WO1991014420A1 - Liquid hand-cleansing agent - Google Patents
Liquid hand-cleansing agent Download PDFInfo
- Publication number
- WO1991014420A1 WO1991014420A1 PCT/EP1991/000497 EP9100497W WO9114420A1 WO 1991014420 A1 WO1991014420 A1 WO 1991014420A1 EP 9100497 W EP9100497 W EP 9100497W WO 9114420 A1 WO9114420 A1 WO 9114420A1
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- Prior art keywords
- weight
- cleaning agent
- agent according
- organic solvent
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Classifications
-
- 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
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
-
- 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
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- 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
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- 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
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- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
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- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- A61K2800/20—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
Definitions
- the present invention relates to a liquid cleaning agent for human skin, in particular a hand cleaning agent.
- cleaning agents When working with paints, varnishes, glazes, oils, tars or similar substances, it is often impossible to avoid soiling your hands.
- cleaning agents often in the form of pastes or creams, which as a rule contain abrasives, surfactants, water, organic solvents and, if appropriate, further auxiliaries.
- aromatic surfactants for example alkylbenzenesulfonates or ethoxylated alkylphenols, and / or water-soluble phosphates, usually in combination with additional ones, are generally used Solubilizers used. These components are increasingly controversial due to their poor biodegradability.
- liquid to gel-like hand cleaning agents for removing paint, dye and tar stains are known, which contain 4-20% by weight of surfactants, 5-15% by weight of emulators, 10 - 35 wt .-% solvent, 1 - 5 wt .-% lipid replenishing agent, the rest water.
- the solvents used there are compounds containing ether and / or ester groups, which are characterized by their boiling point from 100 to 300 ° C., optionally in combination with hydrocarbons, the boiling point of which is preferably in the range from 100 to 240 ° C.
- Alkaline soaps which may be present as additional components in amounts of 0.2-2% by weight, are proposed as "structuring" components.
- the cleaning agents presented there make it possible to dispense with environmentally harmful phosphates, but they can their gasoline content contains difficult-to-decompose aromatic hydrocarbons. In addition, phase separation occurs relatively quickly when such agents are stored.
- Solvent-free, solid to cream-shaped detergents which contain hydrogenated castor oil instead of the mentioned aromatics which are not very compatible with the world are known from German publication DT 1692026.
- the hydrogenated castor oil has the task of stabilizing the solid, non-pourable formulations against water secretion and softening.
- R is an alkyl radical with 1 to 3 C atoms
- n is a number from 1 to 4
- X is an alkyl radical with 1 to 5 C atoms, incorporated into the cleaning agent.
- the hand cleansing agents according to the invention also contain anionic and / or nonionic surfactants, abrasives and optionally other solvents which are as skin-friendly as possible, as well as other substances customary in skin cleansing agents, such as moisturizing agents, perfumes and dyes. They are flowable, largely homogeneous pastes, which show no phase separation even when stored for a long time, at low or elevated temperatures.
- the dermatological contained in them harmless organic solvents, they show very good cleaning effects on human skin against paints, glazes, lacquers, oils and tars.
- the hydrogenated castor oil present in the cleaning agents according to the invention as a thickener and consistency agent is preferably in amounts of 0.1% by weight to 5% by weight, in particular in amounts of 1% by weight to 3% by weight in the cleaning agents according to the invention contain.
- R is an alkyl radical with 1 to 3 C atoms
- n is a number from 1 to 4, which can also be broken as an analytically determined size
- X is an alkyl radical with 1 to 5 C atoms, preferably in quantities of 5 up to 40% by weight, particularly preferably in amounts of 10 to 30% by weight, are incorporated into the cleaning agents according to the invention.
- Esters of the general formula I can be prepared by known processes, as described, for example, in European patent EP 119 833 or EP 163 522.
- the hand cleaning agents according to the invention can contain further organic solvents which are as skin-friendly as possible, including limonene and aromatic-free gasolines such as isoparaffins, preferably in amounts not exceeding 20% by weight, in particular from 5% by weight to 15% by weight. , contain. Limonene is the preferred additional solvent.
- the abrasive materials which are suitable for the cleaning agents according to the invention include micro-glass balls, quartz flours, wood flours, chalks and plastics. Polyurethane flours are preferably used.
- the abrasives are contained in the cleaning agents according to the invention preferably in amounts of 1 to 10% by weight, in particular 2% to 6% by weight.
- the cleaning agents according to the invention also contain anionic and / or nonionic surfactants, preferably in amounts of 5 to 70% by weight, in particular 10 to 30% by weight.
- the aromatic-free anionic surfactants which can preferably be incorporated into the cleaning agents according to the invention include alkyl sulfates, alkanesulfonates and alkyl ether sulfates, in which the alkyl groups preferably contain 10 to 20 carbon atoms, in particular 12 to 18 carbon atoms. These anionic surfactants are preferably used in the form of their sodium salts.
- the nonionic surfactants which are preferably present in the cleaning agents according to the invention include alkyl glycosides and the addition products of preferably 4 to 30 mol equivalents of ethylene oxide and / or propylene oxide to alkyl glycosides, alkanoic acids and / or alkanols, each preferably having 12 to 20 carbon atoms. Atoms in the respective alkyl parts.
- the end-capped derivatives of such alkoxylation products that is to say their terminal O-alkylation products, preferably with end groups which contain 2 to 10 C atoms, are also suitable.
- nonionic surfactants include, for example, the commercial products sold under the names Dehypon ( R ) (manufacturer Henkel), Dehydol ( R ) (manufacturer Henkel), Lutensol ( R ) (manufacturer BASF) or Triton ( R ) (manufacturer Rohm & Haas).
- the hand cleaning agent In order to prevent degreasing of the human skin through the use of the hand cleaning agent according to the invention, they preferably contain refatting agents in addition to the previously mentioned components, which include in particular fatty acid alkanolamides, fatty acid polyalkanolamides, their ethylene and / or propylene oxide addition products and fatty acid monoglycerides. Compounds of which the fatty acid part contains 12 to 18 carbon atoms are particularly suitable.
