES2098200T3 (en) |
| GR (1) | GR960300059T1 (en) |
| WO (1) | WO1995011005A1 (en) |
| ZA (1) | ZA948202B (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19748921C2 (en) | 1997-10-30 | 2001-02-22 | Stockhausen Chem Fab Gmbh | Skin-friendly hand cleaners, especially rough hand cleaners |
| DE19816664A1 (en) * | 1998-04-15 | 1999-10-21 | Henkel Kgaa | Mildly abrasive skin cleanser |
| GB2343189B (en) * | 1998-10-27 | 2002-11-20 | Tetrosyl Ltd | Skin cleansing composition |
| EP1061125A3 (en) * | 1999-06-18 | 2002-11-13 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Composition containing di(2-ethylhexyl) adipate and tricyclic isochroman compounds and use thereof in enzyme-active detergents and fabric softeners |
| US7638144B2 (en) * | 1999-10-04 | 2009-12-29 | Dermanew, Inc. | Composition, apparatus and method for skin rejuvenation |
| US7572238B2 (en) * | 1999-10-04 | 2009-08-11 | Dermanew, Inc. | Handheld sonic microdermabrasion porous applicator |
| US6652888B2 (en) | 1999-10-04 | 2003-11-25 | Dermanew, Inc. | Method for skin rejuvenation with buffing cream |
| JP3629392B2 (en) * | 1999-12-09 | 2005-03-16 | ポーラ化成工業株式会社 | Hair manucia remover and hair manucia set with it as a component |
| US6290976B1 (en) | 2000-04-06 | 2001-09-18 | Donna Messenger | Facial skin dermabrasion cleansing and conditioning composition |
| JP3629400B2 (en) * | 2000-04-19 | 2005-03-16 | ポーラ化成工業株式会社 | Hair manucia remover and hair manucia set comprising it |
| US6670313B1 (en) | 2000-06-05 | 2003-12-30 | Colormetric Laboratories, Inc. | Method and composition for minimizing percutaneous absorption of industrial chemicals |
| CN1313586C (en) * | 2000-12-22 | 2007-05-02 | 荷兰联合利华有限公司 | Fabric care compositions |
| US7749523B2 (en) * | 2001-09-25 | 2010-07-06 | Crabtree & Evelyn, Ltd. | Emollient skin conditioning cream and method |
| DE60327890D1 (en) * | 2002-12-11 | 2009-07-16 | Donaldson Co Inc | Z-FILTER MEDIA WITH AGGREGATE CLEANING SYSTEMS AND METHOD |
| US7179152B1 (en) * | 2003-02-07 | 2007-02-20 | Dermanew, Inc. | Composition suitable for application to human skin |
| US7297668B2 (en) * | 2003-04-03 | 2007-11-20 | Colgate-Palmolive Company | Composition |
| US7309496B2 (en) * | 2003-07-02 | 2007-12-18 | Colgate-Palmolive Company | Composition |
| DE10329933A1 (en) * | 2003-07-02 | 2005-06-23 | Stockhausen Gmbh | Cosmetic abrasive production, for use in skin cleansing, by bleaching ground natural material, e.g. nut shells, and bleaching in two stages at controlled pH |
| US7384405B2 (en) * | 2004-09-10 | 2008-06-10 | Rhoades Dean L | Oxygenating cosmetic instrument having various numbers of heads |
| US20060251597A1 (en) * | 2005-05-04 | 2006-11-09 | Yu Ruey J | Anti-odor compositions and therapeutic use |
| DE102005054976A1 (en) * | 2005-11-16 | 2007-05-31 | Stockhausen Gmbh | Process for the preparation of a cosmetic abrasive |
| US20070166338A1 (en) * | 2006-01-13 | 2007-07-19 | Reilly Dillon | Dermabrasion composition and process |
| DE102007022693A1 (en) | 2007-05-11 | 2009-01-15 | Evonik Stockhausen Gmbh | Skin and hand cleaners with hydrophilic emollients |
| DE102008026051A1 (en) | 2008-05-30 | 2009-12-03 | Evonik Stockhausen Gmbh | Skin and hand cleanser |
| DE102009046272A1 (en) | 2009-11-02 | 2011-05-05 | Evonik Stockhausen Gmbh | Natural resource-based friction agent with rheology enhancing properties |
| WO2012040142A1 (en) * | 2010-09-21 | 2012-03-29 | The Procter & Gamble Company | Liquid cleaning composition |
| EP2431451A1 (en) * | 2010-09-21 | 2012-03-21 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