- the refatting agents are contained in the cleaning agents according to the invention preferably in amounts of not more than 20% by weight, in particular from 2% by weight to 18% by weight.
- the constituents which may additionally be present in the cleaning agents according to the invention include dyes which are preferably used in amounts of not more than 0.1% by weight, in particular not more than 0.01% by weight.
- the hand cleaning agent according to the invention can be used at room temperature or at elevated temperatures. It is easy to wash off with cold or warm water. It can also be used to remove paints, varnishes, oils and tars from hard surfaces or textiles.
- the preparation of the agents according to the invention has no special features.
- the easiest way to do this is to mix the individual components, preferably at an elevated temperature of about 45 ° C. to 80 ° C., in a stirrer apparatus, water preferably being added as the last component, and then filling, if necessary after cooling, into conventional ones Containers such as canisters, tubes, pumping vessels, dispensers or cans.
- polyurethane flour manufactured by manufactureurer Puren-Schaumstoff GmbH
- Henkel 1.0% by weight hydrogenated castor oil (Rilanit ( R ) SM, manufacturer Henkel) - i -.
- lauric acid monoglyceride manufactured by manufacture of lauric acid monoglyceride (manufacturer Grünau) 3.0% by weight polyurethane flour (manufacturer Puren-Schaumstoff GmbH) 47.1% by weight water
- agents VI to V3 free of hydrogenated castor oil were prepared by the process described above:
- the agents B1 to B3 were of a flowable, pumpable consistency. Its viscosity was about 10,000 mPa «s.
- the agents were filled into tubes or canisters after they had cooled completely to room temperature. Alternatively, the filling can take place while still warm, that is to say at about 40 ° C. to 50 ° C.
- the filled cleaning agents according to the invention were stored for 3 months at 0 ° C., 6 months at 40 ° C. or 6 months at room temperature without a change in consistency or even phase separation being observed. Agents VI to V3 became inhomogeneous after 2 weeks, but at most after 4 weeks, under the same storage conditions and showed phase separations.
- the paints and lacquers listed in the table below were each applied as thin, uniform films to glass plates. After drying for 24 hours, approx. 1 gram of the hand cleaner B1 according to the invention or a commercially available pasty hand cleaner based on water (V4), the 3.4% by weight soap (molecular weight 280), 5.3% by weight ethoxylated Nonylphenol, 5.1% by weight fatty acid diethanolamide, 0.2% by weight diethanolamine, 0.9% by weight triethanolamine, 2.7% by weight polyurethane flour, 9.0% by weight limonene and 36.0 Contained wt .-% aromatics-containing gasoline, applied and needed with uniformly strong rubbing with a finger Time to remove the layer determined.
- the cleaners B2 and B3 according to the invention were tested under the same conditions and did not differ in their cleaning performance from that of the hand cleaner Bl.
- Paint 20 larger than 120 (Herbol ( R ) extra white)
- Silicate color 40 50 (Kieselit ())
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Abstract
Description
"Flüssiges Handreinigungsmittel" "Liquid hand cleaning agent"
Die vorliegende Erfindung betrifft ein flüssiges Reinigungsmittel für menschliche Haut, insbesondere ein Handreinigungsmittel.The present invention relates to a liquid cleaning agent for human skin, in particular a hand cleaning agent.
Beim Arbeiten mit Farben, Lacken, Lasuren, Ölen, Teeren oder ähnlichen Substanzen läßt sich oft eine Verschmutzung der Hände nicht vermeiden. Zur Entfernung derartiger hartnäckiger Verschmutzungen werden bisher Reini¬ gungsmittel, oft in Form von Pasten oder Cremes, verwendet, die in der Regel Abrasivstoffe, Tenside, Wasser, organische Lösungsmittel und gege¬ benenfalls weitere Hilfsstoffe enthalten. Um die zur Erzielung einer aus¬ reichenden Reinigungswirkung in relativ hohen Mengenanteilen notwendigen organischen Lösungsmittel stabil in derartige wäßrige Reiniger einarbeiten zu können, werden in der Regel aromatische Tenside, zum Beispiel Alkylbenzolsulfonate oder ethoxylierte Alkylphenole, und/oder wasserlösliche Phosphate, üblicherweise in Kombination mit zusätzlichen Lösungsvermittlern, verwendet. Diese Bestandteile sind aufgrund ihrer mangelhaften biologischen Abbaubarkeit zunehmend umstritten.When working with paints, varnishes, glazes, oils, tars or similar substances, it is often impossible to avoid soiling your hands. To remove such stubborn soiling, cleaning agents, often in the form of pastes or creams, have hitherto been used, which as a rule contain abrasives, surfactants, water, organic solvents and, if appropriate, further auxiliaries. In order to be able to stably incorporate the organic solvents required to achieve a sufficient cleaning action in relatively high proportions into such aqueous cleaners, aromatic surfactants, for example alkylbenzenesulfonates or ethoxylated alkylphenols, and / or water-soluble phosphates, usually in combination with additional ones, are generally used Solubilizers used. These components are increasingly controversial due to their poor biodegradability.
Aus der deutschen Offenlegungsschrift DE 37 17600 sind flüssige bis gel- förmige Handreinigungsmittel zur Entfernung von Lack-, Färb- und Teeran- schmutzungen bekannt, die 4 - 20 Gew.-% Tenside, 5 - 15 Gew.-% Emulato¬ ren, 10 - 35 Gew.-% Lösungsmittel, 1 - 5 Gew.-% Rückfettungsmittel, Rest Wasser, enthalten. Die dort verwendeten Lösungsmittel sind ether-und/oder estergruppenhaltige Verbindungen, die durch ihren Siedepunkt von 100 - 300 °C gekennzeichnet sind, gegebenenfalls in Kombination mit Kohlen¬ wasserstoffen, deren Siedepunkt vorzugsweise im Bereich von 100 - 240 °C liegt. Als "strukturgebende" Bestandteile werden Alkaliseifen, die als zusätzliche Bestandteile in Mengen von 0,2-2 Gew.-% enthalten sein dürfen, vorgeschlagen. Die dort vorgestellten Reinigungsmitteln machen zwar den Verzicht auf umweltbedenkl che Phosphate möglich, können jedoch durch ihren Gehalt an Benzinen schwer abbaubare aromatische Kohlenwasserstoffe enthalten. Außerdem tritt bei der Lagerung derartiger Mittel relativ rasch eine Phasentrennung auf.From German published patent application DE 37 17600, liquid to gel-like hand cleaning agents for removing paint, dye and tar stains are known, which contain 4-20% by weight of surfactants, 5-15% by weight of emulators, 10 - 35 wt .-% solvent, 1 - 5 wt .-% lipid replenishing agent, the rest water. The solvents used there are compounds containing ether and / or ester groups, which are characterized by their boiling point from 100 to 300 ° C., optionally in combination with hydrocarbons, the boiling point of which is preferably in the range from 100 to 240 ° C. Alkaline soaps, which may be present as additional components in amounts of 0.2-2% by weight, are proposed as "structuring" components. The cleaning agents presented there make it possible to dispense with environmentally harmful phosphates, but they can their gasoline content contains difficult-to-decompose aromatic hydrocarbons. In addition, phase separation occurs relatively quickly when such agents are stored.
Lösungsmittelfreie feste bis cremeförmige Waschmittel, die statt der er¬ wähnten wenig u weltverträgliehen Aromaten hydriertes Rizinusöl enthalten, sind aus der deutschen Auslegeschrift DT 1692026 bekannt. In den dort beschriebenen Waschmitteln hat das hydrierte Rizinusöl die Aufgabe, die festen, nicht gießfähigen Formulierungen gegen Wasserabsonderung und Er¬ weichung zu stabilisieren.Solvent-free, solid to cream-shaped detergents which contain hydrogenated castor oil instead of the mentioned aromatics which are not very compatible with the world are known from German publication DT 1692026. In the detergents described there, the hydrogenated castor oil has the task of stabilizing the solid, non-pourable formulations against water secretion and softening.
Es bestand daher nach wie vor die Aufgabe, ein fließfähiges Handreini¬ gungsmittel zu entwickeln, das trotz seiner möglichst umweltfreundlichen Bestandteile ein gutes Reinigungsvermögen gegenüber frischen und ange¬ trockneten Farben, Lacken, Lasuren, Ölen, Teeren und Schmierstoffen auf¬ weist und über längere Zeit eine konstante Viskosität behält.There was therefore still the task of developing a flowable manual cleaning agent which, despite its environmentally friendly components, has good cleaning properties against fresh and dried paints, varnishes, glazes, oils, tars and lubricants and over a long period of time maintains a constant viscosity.
Überraschenderweise wurde nun gefunden, daß sich lösungsmittelhaltige flüssige Handreinigungsmittel auf Wasserbasis erzeugen lassen, die auch nach längerer Lagerung eine unveränderte Konsistenz aufweisen, wenn man eine Kombination von hydriertem Rizinusöl mit einem organischen Lösungs¬ mittel gemäß Formel I,Surprisingly, it has now been found that water-based liquid hand cleaning agents containing solvents can be produced which have an unchanged consistency even after prolonged storage if a combination of hydrogenated castor oil with an organic solvent of the formula I
R-C0-(0CH2CH2)n-0X (I),R-C0- (0CH2CH2) n -0X (I),
in der R einen Alkylrest mit 1 bis 3 C-Atomen, n eine Zahl von 1 bis 4 und X einen Alkylrest mit 1 bis 5 C-Atomen bedeutet, in die Reinigungsmittel einarbeitet.in which R is an alkyl radical with 1 to 3 C atoms, n is a number from 1 to 4 and X is an alkyl radical with 1 to 5 C atoms, incorporated into the cleaning agent.
Die erfindungsgemäßen Handreinigungsmittel enthalten darüberhinaus anio¬ nische und/oder nichtionische Tenside, Abrasivmittel und gegebenenfalls weitere möglichst hautfreundliche Lösungsmittel sowie sonstige in Haut¬ reinigungsmitteln übliche Stoffe wie Rückfettungsmittel, Parfüms und Farbstoffe. Sie sind fließfähige, weitgehend homogene Pasten, die auch bei längerer Lagerung, bei niedrigen oder erhöhten Temperaturen, keine Pha¬ sentrennung zeigen. Durch die in ihnen enthaltenen dermatologisch unbedenklichen organischen Lösungsmittel zeigen sie an menschlicher Haut sehr gute Reinigungswirkungen gegen Farben, Lasuren, Lacke, Öle und Teere.The hand cleansing agents according to the invention also contain anionic and / or nonionic surfactants, abrasives and optionally other solvents which are as skin-friendly as possible, as well as other substances customary in skin cleansing agents, such as moisturizing agents, perfumes and dyes. They are flowable, largely homogeneous pastes, which show no phase separation even when stored for a long time, at low or elevated temperatures. The dermatological contained in them harmless organic solvents, they show very good cleaning effects on human skin against paints, glazes, lacquers, oils and tars.
Die nachfolgend angegebenen Mengenanteile beziehen sich, falls nicht an¬ ders angegeben, auf das gesamte Reinigungsmittel.Unless stated otherwise, the proportions given below relate to the entire cleaning agent.
Das in den erfindungsgemäßen Reinigungsmitteln als Verdickungsmittel und Konsistenzgeber vorhandene hydrierte Rizinusöl ist vorzugsweise in Mengen von 0,1 Gew.-% bis 5 Gew.-%, insbesondere in Mengen von 1 Gew.-% bis 3 Gew.-% in den erfindungsgemäßen Reinigungsmitteln enthalten.The hydrogenated castor oil present in the cleaning agents according to the invention as a thickener and consistency agent is preferably in amounts of 0.1% by weight to 5% by weight, in particular in amounts of 1% by weight to 3% by weight in the cleaning agents according to the invention contain.
Die als organische Lösungsmittel in den erfindungsgemäßen Reinigungsmit¬ teln enthaltenen Carbonsäureester nach Formel I,The carboxylic acid esters of formula I contained as organic solvents in the cleaning agents according to the invention,
R-C0-(0CH2CH2)n-0X (I),R-C0- (0CH 2 CH 2 ) n-0X (I),
in der R einen Alkylrest mit 1 bis 3 C-Atomen, n eine Zahl von 1 bis 4, die als analytisch ermittelte Größe auch gebrochen sein kann, und X einen Alkylrest mit 1 bis 5 C-Atomen bedeutet, werden vorzugsweise in Mengen von 5 bis 40 Gew.-%, insbesondere bevorzugt in Mengen von 10 bis 30 Gew.-% in die erfindungsgemäßen Reinigungsmittel eingearbeitet. Aus der Gruppe der Lösungsmittel nach Formel I werden bevorzugt die Acetate (R=Methyl) und besonders bevorzugt die Verbindung mit R=Methyl, n=2 und X=n-Butyl (n- Butoxy-2-ethoxy-ethylacetat) in den erfindungsgemäßen Reinigungsmitteln eingesetzt.in which R is an alkyl radical with 1 to 3 C atoms, n is a number from 1 to 4, which can also be broken as an analytically determined size, and X is an alkyl radical with 1 to 5 C atoms, preferably in quantities of 5 up to 40% by weight, particularly preferably in amounts of 10 to 30% by weight, are incorporated into the cleaning agents according to the invention. From the group of solvents according to formula I, the acetates (R = methyl) and particularly preferably the compound with R = methyl, n = 2 and X = n-butyl (n-butoxy-2-ethoxy-ethyl acetate) are preferred in the inventive Detergents used.
Ester der allgemeinen Formel I können nach bekannten Verfahren, wie sie zum Beispiel in den europäischen Patentschriften EP 119 833 oder EP 163 522 beschrieben sind, hergestellt werden.Esters of the general formula I can be prepared by known processes, as described, for example, in European patent EP 119 833 or EP 163 522.
Zusätzlich können die erfindungsgemäßen Handreinigungsmittel weitere mög¬ lichst hautfreundliche organische Lösungsmittel, zu denen insbesondere Limonen und aromatenfreie Benzine, wie Isoparaffine, gehören, vorzugsweise in Mengen nicht über 20 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-%, enthalten. Bevorzugtes zusätzliches Lösungsmittel ist Limonen. Zu den Abrasivstoffen, die für die erfindungsgemäßen Reinigungsmitteln geeignet Sind, gehören Mikroglaskugeln, Quarzmehle, Holzmehle, Kreiden und Kunstoff ehle. Bevorzugt werden Polyurethanmehle eingesetzt. Die Abrasiv- stoffe sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise in Mengen von 1 bis 10 Gew.-%, insbesondere von 2 Gew.-% bis 6 Gew.-% ent¬ halten.In addition, the hand cleaning agents according to the invention can contain further organic solvents which are as skin-friendly as possible, including limonene and aromatic-free gasolines such as isoparaffins, preferably in amounts not exceeding 20% by weight, in particular from 5% by weight to 15% by weight. , contain. Limonene is the preferred additional solvent. The abrasive materials which are suitable for the cleaning agents according to the invention include micro-glass balls, quartz flours, wood flours, chalks and plastics. Polyurethane flours are preferably used. The abrasives are contained in the cleaning agents according to the invention preferably in amounts of 1 to 10% by weight, in particular 2% to 6% by weight.
Die erfindungsgemäßen Reinigungsmittel enthalten darüber hinaus anionische und/oder nichtionische Tenside, vorzugsweise in Mengen von 5 bis 70 Gew.-%, insbesondere von 10 Gew.-% bis 30 Gew.-%. Zu den in die erfin¬ dungsgemäßen Reinigungsmittel vorzugsweise einarbeitbaren aromatenfreien anionischen Tensiden gehören Alkylsulfate, Alkansulfonate und Alkylether- sulfate, bei denen die Alkylgruppen vorzugsweise 10 bis 20 C-Atome, ins¬ besondere 12 bis 18 C-Atome enthalten. Diese anionischen Tenside werden vorzugsweise in Form ihrer Natriumsalze eingesetzt. Zu den nichtionischen Tensiden, die bevorzugt in den erfindungsgemäßen Reinigungsmitteln vor¬ handen sind, gehören Alkylglykoside und die Anlagerungsprodukte von vor¬ zugsweise 4 bis 30 Molequivalenten Ethylenoxid und/oder Propylenoxid an Alkylglykoside, Alkansäuren und/oder Alkanole mit bevorzugt jeweils 12 bis 20 C-Atomen in den jeweiligen Alkylteilen. Auch die endgruppenverschlos- senen Derivate deratiger Alkoxylierungsprodukte, das heißt ihre endständigen O-Alkylierungsprodukte, vorzugsweise mit Endgruppen, die 2 bis 10 C-Atome enthalten, kommen in Frage. Zu derartigen nichtionischen Tensiden gehören beispielsweise die unter den Namen Dehypon(R) (Hersteller Henkel), Dehydol(R) (Hersteller Henkel), Lutensol(R) (Hersteller BASF) oder Triton(R) (Hersteller Rohm & Haas) vertriebenen Handelsprodukte.The cleaning agents according to the invention also contain anionic and / or nonionic surfactants, preferably in amounts of 5 to 70% by weight, in particular 10 to 30% by weight. The aromatic-free anionic surfactants which can preferably be incorporated into the cleaning agents according to the invention include alkyl sulfates, alkanesulfonates and alkyl ether sulfates, in which the alkyl groups preferably contain 10 to 20 carbon atoms, in particular 12 to 18 carbon atoms. These anionic surfactants are preferably used in the form of their sodium salts. The nonionic surfactants which are preferably present in the cleaning agents according to the invention include alkyl glycosides and the addition products of preferably 4 to 30 mol equivalents of ethylene oxide and / or propylene oxide to alkyl glycosides, alkanoic acids and / or alkanols, each preferably having 12 to 20 carbon atoms. Atoms in the respective alkyl parts. The end-capped derivatives of such alkoxylation products, that is to say their terminal O-alkylation products, preferably with end groups which contain 2 to 10 C atoms, are also suitable. Such nonionic surfactants include, for example, the commercial products sold under the names Dehypon ( R ) (manufacturer Henkel), Dehydol ( R ) (manufacturer Henkel), Lutensol ( R ) (manufacturer BASF) or Triton ( R ) (manufacturer Rohm & Haas).
Um der Entfettung der menschlichen Haut durch die Anwendung des erfin¬ dungsgemäßen Handreinigungsmittels vorzubeugen, enthalten sie bevorzugt zusätzlich zu den bisher genannten Bestandteilen Rückfettungsmittel, zu denen insbesondere Fettsäurealkanolamide, Fettsäurepolyalkanolamide, deren Ethylen- und/oder Propylenoxid-Anlagerungsprodukte und Fettsäuremonogly- ceride gehören. Besonders gut geeignet sind derartige Verbindungen, deren Fettsäureteil 12 bis 18 C-Atome enthält. Die Rückfettungsmittel sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise in Mengen nicht über 20 Gew.-%, insbesondere von 2 Gew.-% bis 18 Gew.-% enthalten. Zu den Bestandteilen, die zusätzlich in den erfindungsgemäßen Reinigungs¬ mitteln vorhanden sein können, gehören Farbstoffe, die vorzugsweise in Mengen von nicht über 0,1 Gew.-%, insbesondere nicht über 0,01 Gew.-% eingesetzt werden.In order to prevent degreasing of the human skin through the use of the hand cleaning agent according to the invention, they preferably contain refatting agents in addition to the previously mentioned components, which include in particular fatty acid alkanolamides, fatty acid polyalkanolamides, their ethylene and / or propylene oxide addition products and fatty acid monoglycerides. Compounds of which the fatty acid part contains 12 to 18 carbon atoms are particularly suitable. The refatting agents are contained in the cleaning agents according to the invention preferably in amounts of not more than 20% by weight, in particular from 2% by weight to 18% by weight. The constituents which may additionally be present in the cleaning agents according to the invention include dyes which are preferably used in amounts of not more than 0.1% by weight, in particular not more than 0.01% by weight.
Das erfindungsgemäße Handreinigungsmittel kann bei Raumtemperatur oder bei erhöhten Temperaturen angewendet werden. Es läßt sich leicht mit kaltem oder warmem Wasser abwaschen. Es kann auch zur Entfernung von Farben, Lacken, Ölen und Teeren von harten Oberflächen oder Textilien verwendet werden.The hand cleaning agent according to the invention can be used at room temperature or at elevated temperatures. It is easy to wash off with cold or warm water. It can also be used to remove paints, varnishes, oils and tars from hard surfaces or textiles.
Die Herstellung der erfindungsgemäßen Mittel weist keine Besonderheiten auf. Sie erfolgt am einfachsten durch Vermischen der einzelnen Bestand¬ teile, vorzugsweise bei erhöhter Temperatur von etwa 45 °C bis 80 °C, in einer Rührapparatur, wobei Wasser vorzugsweise als letzter Bestandteil zugegeben werden sollte, und anschließendes Abfüllen, gegebenenfalls nach Abkühlen, in übliche Behälter wie Kanister, Tuben, Pumpgefäße, Spender oder Dosen.The preparation of the agents according to the invention has no special features. The easiest way to do this is to mix the individual components, preferably at an elevated temperature of about 45 ° C. to 80 ° C., in a stirrer apparatus, water preferably being added as the last component, and then filling, if necessary after cooling, into conventional ones Containers such as canisters, tubes, pumping vessels, dispensers or cans.
BeispieleExamples
Beispiel 1example 1
Durch Vorlegen der organischen Lösungsmittel in einen Rührkessel, Zugabe des hydrierten Rizinusöls und des Rückfettungsmittels, Erwärmen auf 70 °C bis 75 °C, Zugabe der Tenside, des Abrasivmittels und des Wassers so, daß die Temperatur nicht unter 50 °C sank, und Abkühlen unter Rühren auf Raumtemperatur wurden die folgenden, durch ihre Zusammensetzung charakte¬ risierten Reinigungsmittel hergestellt:By placing the organic solvents in a stirred kettle, adding the hydrogenated castor oil and the refatting agent, heating to 70 ° C to 75 ° C, adding the surfactants, the abrasive and the water so that the temperature did not drop below 50 ° C, and cooling The following cleaning agents, characterized by their composition, were prepared with stirring to room temperature:
BlBl
10,0 Gew.-% ethoxyliertes Rizinusöl (Eumulgin(R) RT 20, Hersteller10.0% by weight of ethoxylated castor oil (Eumulgin ( R ) RT 20, manufacturer
Henkel) 9,0 Gew.-% Natriumlaurylethersulfat (Texapon(R) N 70, HerstellerHenkel) 9.0% by weight sodium lauryl ether sulfate (Texapon ( R ) N 70, manufacturer
Henkel) 20,0 Gew.-% n-Butoxy-2-ethoxyethylacetat 9,0 Gew.-% D-LimonenHenkel) 20.0% by weight of n-butoxy-2-ethoxyethyl acetate 9.0% by weight of D-limonene
2,0 Gew.-% hydriertes Rizinusöl (Rilanit(R) SM, Hersteller Henkel)2.0% by weight hydrogenated castor oil (Rilanit ( R ) SM, manufacturer Henkel)
4,3 Gew.-% Kokosfettsäurediethanolamid (Comperlan(R) KD, Hersteller4.3% by weight of coconut fatty acid diethanolamide (Comperlan ( R ) KD, manufacturer
Henkel)Handle)
2,7 Gew.-% Laurinsäuremonoglycerid (Hersteller Grünau)2.7% by weight lauric acid monoglyceride (manufacturer Grünau)
2,0 Gew.- Polyurethanmehl (Hersteller Puren-Schaumstoff GmbH)2.0% by weight polyurethane flour (manufacturer Puren-Schaumstoff GmbH)
41,0 Gew.-% Wasser41.0 wt% water
B2B2
5,7 Gew.-% Fettsäurepolyethoxylat (Eumulgin(R) KP 92, Hersteller5.7% by weight fatty acid polyethoxylate (Eumulgin ( R ) KP 92, manufacturer
Henkel) 5,5 Gew.-% Fettalkoholpolyalkoxylat (Dehypon(R) LT 45, HerstellerHenkel) 5.5% by weight fatty alcohol polyalkoxylate (Dehypon ( R ) LT 45, manufacturer
Henkel) 8,7 Gew.-% Natriu laurylethersulfat (Texapon(R) N 70, HerstellerHenkel) 8.7% by weight sodium lauryl ether sulfate (Texapon ( R ) N 70, manufacturer
Henkel)Handle)
25.0 Gew.-% n-Butoxy-2-ethoxyethylacetat 9,0 Gew.-% D-Limonen25.0% by weight of n-butoxy-2-ethoxyethyl acetate 9.0% by weight of D-limonene
1,0 Gew.-% hydriertes Rizinusöl (Rilanit(R) SM, Hersteller Henkel)1.0% by weight hydrogenated castor oil (Rilanit ( R ) SM, manufacturer Henkel)
3,0 Gew.-% Kokosfettsäurediethanolamid (Hersteller Henkel)3.0% by weight of coconut fatty acid diethanolamide (manufacturer Henkel)
2,5 Gew.-% Laurinsäuremonoglycerid (Hersteller Grünau)2.5% by weight lauric acid monoglyceride (manufacturer Grünau)
5,5 Gew.-% Polyurethanmehl (Hersteller Puren-Schaumstoff GmbH)5.5% by weight polyurethane flour (manufacturer Puren-Schaumstoff GmbH)
34.1 Gew.-% Wasser34.1% by weight of water
B3B3
5,0 Gew.- Fettsäurepolyethoxylat (Eumulgin(R) KP 92, Hersteller5.0% by weight fatty acid polyethoxylate (Eumulgin ( R ) KP 92, manufacturer
Henkel) 7,0 Gew.-% Natriumlaurylmyristylethersulfat (Texapon(R) K 14 S 70,Henkel) 7.0% by weight sodium lauryl myristyl ether sulfate (Texapon ( R ) K 14 S 70,
Hersteller Henkel) 20,0 Gew.-% n-Butoxy-2-ethoxyethylacetat 9,0 Gew.-% D-Limonen 3,9 Gew.-% Fettalkoholpolyalkoxylat (Dehypon(R) LT 45, HerstellerManufacturer Henkel) 20.0% by weight n-butoxy-2-ethoxyethyl acetate 9.0% by weight D-limonene 3.9% by weight fatty alcohol polyalkoxylate (Dehypon ( R ) LT 45, manufacturer
Henkel) 1,0 Gew.-% hydriertes Rizinusöl (Rilanit(R) SM, Hersteller Henkel) - i - .Henkel) 1.0% by weight hydrogenated castor oil (Rilanit ( R ) SM, manufacturer Henkel) - i -.
4,0 Gew.-% Laurinsäuremonoglycerid (Hersteller Grünau) 3,0 Gew.-% Polyurethanmehl (Hersteller Puren-Schaumstoff GmbH) 47,1 Gew.-% Wasser4.0% by weight lauric acid monoglyceride (manufacturer Grünau) 3.0% by weight polyurethane flour (manufacturer Puren-Schaumstoff GmbH) 47.1% by weight water
Nach dem oben beschriebenen Verfahren wurden zum Vergleich die von hy¬ driertem Rizinusöl freien Mittel VI bis V3 hergestellt :For comparison, agents VI to V3 free of hydrogenated castor oil were prepared by the process described above:
VIVI
10,0 Gew.-% ethoxyliertes Rizinusöl (Eumulgin(R) RT 20, Hersteller10.0% by weight of ethoxylated castor oil (Eumulgin ( R ) RT 20, manufacturer
Henkel) 9,0 Gew.-% Natriumlaurylethersulfat (Texapon(R) N 70, HerstellerHenkel) 9.0% by weight sodium lauryl ether sulfate (Texapon ( R ) N 70, manufacturer
Henkel) 20,0 Gew.-% n-Butoxy-2-ethoxyethylacetat 9,0 Gew.-% D-Limonen 2,0 Gew.-% organisch modifiziertes Schichtsilikat (Bentone(R) SD-2,Henkel) 20.0% by weight n-butoxy-2-ethoxyethyl acetate 9.0% by weight D-limonene 2.0% by weight organically modified layered silicate (Bentone ( R ) SD-2,
Hersteller Kronos) 4,3 Gew.-% Kokosfettsäurediethanolamid (Comperlan(R) KD, HerstellerManufacturer Kronos) 4.3% by weight coconut fatty acid diethanolamide (Comperlan ( R ) KD, manufacturer
Henkel) 2,7 Gew.-% Laurinsäuremonoglycerid (Hersteller Grünau) 2,0 Gew.-% Polyurethanmehl (Hersteller Puren-Schaumstoff GmbH) 41,0 Gew.-% WasserHenkel) 2.7% by weight lauric acid monoglyceride (manufacturer Grünau) 2.0% by weight polyurethane flour (manufacturer Puren-Schaumstoff GmbH) 41.0% by weight water
V2V2
10,0 Gew.-% ethoxyliertes Rizinusöl (Eumulgin(R) RT 20, Hersteller10.0% by weight of ethoxylated castor oil (Eumulgin ( R ) RT 20, manufacturer
Henkel) 4,0 Gew.-% partiell sulfatierte Fettalkylethoxylat (Texapon(R) WW 99,Henkel) 4.0% by weight of partially sulfated fatty alkyl ethoxylate (Texapon ( R ) WW 99,
Hersteller Henkel) 20,0 Gew.-% n-Butoxy-2-ethoxyethylacetat 9,0 Gew.-% D-LimonenManufacturer Henkel) 20.0% by weight n-butoxy-2-ethoxyethyl acetate 9.0% by weight D-limonene
3,0 Gew.-% pyrogene Kieselsäure (Aerosil(R) 200, Hersteller Degussa) 3,0 Gew.-% Kokosfettsäurediethanolamid (Comperlan(R) KD, Hersteller3.0% by weight of pyrogenic silica (Aerosil ( R ) 200, manufacturer Degussa) 3.0% by weight of coconut fatty acid diethanolamide (Comperlan ( R ) KD, manufacturer
Henkel) 3,0 Gew.-% Laurinsäuremonoglycerid (Hersteller Grünau) 3,0 Gew.-% Polyurethanmehl (Hersteller Puren-Schaumstoff GmbH) 45,0 Gew.-% Wasser V3Henkel) 3.0% by weight lauric acid monoglyceride (manufacturer Grünau) 3.0% by weight polyurethane flour (manufacturer Puren-Schaumstoff GmbH) 45.0% by weight water V3
5,0 Gew.-% Fettsäurepolyethoxylat (Eumulgin(R) KP 92, Hersteller5.0% by weight fatty acid polyethoxylate (Eumulgin ( R ) KP 92, manufacturer
Henkel) 7,0 Gew.-% Natriumlaurylethersulfat (Texapon(R) N 70, HerstellerHenkel) 7.0% by weight sodium lauryl ether sulfate (Texapon ( R ) N 70, manufacturer
Henkel)Handle)
25.0 Gew.-% n-Butoxy-2-ethoxyethylacetat 9,0 Gew.-% D-Limonen25.0% by weight of n-butoxy-2-ethoxyethyl acetate 9.0% by weight of D-limonene
3,9 Gew.-% Fettalkoholpolyethoxylat (Produkt Ke-2440, Hersteller3.9% by weight of fatty alcohol polyethoxylate (product Ke-2440, manufacturer
Henkel) 4,0 Gew.-% Laurinsäuremonoglycerid (Hersteller Grünau) 3,0 Gew.-% Polyurethanmehl (Hersteller Puren-Schaumstoff GmbH)Henkel) 4.0% by weight lauric acid monoglyceride (manufacturer Grünau) 3.0% by weight polyurethane flour (manufacturer Puren-Schaumstoff GmbH)
43.1 Gew.-% Wasser43.1% by weight of water
Die Mittel Bl bis B3 waren von fließfähiger, pumpbarer Konsistenz. Ihre Viskosität betrug ca. 10000 mPa«s. Die Abfüllung der Mittel erfolgte nach vollständiger Abkühlung auf Raumtemperatur in Tuben oder Kanister. Alter¬ nativ kann die Abfüllung in noch warmem Zustand, das heißt bei etwa 40 °C bis 50 °C, erfolgen. Zur Prüfung der Lagerstabilitat wurden die abgefüll¬ ten erfindungsgemäßen Reinigungsmittel über 3 Monate bei 0 °C, 6 Monate bei 40 °C oder 6 Monate bei Raumtemperatur gelagert, ohne daß eine Kon¬ sistenzänderung oder gar Phasentrennung beobachtet werden konnte. Die Mittel VI bis V3 wurden unter den gleichen Lagerungsbedingungen schon nach 2 Wochen, höchstens jedoch nach 4 Wochen inhomogen und zeigten Phasen¬ trennungen.The agents B1 to B3 were of a flowable, pumpable consistency. Its viscosity was about 10,000 mPa «s. The agents were filled into tubes or canisters after they had cooled completely to room temperature. Alternatively, the filling can take place while still warm, that is to say at about 40 ° C. to 50 ° C. To check the storage stability, the filled cleaning agents according to the invention were stored for 3 months at 0 ° C., 6 months at 40 ° C. or 6 months at room temperature without a change in consistency or even phase separation being observed. Agents VI to V3 became inhomogeneous after 2 weeks, but at most after 4 weeks, under the same storage conditions and showed phase separations.
Beispiel 2Example 2
Die in der nachfolgenden Tabelle angegebenen Farben und Lacke wurden je¬ weils als dünne, gleichmäßige Filme auf Glasplatten aufgetragen. Nach 24 Stunden Trocknen wurde jeweils ca. 1 Gramm des erfindungsgemäßen Hand¬ reinigers Bl oder eines handelsüblichen, pastenförmigen Handreinigers auf Wasserbasis (V4), der 3,4 Gew.-% Seife (Molgewicht 280), 5,3 Gew.-% ethoxyliertes Nonylphenol, 5,1 Gew.-% Fettsäurediethanolamid, 0,2 Gew.-% Diethanolamin, 0,9 Gew.-% Triethanolamin, 2,7 Gew.-% Polyurethanmehl, 9,0 Gew.-% Limonen und 36,0 Gew.-% aromatenhaltiges Benzin enthielt, aufge¬ tragen und die bei gleichmäßig starkem Reiben mit einem Finger benötigte Zeit bis zur Entfernung der Schicht bestimmt. Die erfindungsgemäßen Rei¬ niger B2 und B3 wurden unter den gleichen Bedingungen getestet und unter¬ schieden sich in ihrer Reinigungsleistung nicht von der des Handreinigers Bl.The paints and lacquers listed in the table below were each applied as thin, uniform films to glass plates. After drying for 24 hours, approx. 1 gram of the hand cleaner B1 according to the invention or a commercially available pasty hand cleaner based on water (V4), the 3.4% by weight soap (molecular weight 280), 5.3% by weight ethoxylated Nonylphenol, 5.1% by weight fatty acid diethanolamide, 0.2% by weight diethanolamine, 0.9% by weight triethanolamine, 2.7% by weight polyurethane flour, 9.0% by weight limonene and 36.0 Contained wt .-% aromatics-containing gasoline, applied and needed with uniformly strong rubbing with a finger Time to remove the layer determined. The cleaners B2 and B3 according to the invention were tested under the same conditions and did not differ in their cleaning performance from that of the hand cleaner Bl.
Tabelle 1Table 1
Farbe / Lack Abriebzeit [Sekunden] Bl V4Paint / lacquer abrasion time [seconds] Bl V4
Fensterlasur 10 20 (Gori(R) Mooreiche)Window glaze 10 20 (Gori ( R ) bog oak)
Malerlack 20 größer 120 (Herbol(R) extra weiß)Paint 20 larger than 120 (Herbol ( R ) extra white)
Schnellgrund 10 60 (Schäfergrau)Schnellgrund 10 60 (shepherd gray)
Metalliclack 10 20 (Icosit(R) 5530)Metallic paint 10 20 (Icosit ( R ) 5530)
lufttrocknender Auto- 20 größer 120 Reparaturlack (Auto-K)air-drying car 20 larger than 120 repair paint (Auto-K)
Silikat-Farbe 40 50 (Kieselit( ))Silicate color 40 50 (Kieselit ())
Sowohl die Anwendungstests wie auch die Lagertests zeigen die Überlegen¬ heit der erfindungsgemäßen Mittel. Besonders bemerkenswert ist die im Vergleich zu dem zwar lagerstabilen, aber schwer abbaubare Inhaltsstoffe enthaltenden Reiniger V4 deutlich bessere Reinigungsleistung der erfindungsge äßen Handreiniger. Both the application tests and the storage tests show the superiority of the agents according to the invention. Particularly noteworthy is that compared to the cleaner V4, which contains storage-stable ingredients that are difficult to decompose, the cleaning performance of the hand cleaners according to the invention is significantly better.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904009534 DE4009534A1 (en) | 1990-03-24 | 1990-03-24 | LIQUID HAND CLEANER |
| DEP4009534.7 | 1990-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1991014420A1 true WO1991014420A1 (en) | 1991-10-03 |
Family
ID=6403001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1991/000497 Ceased WO1991014420A1 (en) | 1990-03-24 | 1991-03-15 | Liquid hand-cleansing agent |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0521899A1 (en) |
| DE (1) | DE4009534A1 (en) |
| WO (1) | WO1991014420A1 (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4335933A1 (en) * | 1993-10-21 | 1995-04-27 | Stockhausen Chem Fab Gmbh | Skin cleansing preparations, process for their preparation and their use |
| US6436690B1 (en) * | 1993-09-15 | 2002-08-20 | The Procter & Gamble Company | BPN′ variants having decreased adsorption and increased hydrolysis wherein one or more loop regions are substituted |
| US6440717B1 (en) * | 1993-09-15 | 2002-08-27 | The Procter & Gamble Company | BPN′ variants having decreased adsorption and increased hydrolysis |
| US6451574B1 (en) * | 1995-03-09 | 2002-09-17 | The Procter & Gamble Company | Proteinase K variants having decreased adsorption and increased hydrolysis |
| US6455295B1 (en) * | 1995-03-08 | 2002-09-24 | The Procter & Gamble Company | Subtilisin Carlsberg variants having decreased adsorption and increased hydrolysis |
| US6475765B1 (en) * | 1995-03-09 | 2002-11-05 | Procter & Gamble Company | Subtilisin DY variants having decreased adsorption and increased hydrolysis |
| US6599730B1 (en) * | 1994-05-02 | 2003-07-29 | Procter & Gamble Company | Subtilisin 309 variants having decreased adsorption and increased hydrolysis |
| WO2012177676A1 (en) * | 2011-06-20 | 2012-12-27 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| WO2012177757A3 (en) * | 2011-06-20 | 2013-02-21 | The Procter & Gamble Company | Personal care compositions comprising shaped abrasive particles |
| US8440603B2 (en) | 2011-06-20 | 2013-05-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising a polylactic acid biodegradable abrasive |
| US8440602B2 (en) | 2009-12-22 | 2013-05-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising a divinyl benzene cross-linked styrene polymer |
| US8440604B2 (en) | 2008-09-30 | 2013-05-14 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
| US8445422B2 (en) | 2010-09-21 | 2013-05-21 | The Procter & Gamble Company | Liquid cleaning composition |
| US8470759B2 (en) | 2011-06-20 | 2013-06-25 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising a polyhydroxy-alkanoate biodegradable abrasive |
| US8546316B2 (en) | 2010-09-21 | 2013-10-01 | The Procter & Gamble Company | Liquid detergent composition with natural abrasive particles |
| US8551932B2 (en) | 2008-09-30 | 2013-10-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
| US8569223B2 (en) | 2008-09-30 | 2013-10-29 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
| US8629095B2 (en) | 2010-04-21 | 2014-01-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising polyurethane foam abrasive particles |
| US8680036B2 (en) | 2009-12-22 | 2014-03-25 | The Procter & Gamble Company | Liquid cleaning composition comprising color-stable polyurethane abrasive particles |
| US8759270B2 (en) | 2011-06-20 | 2014-06-24 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
| WO2014019944A3 (en) * | 2012-08-03 | 2014-10-02 | Pibed Limited | Formulation for gritty foam dispenser |
| US8852643B2 (en) | 2011-06-20 | 2014-10-07 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| US9163201B2 (en) | 2012-10-15 | 2015-10-20 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
| US9353337B2 (en) | 2010-09-21 | 2016-05-31 | The Procter & Gamble Company | Liquid cleaning composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993024603A2 (en) * | 1992-06-02 | 1993-12-09 | Unilever N.V. | Liquid cleaning products |
| DE19748921C2 (en) * | 1997-10-30 | 2001-02-22 | Stockhausen Chem Fab Gmbh | Skin-friendly hand cleaners, especially rough hand cleaners |
| DE102007022693A1 (en) * | 2007-05-11 | 2009-01-15 | Evonik Stockhausen Gmbh | Skin and hand cleaners with hydrophilic emollients |
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| FR1553432A (en) * | 1967-02-07 | 1969-01-10 | ||
| EP0051232A1 (en) * | 1980-10-30 | 1982-05-12 | Henkel Kommanditgesellschaft auf Aktien | Hand cleaner |
| DE3717600A1 (en) * | 1987-05-25 | 1988-12-08 | Henkel Kgaa | Aqueous hand cleaning composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE4009534A1 (en) | 1991-09-26 |
| EP0521899A1 (en) | 1993-01-13 |
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