| DE102011004815A1 (en) | 2011-02-28 | 2012-08-30 | Evonik Stockhausen Gmbh | Skin and hand cleanser containing superabsorbent particles |
| DE102012201668A1 (en) | 2012-02-06 | 2013-08-08 | Evonik Industries Ag | Composition containing hydroxyethyl cellulose |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE327049B (en) * | 1966-01-31 | 1970-08-10 | Medisan Ab | |
| US4344446A (en) * | 1980-03-17 | 1982-08-17 | Susan Bjurman | Combined scalp and hair care products and method |
| ATE81449T1 (en) * | 1984-03-05 | 1992-10-15 | Tonfer Inc | CLEANING SUPPLIES. |
| ATE65388T1 (en) * | 1984-05-24 | 1991-08-15 | Pegel Karl Heinrich | COSMETIC AGENT. |
| DE3785365T2 (en) * | 1986-01-08 | 1993-09-16 | Kao Corp | BATH ACCESSORIES. |
| DE3736970C3 (en) * | 1987-10-30 | 1996-08-01 | Stockhausen Chem Fab Gmbh | Anhydrous skin cleanser and its use |
| US5093360A (en) * | 1989-04-07 | 1992-03-03 | Yu Ruey J | Retinal, derivatives and their therapeutic use |
| DE4009534A1 (en) * | 1990-03-24 | 1991-09-26 | Henkel Kgaa | LIQUID HAND CLEANER |
| DE4038076A1 (en) * | 1990-11-29 | 1992-06-04 | Stockhausen Chem Fab Gmbh | ABRASIVUM IN COSMETIC PRODUCTS AND METHOD FOR THE PRODUCTION AND USE THEREOF |
| TW218849B (en) * | 1991-05-17 | 1994-01-11 | Bristol Myers Squibb Co | |
| DE4122033A1 (en) * | 1991-07-03 | 1993-01-07 | Henkel Kgaa | PRESERVATIVE-FREE WATER-IN-OIL EMULSIONS |
| US5476661A (en) * | 1994-10-21 | 1995-12-19 | Elizabeth Arden Co., Division Of Conopco, Inc. | Compositions for topical application to skin, hair and nails |
| JPH09281620A (en) * | 1996-04-18 | 1997-10-31 | Fuji Photo Film Co Ltd | Silver halide emulsion and silver halide photographic sensitive material using the same |
-
1993
- 1993-10-21 DE DE4335933A patent/DE4335933C2/en not_active Expired - Fee Related
-
1994
- 1994-10-19 ZA ZA948202A patent/ZA948202B/en unknown
- 1994-10-20 DK DK94929563T patent/DK0724426T3/en active
- 1994-10-20 ES ES94929563T patent/ES2098200T3/en not_active Expired - Lifetime
- 1994-10-20 BR BR9407861A patent/BR9407861A/en not_active Application Discontinuation
- 1994-10-20 CA CA002173120A patent/CA2173120A1/en not_active Abandoned
- 1994-10-20 JP JP7504778A patent/JP2946238B2/en not_active Expired - Fee Related
- 1994-10-20 AU AU78569/94A patent/AU684841B2/en not_active Ceased
- 1994-10-20 EP EP94929563A patent/EP0724426B1/en not_active Expired - Lifetime
- 1994-10-20 AT AT94929563T patent/ATE166226T1/en not_active IP Right Cessation
- 1994-10-20 US US08/632,435 patent/US5891449A/en not_active Expired - Fee Related
- 1994-10-20 WO PCT/EP1994/003448 patent/WO1995011005A1/en active IP Right Grant
- 1994-10-20 DE DE59406049T patent/DE59406049D1/en not_active Expired - Fee Related
-
1996
- 1996-11-30 GR GR960300059T patent/GR960300059T1/en unknown
-
1998
- 1998-11-25 US US09/199,486 patent/US6235296B1/en not_active Expired - Fee Related
-
1999
- 1999-02-03 JP JP11026672A patent/JPH11286437A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE4335933A1 (en) | 1995-04-27 |
| DK0724426T3 (en) | 1999-03-08 |
| ATE166226T1 (en) | 1998-06-15 |
| DE4335933C2 (en) | 1998-09-03 |
| JP2946238B2 (en) | 1999-09-06 |
| ES2098200T3 (en) | 1998-08-16 |
| AU7856994A (en) | 1995-05-08 |
| JPH09501151A (en) | 1997-02-04 |
| ES2098200T1 (en) | 1997-05-01 |
| EP0724426B1 (en) | 1998-05-20 |
| US5891449A (en) | 1999-04-06 |
| GR960300059T1 (en) | 1996-11-30 |
| ZA948202B (en) | 1995-06-12 |
| JPH11286437A (en) | 1999-10-19 |
| EP0724426A1 (en) | 1996-08-07 |
| WO1995011005A1 (en) | 1995-04-27 |
| BR9407861A (en) | 1997-05-20 |
| DE59406049D1 (en) | 1998-06-25 |
| US6235296B1 (en) | 2001-05-22 |
| AU684841B2 (en) | 1998-01-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |