EP1174493B1 - Soap bar comprising talc, alkali fatty acid and emollient, but not comprising alkyl oligoglycosides - Google Patents

Soap bar comprising talc, alkali fatty acid and emollient, but not comprising alkyl oligoglycosides Download PDF

Info

Publication number
EP1174493B1
EP1174493B1 EP01115784A EP01115784A EP1174493B1 EP 1174493 B1 EP1174493 B1 EP 1174493B1 EP 01115784 A EP01115784 A EP 01115784A EP 01115784 A EP01115784 A EP 01115784A EP 1174493 B1 EP1174493 B1 EP 1174493B1
Authority
EP
European Patent Office
Prior art keywords
soap
fatty acids
weight
alcohols
product according
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.)
Revoked
Application number
EP01115784A
Other languages
German (de)
French (fr)
Other versions
EP1174493A1 (en
Inventor
Andreas Lenuck
Jens Dr. Treu
Erich Karcher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beiersdorf AG
Original Assignee
Beiersdorf AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7649527&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1174493(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Beiersdorf AG filed Critical Beiersdorf AG
Publication of EP1174493A1 publication Critical patent/EP1174493A1/en
Application granted granted Critical
Publication of EP1174493B1 publication Critical patent/EP1174493B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/48Superfatting agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/18Water-insoluble compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/24Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/26Organic compounds, e.g. vitamins containing oxygen

Definitions

  • the present invention relates to cosmetic cleansers in the form of shaped soap products. Such agents are known per se. It is essentially about surface-active substances or mixtures of substances which are available to the consumer in various Preparations are offered.
  • the invention particularly relates to bar soaps with improved Smoothness and increased lime soap dispersibility due to a content of talc and one or more lubricating substances in simultaneous absence of alkyl (oligo) glycosides.
  • US-A-5264145 discloses a molded soap product containing C12-C22. Alkaline fatty acid, free fatty acid, waxes and optionally talc.
  • Skin-specific surface-active substances also make skin fats to a certain extent solved and washed out. This requires a subsequent swelling after a subsequent Significant dehydration of the skin, which are reinforced by detergent additives can.
  • bar soaps not only have to cleanse the skin, but also maintain it, d. H. prevent drying out, grease and provide protection against outside influences Offer.
  • the soap will be especially tolerated by the skin is, but it should still result in the application as much and creamy foam and cause a pleasant feeling on the skin.
  • manufacturers are looking for Bar soaps constantly looking for new ingredients that meet this increased requirement profile Take into account.
  • Main components are the alkali salts of the fatty acids of natural oils u. Fats, preferably the chain lengths C 12 -C 18 . Since lauric acid soaps foam particularly well, the lauric acid-rich coconut and palm kernel oils are preferred raw materials for the production of fine soap.
  • the sodium salts of the fatty acid mixtures are solid, the potassium salts soft-pasty.
  • saponification the diluted sodium or potassium hydroxide solution is added to the fatty raw materials in a stoichiometric ratio so that an excess of alkali of not more than 0.05% is present in the finished soap. In many cases, the soaps are no longer produced directly from the fats, but from the fatty acids obtained by lipolysis.
  • Common soap additives are fatty acids, fatty alcohols, lanolin, lecithin, vegetable oils, partial glycerides and other fat-like substances to restore the cleansed skin, antioxidants like ascorbyl palmitate or tocopherol to prevent autoxidation of the Soap (rancidity), complexing agent such as nitrilotriacetate for binding heavy metal traces, which could catalyze the autoxidative spoilage, perfume oils to achieve the desired fragrances, dyes for coloring the soap bars and if desired special additives.
  • Surfactants are amphiphilic substances that can dissolve organic, nonpolar substances in water. They provide, due to their specific molecular structure with at least one hydrophilic and a hydrophobic part of the molecule, for a lowering of the surface tension water, wetting the skin, facilitating the removal of dirt and solution, a light rinse and, as desired, foam control.
  • the object of the invention was therefore to provide bar soaps available, which are free of the described disadvantages. It was particularly important to take into account that new bar soap compositions must also be able to be produced industrially, d. H. that the compositions, for example, a sufficient, but not too have high ductility and do not tend to crack during drying.
  • the foam also gets an even better creaminess and more volume, which also was not expected.
  • Another advantage of this invention is that the compatibility of the washing piece is improved because the total content of surface-active substances is reduced becomes.
  • the molded soap products according to the invention also possess the mechanical properties Deformation a particularly smooth surface. At the application they produce a creamy, stable foam. The lime soap precipitate formed in hard water remains dispersed in the water and does not lead to the gray-greasy deposits on the surface of sanitary objects.
  • Talc is a hydrated magnesium silicate of composition 3MgO ⁇ 4SiO 2 . H 2 O or Mg 3 (Si 4 O 10 ). (OH) 2 or Mg 6 (OH) 4 [Si 8 O 20 ] or Mg 12 [Si 16 O 40 ], however, the proportions of hydrated magnesium aluminum silicate of may contain up to 12% by weight of Al 2 O 3 , based on the total product.
  • Talc is a white, usually very fine, virtually odorless to slightly earthy-smelling powder, which feels greasy when rubbing, without being fatty. It is insoluble in water, cold acids or alkalis.
  • talc based on the content of anhydrous magnesium silicate
  • Talcum is used for the production of pharmaceutical, but especially for the production of cosmetic powders, which are used for personal care, but is also suitable for tablet production as a lubricant or superplasticizer.
  • the particle diameter (equivalent spherical diameter) of the talc is in the range of 0.5-50 ⁇ m. In general, such talcum qualities have been proven, not more than 5% by weight of particles below 1 ⁇ m and not more than 5% by weight of particles 50 ⁇ m size included. Preferably, the proportion of particles larger than 40 microns in Diameters are (sieve residue), at most 2 wt .-%.
  • the mean particle diameter (D 50) is preferably 5 -15 ⁇ m.
  • the content of impurities should not exceed 1.6% by weight of Fe 2 O 3 , 1% by weight of CaO and 1% by weight of unbound water (dry loss at 1050 ° C.).
  • the content of hydrated magnesium aluminum silicate may be up to 60% by weight, calculated as Al 2 O 3 , up to 12% by weight.
  • the shaped soap products contain from 1 to 20% by weight of talcum.
  • the shaped soap products also contain 1 - 99 wt .-% of a base soap, for example one whose soap components composed of sodium tallowate, sodium cocoate and sodium palm kernel fatty acid salt.
  • the shaped soap products of the invention advantageously contain water in an amount of 5-35% by weight.
  • the water content is partly due to the Manufacturing process, on the other hand, it has a favorable effect on the performance characteristics of Soap off.
  • fatty acids for the preparation of the basic soap are the linear fatty acids having 12 to 22 carbon atoms, eg. As the lauric, myristic, palmitic, stearic, arachin and behenic acid, but also the unsaturated fatty acids, eg. As the palmitoleic, oleic, linoleic, linolenic, arachidonic and erucic acid used. Preference is given to technical mixtures, such as are available from vegetable and animal fats and oils used, for. As coconut oil fatty acid and tallow fatty acid. Particular preference is given to mixtures of coconut oil and tallow fatty acid slices, in particular a mixture of 50-80% by weight C 16 -C 18 tallow fatty acid and 20-50% by weight C 12 -C 14 coconut fatty acid.
  • the fatty acids are used in the form of their alkali soap, usually as sodium soaps.
  • the soaps can also be obtained from the fats and oils directly by saponification (hydrolysis) be generated with sodium hydroxide solution and separating the glycerol.
  • the inventive molded soap products an additional proportion of 1-10 wt .-% of free fatty acids with 12-22 carbon atoms.
  • These can be identical to the fatty acids of the basic soap and by a corresponding Alkalikalunterschuß in the saponification in the Basic soap are introduced.
  • the free fatty acids are preferred after saponification and after concentration, before drying, metered.
  • R 1 is a primary C 12 -C 16 - Alkyl group
  • the alkyl (oligo) glycosides can be derived from aldoses or ketoses with 5 or 6 carbons.
  • alkyl (oligo) glucosides derived primarily from glucose are produced on an industrial scale. Absence of these substances means that they may at most be present as impurities in the mass underlying the invention combibar, at least less than 1 wt .-% must be.
  • the soap bars according to the invention can be used as further auxiliaries and additives Emulsifiers, superfatting agents, fats, waxes, stabilizers, cationic polymers, silicone compounds, Pigments, biogenic agents, preservatives, dyes and fragrances contain.
  • greasing agents are oil bodies such as Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 20 fatty acids with linear C 6 -C 20 fatty alcohols, esters of branched C 6 - C 13 -carboxylic acids with linear C 6 -C 20 -fatty alcohols, esters of linear C 6 -C 18 -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (for example Dimerdiol or trimerdiol) and / or Guerbetalkoho triglycerides based on C 6 -C 10 fatty acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbetcarbon dialkyl ethers and / or aliphatic or naphthenic hydrocarbons into consideration.
  • oils for example Dimerdi
  • Soap products according to the invention are particularly advantageously characterized in that they contain 1 - 30 wt .-% of moisturizing effective substances.
  • emulsifiers or co-emulsifiers can nonionic, ampholytic and / or zwitterionic surfactants which are characterized by a lipophilic, preferably linear, alkyl or alkenyl group and at least one hydrophilic group.
  • This hydrophilic group can be both ionogenic and nonionic Be a group.
  • Nonionic emulsifiers contain as hydrophilic group z.
  • polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate are also suitable.
  • mixtures of compounds of several of these classes of substances are known, commercially available products. These are mixtures of homologs whose mean Alkoxyl michsgrad the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds.
  • C 12/14 fatty acid mono- and diesters of addition products of ethylene oxide with glycerol are known from DE-20 24 051 as refatting agents for cosmetic preparations.
  • Suitable w / o emulsifiers are: (b1) addition products of from 2 to 15 mol of ethylene oxide with castor oil and / or hydrogenated castor oil; (b2) partial esters based on linear, branched, unsaturated or saturated C 12/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol) and polyglucosides (eg.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic Strong, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / Vinylimidazole polymers such.
  • B. Luviquat TM (BASF AG) condensation products of polyglycols and amines, quaternized collagen polypeptides such as "Lauryldimonium hydroxypropyl hydrolyzed collagen" (Lamequat TM L, Grünau GmbH) or "Lauryldimmonium-hydroxypropyl-hydroxylated-wheat-protein” (Gluadin TM WQ, Grünau GmbH), polyethyleneimine, cationic silicone polymers such.
  • Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty, alcohol, polyether, epoxy, fluorine- and / or alkyl-modified silicone compounds.
  • superfatting agents can substances such as polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, Monoglycerides and fatty acid alkanolamides are used, the latter being simultaneously serve as foam stabilizers.
  • Typical examples of fats are glycerides, as Waxes come u. a. Beeswax, paraffin wax or microwaxes optionally in Combination with hydrophilic waxes, e.g. As cetylstearyl alcohol in question.
  • As stabilizers Metal salts of fatty acids such. As magnesium, aluminum and / or zinc stearate be used.
  • titanium dioxide may be considered as a pigment under biogenic Active ingredients are understood, for example, as plant extracts and vitamin complexes.
  • Preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, Pentanediol or sorbic acid.
  • dyes can be used for cosmetic purposes suitable and approved substances are used, as for example in the Publication "Cosmetic Colorants" of the Dye Commission of the Irish Kla Klasisme, Verlag Chemie, Weinheim, 1984, pp. 81-106. These Dyestuffs are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the entire mixture used.
  • the total amount of auxiliaries and additives can 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount.
  • the shaped soap products of the present invention may be perfumes and others customary auxiliaries and additives in an amount of up to 5 wt .-%.
  • suitable Auxiliary substances are z.
  • binders or plasticizers As such are z.
  • Glycerol Fatty acid partial glycerides or fatty alcohols with 12-22 C atoms.
  • the fatty alcohols may, for. B. as a by-product of alkyl (oligo) glucosides are added together with these, if the alkyl (oligo) glucosides are used as crude product with a content of up to 50% by weight uses free fatty alcohol.
  • auxiliaries are z.
  • dyes antimicrobial agents, deodorant agents, pigments (TiO 2 ), optical brighteners and complexing agents.
  • the preparation of the molded soap products according to the invention can be carried out in soaps usual way.
  • soaps usual way.
  • initially from fatty acid approach and sodium hydroxide solution Grundseife having a solids content of 25-50 wt .-% and prepared to a solids content of 50-70 wt .-% concentrated.
  • this z. B. 60% basic soap can already the talc, optionally also free fatty acid, an anionic surfactant and a complexing agent be mixed.
  • the basic soap z. B. in a vacuum expansion dryer further dehydrated at 120 ° C to 130 ° C. During expansion, the soap cools spontaneously to temperatures below 60 ° C and solidifies. This fall soap noodles with a Solids content of 73-85 wt .-% of.
  • this basic soap represents the finishing of fine soap. It takes place in a soap mixer in which a slurry of the alkyl (oligo) glucoside and the other additives and additives in the soap noodles is mixed.
  • a soap mixer in which a slurry of the alkyl (oligo) glucoside and the other additives and additives in the soap noodles is mixed.
  • Molded soap products according to the invention can also be used as noodles, needles, Granules, extrudates, flakes and in any other usual for soap products shaping available.
  • the talc can also be added only during the preparation be incorporated into the 73-85% basic soap.
  • the talcum powder via suitable dosing devices, eg. B. belt scale and shaker at the same time the slurry of perfumes and auxiliaries supplied to the soap mixer.
  • the soap products of the invention are characterized by a particularly smooth surface from what pleasantly noticeable especially when processing to bar soap power. In use, it forms abundantly fine bubbles, creamy foam. In hard water Although Kalkseifenausmatlitch form, but they remain dispersed in the solution and do not strike on hard surfaces as greasy-gray stains or cheesier ones Edge, but at best as a light, finely divided veil down.
  • the ground soap noodles are dosed with the color slurry and the other components in a conventional soap mixer (screw mixer with perforated screen), homogenized by repeated mixing, discharged via an extruder, cut and processed in the usual way to pieces.
  • a conventional soap mixer screw mixer with perforated screen
  • Example 2 Wt .-% color slurry 3.00 basic soaps 85,00 paraffin 1.00 talc 7.00 Perfume 1.00 Na 2 S 2 O 3 0.40 octyldodecanol 0.50 water ad 100.00
  • the ground soap noodles are dosed with the color slurry and the other components in a conventional soap mixer (screw mixer with perforated screen), homogenized by repeated mixing, discharged via an extruder, cut and processed in the usual way to pieces.
  • a conventional soap mixer screw mixer with perforated screen
  • Example 3 Wt .-% color slurry 3.00 basic soaps 81.80 paraffin 1.00 talc 9.00 Perfume 1.00 Na 2 S 2 O 3 0.40 octyldodecanol 0.50 water ad 100.00
  • the ground soap noodles are dosed with the color slurry and the other components in a conventional soap mixer (screw mixer with perforated screen), homogenized by repeated mixing, discharged via an extruder, cut and processed in the usual way to pieces.
  • a conventional soap mixer screw mixer with perforated screen
  • Example 4 Wt .-% color slurry 3.00 basic soaps 78,90 paraffin 1.00 talc 12,00 Perfume 1.00 Na 2 S 2 O 3 0.40 octyldodecanol 0.50 water ad 100.00
  • the basic soap noodles become with the color slurry and the remaining components in one usual soap mixer (screw mixer with perforated sieve) dosed, by repeated mixing Homogenized, discharged via an extruder, cut and in the usual Way to pieces processed.
  • soap mixer screw mixer with perforated sieve

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

A shaped soap product free of alkyl-(oligo)-glycosides contains (a) talc, (b) a 12-22C fatty acid in alkali soap form and (c) an oil replacement material.

Description

Die vorliegende Erfindung betrifft kosmetische Reinigungsmittel in Form geformter Seifenprodukte. Derartige Mittel sind an sich bekannt. Es handelt sich dabei im wesentlichen um oberflächenaktive Substanzen oder Stoffgemische, die dem Verbraucher in verschiedenen Zubereitungen angeboten werden. Die Erfindung betrifft insbesondere Stückseifen mit verbesserter Glätte und erhöhtem Kalkseifendispergiervermögen durch einen Gehalt an Talkum und einer oder mehreren rückfettend wirkenden Substanzen bei gleichzeitiger Abwesenheit von Alkyl-(oligo)-glycosiden.The present invention relates to cosmetic cleansers in the form of shaped soap products. Such agents are known per se. It is essentially about surface-active substances or mixtures of substances which are available to the consumer in various Preparations are offered. The invention particularly relates to bar soaps with improved Smoothness and increased lime soap dispersibility due to a content of talc and one or more lubricating substances in simultaneous absence of alkyl (oligo) glycosides.

US-A-5264145 offenbart ein geformtes seifenproduckt enthaltend C12-C22. Alkalifettsaüre, freie Fettsaüre, wachse und fakultativ Talkum.US-A-5264145 discloses a molded soap product containing C12-C22. Alkaline fatty acid, free fatty acid, waxes and optionally talc.

Oberflächenaktive Stoffe - am bekanntesten die Alkalisalze der höheren Fettsäuren, also die klassischen "Seifen" - sind amphiphile Stoffe, die organische unpolare Substanzen in Wasser emulgieren können.Surface-active substances - most prominently the alkali salts of the higher fatty acids, thus the classic "soaps" - are amphiphilic substances that are organic nonpolar substances in water can emulsify.

Diese Stoffe schwemmen nicht nur Schmutz von Haut und Haaren, sie reizen, je nach Wahl des Tensids oder des Tensidgemisches, Haut und Schleimhäute mehr oder minder stark. Es ist zwar eine große Zahl recht milder Tenside erhältlich, jedoch sind die Tenside des Standes der Technik entweder mild, reinigen aber schlecht, oder aber sie reinigen gut, reizen jedoch Haut oder Schleimhäute.These fabrics not only soak up dirt from the skin and hair, they irritate, depending on your choice the surfactant or surfactant mixture, skin and mucous membranes more or less strong. It Although a large number of fairly mild surfactants is available, however, the surfactants of the prior art The technique either mild, but clean poor, or they clean well, but irritate Skin or mucous membranes.

Schon bei einem einfachen Wasserbade ohne Zusatz von Tensiden kommt es zunächst zu einer Quellung der Hornschicht der Haut, wobei der Grad dieser Quellung beispielsweise von der Dauer des Bades und dessen Temperatur abhängt. Zugleich werden wasserlösliche Stoffe, z.B. wasserlösliche Schmutzbestandteile, aber auch hauteigene Stoffe, die für das Wasserbindungsvermögen der Hornschicht verantwortlich sind, ab- bzw. ausgewaschen. Even in a simple water bath without the addition of surfactants, it comes first a swelling of the horny layer of the skin, the degree of swelling of, for example, the duration of the bath and its temperature depends. At the same time become water-soluble Fabrics, e.g. water-soluble dirt components, but also skin-own substances, which are responsible for the Water binding capacity of the horny layer are responsible, washed off or washed out.

Durch hauteigene oberflächenaktive Stoffe werden zudem auch Hautfette in gewissem Ausmaße gelöst und ausgewaschen. Dies bedingt nach anfänglicher Quellung eine nachfolgende deutliche Austrocknung der Haut, die durch waschaktive Zusätze nach verstärkt werden kann.Skin-specific surface-active substances also make skin fats to a certain extent solved and washed out. This requires a subsequent swelling after a subsequent Significant dehydration of the skin, which are reinforced by detergent additives can.

Diesen Übelständen galt es also, Abhilfe zu schaffen.So it was a matter of remedying these evils.

Bei gesunder Haut sind diese Vorgänge im allgemeinen belanglos, da die Schutzmechanismen der Haut solche leichten Störungen der oberen Hautschichten ohne weiteres kompensieren können. Aber bereits im Falle nichtpathologischer Abweichungen vom Normalstatus, z.B. durch umweltbedingte Abnutzungsschäden bzw. Irritationen, Lichtschäden, Altershaut usw., ist der Schutzmechanismus der Hautoberfläche gestört. Unter Umständen ist er dann aus eigener Kraft nicht mehr imstande, seine Aufgabe zu erfülten und muß durch exteme Maßnahmen regeneriert werden. Aufgabe der vorliegenden Erfindung war somit, diesem Mangel des Standes der Technik Abhilfe zu schaffen.In healthy skin, these processes are generally trivial, since the protective mechanisms The skin easily compensate for such minor disorders of the upper layers of the skin can. But even in the case of non-pathological deviations from normal status, e.g. due to environmental damage or irritation, photodamage, aging skin etc., the protective mechanism of the skin surface is disturbed. It may be He then, on his own, is no longer able to fulfill his task and must go through external measures are regenerated. The object of the present invention was thus to To remedy this deficiency of the prior art.

Bei der Körperreinigung spielen Stückseifen eine große Rolle, die heutzutage großtechnisch durch kontinuierliche Verseifung von freien Fettsäuren mit Alkalien, Aufkonzentrieren der Grundseifen und Sprühtrocknung hergestellt werden. Man unterscheidet dabei zwischen echten Alkaliseifen, die ausschließlich Fettsäuresalze und gegebenenfalls noch freie Fettsäuren enthalten und sogenannten "Combibars", Stückseifen, die neben Fettsäuresalzen noch weitere synthetische Tenside, in der Regel Fettalkoholethersulfate oder Fettsäureisothionate aufweisen. Eine Sonderstellung nehmen hingegen die Syndetstückseifen, sogenannte "Syndetbars" ein, die bis auf Verunreinigungen frei von Fettsäuresalzen sind und ausschließlich synthetische Tenside enthalten.When it comes to body cleansing, bar soaps play an important role, and these are nowadays large-scale by continuous saponification of free fatty acids with alkalis, concentrating the Grundseifen and spray drying are produced. One differentiates between genuine alkali soaps containing exclusively fatty acid salts and optionally free fatty acids contain and so-called "Combibars", bar soaps, in addition to fatty acid salts still other synthetic surfactants, usually fatty alcohol ether or fatty acid isothionates exhibit. A special position, however, take the Syndetstückseifen, so-called "Syndetbars", which are free from impurities except fatty acid salts and contain only synthetic surfactants.

Allein in Deutschland werden jährlich mehrere Millionen Stück Seifen für die Körperhygiene verkauft. Die Anforderungen des Marktes an diesen Massenverbrauchsartikel werden dabei jedoch immer höher: Stückseifen müssen die Haut nicht nur reinigen, sondern auch pflegen, d. h. ein Austrocknen verhindem, rückfetten und einen Schutz gegen Einflüsse von außen bieten. Selbstverständlich wird erwartet, daß die Seife in besonderem Masse hautverträglich ist, sie soll aber in der Anwendung dennoch möglichst viel und cremigen Schaum ergeben und ein angenehmes Hautgefühl bewirken. In diesem Zusammenhang suchen Hersteller von Stückseifen ständig nach neuen Inhaltsstoffen, die diesem gestiegenen Anforderungsprofil Rechnung tragen.In Germany alone, several million pieces of soaps are used for personal hygiene every year sold. The requirements of the market for these mass consumables are included but always higher: bar soaps not only have to cleanse the skin, but also maintain it, d. H. prevent drying out, grease and provide protection against outside influences Offer. Of course, it is expected that the soap will be especially tolerated by the skin is, but it should still result in the application as much and creamy foam and cause a pleasant feeling on the skin. In this regard, manufacturers are looking for Bar soaps constantly looking for new ingredients that meet this increased requirement profile Take into account.

Man unterscheidet feste, meist stückförmige, und flüssige Seifen. Hauptbestandteile sind die Alkalisalze der Fettsäuren natürlicher Öle u. Fette, vorzugsweise der Kettenlängen C12-C18. Da Laurinsäureseifen besonders gut schäumen, sind die laurinsäurereichen Kokos- und Palmkernöle bevorzugte Rohstoffe für die Feinseifenherstellung. Die Natriumsalze der Fettsäuregemische sind fest, die Kaliumsalze weich-pastös. Zur Verseifung wird die verdünnte Natron- oder Kalilauge den Fettrohstoffen im stöchiometrischen Verhältnis so zugesetzt, daß in der fertigen Seife ein Laugenüberschuß von höchstens 0,05% vorhanden ist. Vielfach werden die Seifen heute nicht mehr direkt aus den Fetten, sondem aus den durch Fettspaltung gewonnenen Fettsäuren hergestellt.One differentiates between solid, usually piece-shaped, and liquid soaps. Main components are the alkali salts of the fatty acids of natural oils u. Fats, preferably the chain lengths C 12 -C 18 . Since lauric acid soaps foam particularly well, the lauric acid-rich coconut and palm kernel oils are preferred raw materials for the production of fine soap. The sodium salts of the fatty acid mixtures are solid, the potassium salts soft-pasty. For saponification, the diluted sodium or potassium hydroxide solution is added to the fatty raw materials in a stoichiometric ratio so that an excess of alkali of not more than 0.05% is present in the finished soap. In many cases, the soaps are no longer produced directly from the fats, but from the fatty acids obtained by lipolysis.

Übliche Seifen-Zusätze sind Fettsäuren, Fettalkohole, Lanolin, Lecithin, pflanzliche Öle, Partialglyceride und andere fettähnliche Substanzen zur Rückfettung der gereinigten Haut, Antioxidantien wie Ascorbylpalmitat oder Tocopherol zur Verhinderung der Autoxidation der Seife (Ranzigkeit), Komplexierungsmittel wie Nitrilotriacetat zur Bindung von SchwermetallSpuren, die den autoxidativen Verderb katalysieren könnten, Parfümöle zur Erzielung der gewünschten Duftnoten, Farbstoffe zur Einfärbung der Seifenstücke und gewünschtenfalls spezielle Zusätze.Common soap additives are fatty acids, fatty alcohols, lanolin, lecithin, vegetable oils, partial glycerides and other fat-like substances to restore the cleansed skin, antioxidants like ascorbyl palmitate or tocopherol to prevent autoxidation of the Soap (rancidity), complexing agent such as nitrilotriacetate for binding heavy metal traces, which could catalyze the autoxidative spoilage, perfume oils to achieve the desired fragrances, dyes for coloring the soap bars and if desired special additives.

Wichtigste Typen der Feinseifen sind:

  • Toilettenseifen mit 20 - 50 % Kokosöl im Fettansatz, bis 5 % Rückfetter-Anteil und 0,5 - 2 % Parfümöl, sie bilden den größten Anteil der Feinseifen;
  • Luxusseifen mit bis zu 5% besonders kostbarer Parfümöle;
  • Deoseifen mit Zusätzen desodorierender Wirkstoffe, wie z. B. 3,4,4'-Trichlorcarbanilid (Triclocarban);
  • Cremeseifen mit besonders hohen Anteilen rückfettender und die Haut cremender Substanzen;
  • Babyseifen mit guter Rückfettung und zusätzlich pflegenden Anteilen wie z. B. Kamille-Extrakten, allenfalls sehr schwach parfümiert;
  • Hautschutzseifen mit hohen Anteilen rückfettender Substanzen sowie weiteren pflegenden und schützenden Zusätzen, wie z. B. Proteinen;
  • Transparentseifen mit Zusätzen von Glycerin, Zucker u. a., welche die Kristallisation der Fettsäuresalze in der erstarrten Seifenschmelze verhindern und so ein transparentes Aussehen bewirken;
  • Schwimmseifen mit einer Dichte < 1, hervorgerufen durch bei der Herstellung kontrolliert eingearbeitete Luftbläschen.
    • Seifen mit abrasiven Zusätzen zur Reinigung stark verschmutzter Hände.
The most important types of fine soap are:
  • Toilet soaps with 20 - 50% coconut oil in the fat mixture, up to 5% Rückfetter share and 0.5 - 2% perfume oil, they form the largest proportion of fine soaps;
  • Luxury soaps with up to 5% of particularly precious perfume oils;
  • Deo-soaps with additives of deodorizing agents such. B. 3,4,4'-trichlorocarbanilide (triclocarban);
  • Cream soaps with particularly high levels of moisturizing and creaming substances;
  • Baby soaps with good moisturizing and additional nourishing shares such. B. chamomile extracts, at best very poorly perfumed;
  • Skin protection soaps with high levels of moisturizing substances as well as other nourishing and protective additives, such as: Proteins;
  • Transparent soaps with additions of glycerine, sugar, etc., which prevent the crystallization of the fatty acid salts in the solidified soap melt and thus produce a transparent appearance;
  • Floating soaps with a density <1, caused by controlled air bubbles during manufacture.
    • Soaps with abrasive additives to clean heavily soiled hands.

Beim Waschen mit Seife stellt sich in der Waschlauge ein pH-Wert von 8-10 ein. Diese Alkalität neutralisiert den natürlichen Säuremantel der Haut (pH-Wert 5-6). Dieser wird bei normaler Haut zwar relativ schnell rückgebildet, bei empfindlicher oder vorgeschädigter Haut kann es jedoch zu Irritationen kommen. Ein weiterer Nachteil der Seifen ist die Bildung unlöslicher Kalkseifen in hartem Wasser. Diese Nachteile liegen nicht vor bei Syndet-Seifen. Ihre Basis sind synthetische Aniontenside, die mit Gerüstsubstanzen, Rückfettem und weiteren Zusätzen zu seifenähnlichen Stücken verarbeitet werden können. Ihr pH-Wert ist in weiten Grenzen variierbar und wird meist neutral auf pH 7 oder dem Säuremantel der Haut angepaßt auf pH 5,5 eingestellt. Sie haben hervorragende Reinigungskraft, schäumen in jeder Wasserhärte, sogar in Meerwasser, der Anteil rückfettender Zusätze muß wegen ihrer intensiven Reinigungs- und Entfettungswirkung deutlich höher als bei normalen Seifen sein. Ihr Nachteil ist der relativ hohe Preis.When washing with soap, the pH of the wash liquor is 8-10. This alkalinity neutralizes the natural acid mantle of the skin (pH 5-6). This one is added Normal skin, although relatively quickly regressed, in sensitive or damaged skin however, it can cause irritation. Another disadvantage of the soaps is the formation of insoluble Lime soaps in hard water. These disadvantages are not present in syndet soaps. They are based on synthetic anionic surfactants, which contain builders, backfats and others Additives can be processed to soap-like pieces. Their pH is in wide Borders variable and is usually neutral adjusted to pH 7 or the acid mantle of the skin adjusted to pH 5.5. They have excellent cleaning power, lather in everyone Water hardness, even in sea water, the proportion of lipid-reducing additives must because of their intensive Cleaning and degreasing effect to be significantly higher than normal soaps. you Disadvantage is the relatively high price.

Tenside sind amphiphile Stoffe, die organische, unpolare Substanzen in Wasser lösen können. Sie sorgen, bedingt durch ihren spezifischen Molekülaufbau mit mindestens einem hydrophilen und einem hydrophoben Molekülteil, für eine Herabsetzung der Oberflächenspannung des Wassers, die Benetzung der Haut, die Erleichterung der Schmutzentfernung und -lösung, ein leichtes Abspülen und - je nach Wunsch - für Schaumregulierung.Surfactants are amphiphilic substances that can dissolve organic, nonpolar substances in water. They provide, due to their specific molecular structure with at least one hydrophilic and a hydrophobic part of the molecule, for a lowering of the surface tension water, wetting the skin, facilitating the removal of dirt and solution, a light rinse and, as desired, foam control.

Bei den hydrophilen Anteilen eines Tensidmoleküls handelt es sich meist um polare funktionelle Gruppen, beispielweise -COO-, -OSO3 2-, -SO3 -, während die hydrophoben Teile in der Regel unpolare Kohlenwasserstoffreste darstellen. Tenside werden im allgemeinen nach Art und Ladung des hydrophilen Molekülteils klassifiziert. Hierbei können vier Gruppen unterschieden werden:

  • anionische Tenside,
  • kationische Tenside,
  • amphotere Tenside und
  • nichtionische Tenside.
The hydrophilic portions of a surfactant molecule are usually polar functional groups, for example -COO - , -OSO 3 2- , -SO 3 - , while the hydrophobic parts are usually nonpolar hydrocarbon radicals. Surfactants are generally classified according to the nature and charge of the hydrophilic part of the molecule. Here four groups can be distinguished:
  • anionic surfactants,
  • cationic surfactants,
  • amphoteric surfactants and
  • nonionic surfactants.

Es ist bekannt, daß Feinseifen auf Basis von Talg- und Kokosfettsäuren durch zahlreiche Zusatzstoffe in ihren anwendungstechnischen Eigenschaften verändert und verbessert werden können. In gängigen Handbüchem, z. B. Geoffrey Martin: The Modern Soap and Detergent Industry, Vol. 1, (1959), Kapitel VI, sind zwar anorganische Füllstoffe als Streckmittel für Seifen beschrieben, dabei wird dem Talkum jedoch eher eine nachteilige Wirkung in Stückseifen zugeschrieben. Der Zusatz von 5-20% Talkum in Combibars wird in DE 196 49 896 beschrieben. Durch diesen Zusatz soll die Glätte und das Kalkseifendispergiervermögen verbessert werden.It is known that fine soaps based on tallow and coconut fatty acids by numerous Additives can be changed and improved in their performance properties can. In common Handbüchem, z. B. Geoffrey Martin: The Modern Soap and Detergent Industry, Vol. 1, (1959), Chapter VI, although inorganic fillers as extenders for Soaps described, but the talc is rather a disadvantageous effect in bar soaps attributed. The addition of 5-20% talc in Combibars is described in DE 196 49 896 described. By this addition, the smoothness and Kalkseifendispergiervermögen be improved.

Die Aufgabe der Erfindung hat somit darin bestanden, Stückseifen zur Verfügung zu stellen, die frei von den geschilderten Nachteilen sind. Dabei war insbesondere auch zu berücksichtigen, daß neue Stückseifenzusammensetzungen auch großtechnisch herstellbar sein müssen, d. h. daß die Zusammensetzungen beispielsweise eine ausreichende, aber nicht zu hohe Verformbarkeit besitzen und beim Trocknen nicht zur Rißbildung neigen.The object of the invention was therefore to provide bar soaps available, which are free of the described disadvantages. It was particularly important to take into account that new bar soap compositions must also be able to be produced industrially, d. H. that the compositions, for example, a sufficient, but not too have high ductility and do not tend to crack during drying.

Gegenstand der Erfindung ist daher ein geformtes kosmetisches Seifenprodukt, enthaltend

  • Talkum, dessen Teilchendurchmesser im Bereich von 0,5-50 µm liegt
  • eine oder mehrere Fettsäuren mit 12-22 C-Atomen in Form ihrer Alkaliseifen und
  • eine oder mehrere rückfettend wirksame Substanzen
wobei das Seifenprodukt weniger als 1 Gew.-% an Alkyl-(oligo)-glycosiden enthäl.The invention therefore relates to a molded cosmetic soap product containing
  • Talc whose particle diameter is in the range of 0.5-50 microns
  • one or more fatty acids with 12-22 carbon atoms in the form of their alkali soaps and
  • one or more moisturizing substances
wherein the soap product contains less than 1% by weight of alkyl (oligo) glycosides.

Entgegen den aus dem Stand der Technik zu erwartenden Einbußen wurde überraschend festgestellt, daß bei Stückseifen, die keine Alkylglycoside als Zusatz enthalten, durch einen Zusatz von Talkum und einen weiteren Gehalt an einer oder mehreren rückfettend wirkenden Substanzen eine weitere Verbesserung der physikalischen und anwendungstechnischen Eigenschaften, i nsbesondere d es Wasch- u nd Kalkseifendispergiervermögens, d er S eifenglätte wie auch insbesondere des Hautgefühls bei der Wasche erzielt wird. Darüberhinaus wurde festgestellt, daß die rückfettende Wirkung der rückfettend wirksamen Substanzen durch die Verwendung von Talkum in geformten Seifenprodukten gemäß der Erfindung in synergistischer Weise gesteigert wird. Contrary to the losses to be expected from the prior art, it was surprising found that in bar soaps that contain no alkyl glycosides as an additive, by a Addition of talc and a further content of one or more moisturizers Substances further improve the physical and performance engineering Properties, in particular the washing and lime soap dispersing power, the sifting smoothness as well as in particular the skin feeling in the wash is achieved. Furthermore It was found that the moisturizing effect of the lipid-replenishing substances by the use of talc in shaped soap products according to the invention in is increased synergistically.

Trotz geringen Gesamtgehalts an oberflächenaktiven Substanzen in der Formulierung bleiben die Reinigungsleistung und Schaumentwicklung unbeeinflußt. Das Hautgefühl wird bei der Verwendung dieses Waschstücks selbst ohne zusätzliche Hautpflegesubstanzen entscheidend verbessert.Despite low total content of surfactants remain in the formulation the cleaning performance and foaming unaffected. The skin feeling is added the use of this wash even without additional skin care substances crucial improved.

Der Schaum bekommt zudem eine noch bessere Cremigkeit und mehr Volumen, was ebenfalls nicht zu erwarten war. Ein weiterer Vorteil dieser Erfindung ist, das die Verträglichkeit des Waschstücks verbessert wird, da der Gesamtgehalt an oberflächenaktiven Substanzenreduziert wird.The foam also gets an even better creaminess and more volume, which also was not expected. Another advantage of this invention is that the compatibility of the washing piece is improved because the total content of surface-active substances is reduced becomes.

Die erfindungsgemäßen geformten Seifenprodukte besitzen darüber hinaus nach der mechanischen Verformung eine besonders glatte Oberfläche. Bei der Anwendung erzeugen sie einen cremigen, stabilen Schaum. Der in hartem Wasser gebildete Kalkseifenniederschlag bleibt im Wasser dispergiert und führt nicht zu den grau-schmierigen Belägen auf der Oberfläche von Sanitärobjekten.The molded soap products according to the invention also possess the mechanical properties Deformation a particularly smooth surface. At the application they produce a creamy, stable foam. The lime soap precipitate formed in hard water remains dispersed in the water and does not lead to the gray-greasy deposits on the surface of sanitary objects.

Talkum ist ein hydratisiertes Magnesiumsilikat der Zusammensetzung 3MgO·4SiO2. H2O bzw. Mg3(Si4O10)· (OH)2 bzw. Mg6(OH)4[Si8O20] bzw. Mg12[Si16O40], das jedoch Anteile an hydratisiertem Magnesiumalminiumsilikat von bis zu 12 Gew.-% Al2O3, bezogen auf das gesamte Produkt, enthalten kann. Talkum ist ein weißes, meist sehr feines, praktisch geruchloses bis etwas erdig riechendes Pulver, das sich beim Reiben fettig anfühlt, ohne fetthaltig zu sein. Es ist unlöslich in Wasser, kalten Säuren oder Alkalien. Je nach Ursprungsland soll die chemische Reinheit des Talkums (bezogen auf den Gehalt an wasserfreiem Magnesiumsilikat) 93-98 % betragen. Talkum wird zur Herstellung von pharmazeutischen, vor allem aber zur Herstellung kosmetischer Puder, die der Körperpflege dienen, verwendet, ist aber auch zur Tablettenherstellung als Schmier- bzw. Fließmittel geeignet.Talc is a hydrated magnesium silicate of composition 3MgO · 4SiO 2 . H 2 O or Mg 3 (Si 4 O 10 ). (OH) 2 or Mg 6 (OH) 4 [Si 8 O 20 ] or Mg 12 [Si 16 O 40 ], however, the proportions of hydrated magnesium aluminum silicate of may contain up to 12% by weight of Al 2 O 3 , based on the total product. Talc is a white, usually very fine, virtually odorless to slightly earthy-smelling powder, which feels greasy when rubbing, without being fatty. It is insoluble in water, cold acids or alkalis. Depending on the country of origin, the chemical purity of the talc (based on the content of anhydrous magnesium silicate) should be 93-98%. Talcum is used for the production of pharmaceutical, but especially for the production of cosmetic powders, which are used for personal care, but is also suitable for tablet production as a lubricant or superplasticizer.

Der Teilchendurchmesser (equivalent spherical diameter) des Talkums liegt im Bereich von 0,5-50 µm. Im allgemeinen haben sich solche Talkumqualitäten bewährt, die nicht mehr als 5 Gew.-% an Teilchen unter 1 µm und nicht mehr als 5 Gew.-% an Teilchen über 50 µm Größe enthalten. Vorzugsweise ist der Anteil an Teilchen, die größer als 40 µm im Durchmesser sind (Siebrückstand), höchstens 2 Gew.-%. Der mittlere Teilchendurchmesser (D 50) liegt bevorzugt bei 5 -15 µm. The particle diameter (equivalent spherical diameter) of the talc is in the range of 0.5-50 μm. In general, such talcum qualities have been proven, not more than 5% by weight of particles below 1 μm and not more than 5% by weight of particles 50 μm size included. Preferably, the proportion of particles larger than 40 microns in Diameters are (sieve residue), at most 2 wt .-%. The mean particle diameter (D 50) is preferably 5 -15 μm.

Der Gehalt an Begleitstoffen sollte nicht mehr als 1,6 Gew.-% Fe2O3, 1 Gew.-% CaO und 1 Gew.-% an ungebundenem Wasser (Trockenverlust bei 1050 °C) ausmachen. Der Gehalt an hydratisiertem Magnesiumaluminiumsilikat kann bis zu 60 Gew.-%, berechnet als Al2O3, bis zu 12 Gew.-% liegen.The content of impurities should not exceed 1.6% by weight of Fe 2 O 3 , 1% by weight of CaO and 1% by weight of unbound water (dry loss at 1050 ° C.). The content of hydrated magnesium aluminum silicate may be up to 60% by weight, calculated as Al 2 O 3 , up to 12% by weight.

Erfindungsgemäß vorteilhaft enthalten die geformten Seifenprodukte 1 - 20 Gew.-% Talkum.Advantageously according to the invention, the shaped soap products contain from 1 to 20% by weight of talcum.

Erfindungsgemäß gegebenenfalls vorteilhaft enthalten die geformten Seifenprodukte ebenfalls 1 - 99 Gew.-% an einer Grundseife, beispielsweise einer solchen, deren Seifenbestandteile sich aus Natriumtallowat, Natriumcocoat und Natrium-Palmkemfettsäuresalz zusammensetzen.Optionally advantageous according to the invention, the shaped soap products also contain 1 - 99 wt .-% of a base soap, for example one whose soap components composed of sodium tallowate, sodium cocoate and sodium palm kernel fatty acid salt.

Die erfindungsgemäßen geformten Seifenprodukte enthalten darüber hinaus vorteilhaft Wasser in einer Menge von 5-35 Gew.-%. Der Wassergehalt ist einerseits bedingt durch das Herstellungsverfahren, andererseits wirkt er sich günstig auf die Gebraucheigenschaften der Seife aus.In addition, the shaped soap products of the invention advantageously contain water in an amount of 5-35% by weight. The water content is partly due to the Manufacturing process, on the other hand, it has a favorable effect on the performance characteristics of Soap off.

Als Fettsäuren zur Herstellung der Grundseife werden die linearen Fettsäuren mit 12 bis 22 C-Atomen, z. B. die Laurin-, Myristin-, Palmitin-, Stearin-, Arachin- und Behensäure, aber auch die ungesättigten Fettsäuren, z. B. die Palmitolein-, Öl-, Linol-, Linolen-, Arachidon- und Erucasäure verwendet. Bevorzugt werden technische Gemische, wie sie aus pflanzlichen und tierischen Fetten und Ölen erhältlich sind, eingesetzt, z. B. Kokosölfettsäure und Talgfettsäure. Besonders bevorzugt sind Gemische aus Kokos- und Talgfettsäureschnitten, insbesondere ein Gemisch aus 50-80 Gew.-% C16-C18- Talgfettsäure und 20-50 Gew.-% C12-C14-Kokosfettsäure.As fatty acids for the preparation of the basic soap are the linear fatty acids having 12 to 22 carbon atoms, eg. As the lauric, myristic, palmitic, stearic, arachin and behenic acid, but also the unsaturated fatty acids, eg. As the palmitoleic, oleic, linoleic, linolenic, arachidonic and erucic acid used. Preference is given to technical mixtures, such as are available from vegetable and animal fats and oils used, for. As coconut oil fatty acid and tallow fatty acid. Particular preference is given to mixtures of coconut oil and tallow fatty acid slices, in particular a mixture of 50-80% by weight C 16 -C 18 tallow fatty acid and 20-50% by weight C 12 -C 14 coconut fatty acid.

Die Fettsäuren werden in Form ihrer Alkaliseife, üblicherweise als Natriumseifen eingesetzt. Die Seifen können aber auch aus den Fetten und Ölen direkt durch Verseifung (Hydrolyse) mit Natronlauge und Abtrennen des Glycerins erzeugt werden. Bevorzugt enthalten die erfindungsgemäßen geformten Seifenprodukte einen zusätzlichen Anteil von 1-10 Gew.-% an freien Fettsäuren mit 12-22 C-Atomen. Diese können mit den Fettsäuren der Grundseife identisch sein und durch einen entsprechenden Alkaliunterschuß bei der Verseifung in die Grundseife eingebracht werden. Bevorzugt werden die freien Fettsäuren aber nach der Verseifung und nach dem Aufkonzentrieren, vor der Trocknung, zudosiert. The fatty acids are used in the form of their alkali soap, usually as sodium soaps. The soaps can also be obtained from the fats and oils directly by saponification (hydrolysis) be generated with sodium hydroxide solution and separating the glycerol. Preferably, the inventive molded soap products an additional proportion of 1-10 wt .-% of free fatty acids with 12-22 carbon atoms. These can be identical to the fatty acids of the basic soap and by a corresponding Alkalikalunterschuß in the saponification in the Basic soap are introduced. However, the free fatty acids are preferred after saponification and after concentration, before drying, metered.

Erfindungsgemäß ist die Abwesenheit von Alkyl-(oligo)-Glycosiden. Alkyl-(oligo)-glycoside sind bekannte, im Handel erhältliche nichtionogene Tenside, die nach einschlägigen Verfahren der organischen Chemie zugänglich sind und der Formel R1-O(G)x entsprechen, in der R1 eine primäre C12-C16-Alkylgruppe und (G)x ein Oligoglycosidrest ist, dessen Oligomerisationsgrad x = 1 bis 2 ist. Stellvertretend für das umfangreiche Schrifttum sei hier auf EP-A-0 301 298 und WO-A-90/3977 verwiesen. Die Alkyl-(oligo)-glycoside können sich von Aldosen oder Ketosen mit 5 oder 6 Kohlenstoffen ableiten. Wegen der leichten Zugänglichkeit werden im großtechnischen Maßstab hauptsächlich von Glucose abgeleitete Alkyl-(oligo)-glucoside hergestellt. Abwesenheit dieser Substanzen bedeutet, daß sie allenfalls als Verunreinigungen in der dem erfindungemäßen Combibar zugrundeliegenden Masse zugegen sein dürfen, jedenfalls weniger als 1 Gew.-% betragen müssen.According to the invention, the absence of alkyl (oligo) glycosides. Alkyl (oligo) glycosides are known, commercially available nonionic surfactants which are accessible by relevant methods of organic chemistry and corresponding to the formula R 1 -O (G) x , in which R 1 is a primary C 12 -C 16 - Alkyl group and (G) x is an oligoglycoside whose degree of oligomerization x = 1 to 2. Representative of the extensive literature, reference is hereby made to EP-A-0 301 298 and WO-A-90/3977. The alkyl (oligo) glycosides can be derived from aldoses or ketoses with 5 or 6 carbons. For ease of accessibility, alkyl (oligo) glucosides derived primarily from glucose are produced on an industrial scale. Absence of these substances means that they may at most be present as impurities in the mass underlying the invention combibar, at least less than 1 wt .-% must be.

Erfindungsgemäß ist femer bevorzugt, den Gehalt an anderen oberflächenaktiven Tenside, außer den erfindungsgemäßen, so klein wie möglich zu halten, vorteilhaft unter 5 Gew.-%, bezogen auf das Gesamtgewicht der erfindungsgemäßen geformten Seifenprodukte. Es ist bevorzugt, gänzlich auf solche Tenside zu verzichten.It is furthermore preferred according to the invention to determine the content of other surface-active surfactants, other than the invention, as small as possible, advantageously less than 5 wt .-%, based on the total weight of the shaped soap products according to the invention. It is preferred to dispense entirely with such surfactants.

Die Seifenstücke gemäß der Erfindung können als weitere Hilfs- und Zusatzstoffe Ölkörper, Emulgatoren, Überfettungsmittel, Fette, Wachse, Stabilisatoren, kationische Polymere, Siliconverbindungen, Pigmente, biogene Wirkstoffe, Konservierungsmittel, Farb- und Duftstoffe enthalten.The soap bars according to the invention can be used as further auxiliaries and additives Emulsifiers, superfatting agents, fats, waxes, stabilizers, cationic polymers, silicone compounds, Pigments, biogenic agents, preservatives, dyes and fragrances contain.

Als erfindungsgemäß einzusetzende Rückfetter können beispielsweise vorteilhaft zum Einsatz kommen:

  • 1. Langkettige Alkohole z.B. Lanolin, Cetylalkohol
  • 2. Mono- und Diglyceride bzw. die entsprechenden Glycolester
  • 3. Mono-, Di- und Triglyceride pflanzlichen Ursprungs z.B. Mandelöl
  • 4. Hydrierte Fette
  • 5. Vaseline
  • 6. Wachse
  • For example, backfats to be used according to the invention can advantageously be used:
  • 1. Long-chain alcohols such as lanolin, cetyl alcohol
  • 2. Mono- and diglycerides or the corresponding glycol esters
  • 3. mono-, di- and triglycerides of plant origin eg almond oil
  • 4. Hydrogenated fats
  • 5. Vaseline
  • 6. waxes
  • Als Rückfetter kommen femer beispielsweise Ölkörper wie etwa Guerbetalkohole auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, Ester von linearen C6-C20-Fettsäuren mit linearen C6-C20- Fettalkoholen, Ester von verzweigten C6-C13-Carbonsäuren mit linearen C6-C20-Fettalkoholen, Ester von linearen C6-C18-Fettsäuren mit verzweigten Alkoholen, insbesondere 2-Ethylhexanol, Ester von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen (wie z. B. Dimerdiol oder Trimerdiol) und/oder Guerbetalkoho Triglyceride auf Basis C6-C10-Fettsäuren, pflanzliche Öle, verzweigte primäre Alkohole, substituierte Cyclohexane, Guerbetcarbon Dialkylether und/oder aliphatische bzw. naphthenische Kohlenwasserstoffe in Betracht.Further examples of greasing agents are oil bodies such as Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 20 fatty acids with linear C 6 -C 20 fatty alcohols, esters of branched C 6 - C 13 -carboxylic acids with linear C 6 -C 20 -fatty alcohols, esters of linear C 6 -C 18 -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (for example Dimerdiol or trimerdiol) and / or Guerbetalkoho triglycerides based on C 6 -C 10 fatty acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbetcarbon dialkyl ethers and / or aliphatic or naphthenic hydrocarbons into consideration.

    Erfindungsgemäße Seifenprodukte sind besonders vorteilhaft dadurch gekennzeichnet, daß sie 1 - 30 Gew.-% an rückfettend wirksamen Substanzen enthalten.Soap products according to the invention are particularly advantageously characterized in that they contain 1 - 30 wt .-% of moisturizing effective substances.

    Als Emulgatoren bzw. Co-Emulgatoren können nichtionogene, ampholytische und/oder zwitterionische grenzflächenaktive Verbindun verwendet werden, die sich durch eine lipophile, bevorzugt lineare, Alkyl- oder Alkenylgruppe und mindestens eine hydrophile Gruppe auszeichnen. Diese hydrophile Gruppe kann sowohl eine ionogene als auch eine nichtionogene Gruppe sein.As emulsifiers or co-emulsifiers can nonionic, ampholytic and / or zwitterionic surfactants which are characterized by a lipophilic, preferably linear, alkyl or alkenyl group and at least one hydrophilic group. This hydrophilic group can be both ionogenic and nonionic Be a group.

    Nichtionogene Emulgatoren enthalten als hydrophile Gruppe z. B. eine Polyolgruppe, eine Polyalkylenglycolethergruppe oder ein Kombination aus Polyol- und Polyglycolethergruppe. Bevorzugt sind solche Mittel, die als O/W-Emulgatoren nichtionogene Tenside aus mindestens einer der folgenden Gruppen enthalten: (a1) Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe; (a2) C12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin; (a3) Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte und (a4) Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl; (a5) Polyol- und insbesondere Polyglycerinester wie z. B. Polyglycerinpolyricinoleat oder Polyglycerinpoly-12-hydroxystearat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen. Die Anlagerungsprodukte von Ethylenoxid und/oder von Propylenoxid an Fettalkohole, Fettsäuren, Alkylphenole, Glycerinmono- und -diester sowie Sorbitanmono- und -diester von Fettsäuren oder an Ricinusöl stellen bekannte, im Handel erhältliche Produkte dar. Es handelt sich dabei um Homologengemische, deren mittlerer Alkoxylierungsgrad dem Verhältnis der Stoffmengen von Ethylenoxid und/oder Propylenoxid und Substrat, mit denen die Anlagerungsreaktion durchgeführt wird, entspricht. C12/14-Fettsäuremono- und -diester von Anlagerungsprodukten von Ethylenoxid an Glycerin sind aus DE-20 24 051 als Rückfettungsmittel für kosmetische Zubereitungen bekannt.Nonionic emulsifiers contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Preference is given to those compositions which contain nonionic surfactants from at least one of the following groups as O / W emulsifiers: (a1) addition products of from 2 to 30 mol of ethylene oxide and / or from 0 to 5 mol of propylene oxide onto linear fatty alcohols containing from 8 to 22 carbon atoms , fatty acids having 12 to 22 C atoms and alkylphenols having 8 to 15 C atoms in the alkyl group; (a2) C 12/18 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol; (a3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products and (a4) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil; (a5) polyol and especially polyglycerol esters such. As polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate. Also suitable are mixtures of compounds of several of these classes of substances. The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are mixtures of homologs whose mean Alkoxylierungsgrad the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. C 12/14 fatty acid mono- and diesters of addition products of ethylene oxide with glycerol are known from DE-20 24 051 as refatting agents for cosmetic preparations.

    Als W/O-Emulgatoren kommen in Betracht: (b1) Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl; (b2) Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C12/22-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z. B. Sorbit) sowie Polyglucoside (z. B. Cellulose); (b3) Trialkylphosphate; (b4) Wollwachsalkohole; (b5) Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate; (b6) Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 11 65 574 sowie (b7) Polyalkylenglycole.Suitable w / o emulsifiers are: (b1) addition products of from 2 to 15 mol of ethylene oxide with castor oil and / or hydrogenated castor oil; (b2) partial esters based on linear, branched, unsaturated or saturated C 12/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol) and polyglucosides (eg. cellulose); (b3) trialkyl phosphates; (b4) wool wax alcohols; (b5) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; (b6) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and (b7) polyalkylene glycols.

    Geeignete kationische Polymere sind beispielsweise kationischen Cellulosederivate, kationischen Starke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vinylpyrrolidon/ Vinylimidazol-Polymere wie z. B. Luviquat TM (BASF AG), Kondensationsprodukte von Polyglycolen und Aminen, quaternierte Kollagenpolypeptide wie beispielsweise "Lauryldimonium- hydroxypropyl-hydrolyzed-collagen" (Lamequat TM L, Grünau GmbH) oder "Lauryldimmonium-hydroxypropyl-hydroxylated-wheat-protein" (Gluadin TM WQ, Grünau GmbH), Polyethylenimin, kationische Siliconpolymere wie z. B. Amidomethicone oder Dow Coming, Dow Coming Co./US, Copolymere der Adipinsäure und Dimethylaminohydroxypropyl-diethylentriamin (Cartaretine TM , Sandoz/CH), Polyaminopolyamide wie z. B. beschrie in der FR 22 52 840-A sowie deren vernetzte wasserlöslichen Polymere, kationische Chitinderivate wie beispielsweise quaterniertes Chitosan, gegebenenfalls mikrokristallin verteilt, kationischer Guar-Gum wie z. B. Jaguar TM CBS, Jaguar TM C-17, Jaguar TM C-16 (Celanese) oder Cosmedia Guar TM C 261 (Henkel KGaA), quaternierte Ammoniumsalz-Polymere wie z. B. Mirapol TM A-15, Mirapol TM AD-1, Mirapol TM AZ-1 der Miranol/US. Geeignete Siliconverbindungen sind beispielsweise Dimethylpolysiloxane, Methylphenylpolysiloxane, cyclische Silicone sowie amino-, fettsäure-, alkohol-, polyether-, epoxy-, fluor- und/oder alkylmodifizierte Siliconverbindungen. Als Überfettungsmittel können Substanzen wie beispielsweise polyethoxylierte Lanolinderivate, Lecithinderivate, Polyolfettsäureester, Monoglyceride und Fettsäurealkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen. Typische Beispiele für Fette sind Glyceride, als Wachse kommen u. a. Bienenwachs, Paraffinwachs oder Mikrowachse gegebenenfalls in Kombination mit hydrophilen Wachsen, z. B. Cetylstearylalkohol in Frage. Als Stabilisatoren können Metallsalze von Fettsäuren wie z. B. Magnesium-, Aluminium- und/oder Zinkstearat eingesetzt werden. Als Pigment kommt beispielsweise Titandioxid in Frage Unter biogenen Wirkstoffen sind beispielsweise Pflanzenextrakte und Vitaminkomplexe zu verstehen. Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentandiol oder Sorbinsäure. Als Farbstoffe können die für kosmetische Zwecke geeigneten und zugelassenen Substanzen verwendet werden, wie sie beispielsweise in der Publikation "Kosmetische Färbemittel" der Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, S. 81-106 zusammengestellt sind. Diese Farbstoff werden üblicherweise in Konzentrationen von 0,001 bis 0,1 Gew.-%, bezogen auf die gesamte Mischung, eingesetzt. Der Gesamtanteil der Hilfs- und Zusatzstoffe kann 1 bis 50, vorzugsweise 5 bis 40 Gew.-% - bezogen die Mittel - betragen.Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic Strong, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / Vinylimidazole polymers such. B. Luviquat ™ (BASF AG), condensation products of polyglycols and amines, quaternized collagen polypeptides such as "Lauryldimonium hydroxypropyl hydrolyzed collagen" (Lamequat ™ L, Grünau GmbH) or "Lauryldimmonium-hydroxypropyl-hydroxylated-wheat-protein" (Gluadin ™ WQ, Grünau GmbH), polyethyleneimine, cationic silicone polymers such. As amidomethicones or Dow Coming, Dow Coming Co./US, copolymers of adipic acid and dimethylaminohydroxypropyl-diethylenetriamine (Cartaretine ™, Sandoz / CH), polyaminopolyamides such as e.g. B. described in FR 22 52 840-A and their crosslinked water-soluble polymers, cationic Chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, cationic guar gum such. Jaguar ™ CBS, Jaguar ™ C-17, Jaguar ™ C-16 (Celanese) or Cosmedia Guar ™ C 261 (Henkel KGaA), quaternized ammonium salt polymers such as Mirapol ™ A-15, Mirapol ™ AD-1, Mirapol ™ AZ-1 from Miranol / US. Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty, alcohol, polyether, epoxy, fluorine- and / or alkyl-modified silicone compounds. As superfatting agents can substances such as polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, Monoglycerides and fatty acid alkanolamides are used, the latter being simultaneously serve as foam stabilizers. Typical examples of fats are glycerides, as Waxes come u. a. Beeswax, paraffin wax or microwaxes optionally in Combination with hydrophilic waxes, e.g. As cetylstearyl alcohol in question. As stabilizers Metal salts of fatty acids such. As magnesium, aluminum and / or zinc stearate be used. For example, titanium dioxide may be considered as a pigment under biogenic Active ingredients are understood, for example, as plant extracts and vitamin complexes. When Preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, Pentanediol or sorbic acid. As dyes can be used for cosmetic purposes suitable and approved substances are used, as for example in the Publication "Cosmetic Colorants" of the Dye Commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-106. These Dyestuffs are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the entire mixture used. The total amount of auxiliaries and additives can 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount.

    Schließlich können die erfindungsgemäßen geformten Seifenprodukte Duftstoffe und weitere übliche Hilfs- und Zusatzstoffe in einer Menge von bis zu 5 Gew.-% enthalten. Geeignete Hilfsstoffe sind z. B. Bindemittel oder Plastifikatoren. Als solche eignen sich z. B. Glycerin, Fettsäurepartialglyceride oder Fettalkohole mit 12-22 C-Atomen. Die Fettalkohole können z. B. als Nebenprodukt der Alkyl-(oligo)-glucoside gemeinsam mit diesen zugesetzt werden, wenn man die Alkyl-(oligo)-glucoside als Rohprodukt mit einem Gehalt an bis zu 50 Gew.-% freiem Fettalkohol einsetzt.Finally, the shaped soap products of the present invention may be perfumes and others customary auxiliaries and additives in an amount of up to 5 wt .-%. suitable Auxiliary substances are z. As binders or plasticizers. As such are z. Glycerol, Fatty acid partial glycerides or fatty alcohols with 12-22 C atoms. The fatty alcohols may, for. B. as a by-product of alkyl (oligo) glucosides are added together with these, if the alkyl (oligo) glucosides are used as crude product with a content of up to 50% by weight uses free fatty alcohol.

    Weitere Hilfsstoffe sind z. B. Farbstoffe, antimikrobielle Stoffe, Deodorantwirkstoffe, Pigmente (TiO2), optische Aufheller und Komplexbildner.Other auxiliaries are z. As dyes, antimicrobial agents, deodorant agents, pigments (TiO 2 ), optical brighteners and complexing agents.

    Die Herstellung der erfindungsgemäßen geformten Seifenprodukte kann in der für Seifen üblichen Weise erfolgen. Dabei wird zunächst aus Fettsäureansatz und Natronlauge eine Grundseife mit einem Feststoffgehalt von 25-50 Gew.-% hergestellt und auf einen Feststoffgehalt von 50-70 Gew.-% aufkonzentriert. In diese z. B. 60%-ige Grundseife kann bereits das Talkum, gegebenenfalls auch freie Fettsäure, ein anionisches Tensid und ein Komplexbildner eingemischt werden. Danach wird die Grundseife z. B. in einem Vakuumexpansionstrockner bei 120 °C bis 130 °C weiter entwässert. Bei der Expansion kühlt sich die Seife spontan auf Temperaturen unter 60 °C ab und wird fest. Dabei fallen Seifennudeln mit einem Feststoffgehalt von 73-85 Gew.-% an.The preparation of the molded soap products according to the invention can be carried out in soaps usual way. In this case, initially from fatty acid approach and sodium hydroxide solution Grundseife having a solids content of 25-50 wt .-% and prepared to a solids content of 50-70 wt .-% concentrated. In this z. B. 60% basic soap can already the talc, optionally also free fatty acid, an anionic surfactant and a complexing agent be mixed. Thereafter, the basic soap z. B. in a vacuum expansion dryer further dehydrated at 120 ° C to 130 ° C. During expansion, the soap cools spontaneously to temperatures below 60 ° C and solidifies. This fall soap noodles with a Solids content of 73-85 wt .-% of.

    Die Weiterverarbeitung dieser Grundseife stellt dann die Konfektionierung zur Feinseife dar. Sie erfolgt in einem Seifenmischer, in dem ein Slurry aus dem Alkyl-(oligo)-glucosid und den übrigen Hilfs- und Zusatzmitteln in die Seifennudeln eingemischt wird. Dabei werden die Grundseifennudeln und der Slurry aus Alkyl-(oligo)-glycosid und z. B. Duftstoffen, Farbstof fen, Pigmenten und anderen Hilfsmitteln in einem Schneckenmischer mit Lochsieben intensiv gemischt und schließlich über eine Strangpresse ausgetragen und gegebenenfalls einer Stückpresse zugeführt, wenn Seifenstücke hergestellt werden sollen.The further processing of this basic soap then represents the finishing of fine soap. It takes place in a soap mixer in which a slurry of the alkyl (oligo) glucoside and the other additives and additives in the soap noodles is mixed. Here are the Ground soap noodles and the slurry of alkyl (oligo) glycoside and z. B. fragrances, dye fen, pigments and other auxiliaries in a screw mixer with perforated sieves mixed and finally discharged via an extruder and optionally one Piece press fed when soap bars are to be produced.

    Geformte Seifenprodukte im Sinne der Erfindung können aber auch als Nudeln, Nadeln, Granulate, Extrudate, Schuppen und in jeder anderen für Seifenprodukte übliche Formgebung vorliegen.Molded soap products according to the invention can also be used as noodles, needles, Granules, extrudates, flakes and in any other usual for soap products shaping available.

    Altemativ zu dem beschriebenen Verfahren kann das Talkum auch erst bei der Konfektionierung in die 73-85%ige Grundseife eingearbeitet werden. In diesem Falle wird das Talkumpulver über geeignete Dosiergeräte, z. B. Bandwaage und Schütteldosierer gleichzeitig mit dem Slurry aus Duftstoffen und Hilfsmitteln dem Seifenmischer zugeführt.As an alternative to the process described, the talc can also be added only during the preparation be incorporated into the 73-85% basic soap. In this case, the talcum powder via suitable dosing devices, eg. B. belt scale and shaker at the same time the slurry of perfumes and auxiliaries supplied to the soap mixer.

    Die erfindungsgemäßen Seifenprodukte zeichnen sich durch eine besonders glatte Oberfläche aus, was sich insbesondere bei Verarbeitung zu Stückseife angenehm bemerkbar macht. Bei Gebrauch bildet sich reichlich feinblasiger, cremiger Schaum. In hartem Wasser bilden sich zwar auch Kalkseifenausfällungen, diese bleiben aber in der Lösung dispergiert und schlagen sich auf harten Oberflächen nicht als schmierig-graue Flecken oder käsiger Rand, sondem allenfalls als leichter, feinteiliger Schleier nieder.The soap products of the invention are characterized by a particularly smooth surface from what pleasantly noticeable especially when processing to bar soap power. In use, it forms abundantly fine bubbles, creamy foam. In hard water Although Kalkseifenausfällungen form, but they remain dispersed in the solution and do not strike on hard surfaces as greasy-gray stains or cheesier ones Edge, but at best as a light, finely divided veil down.

    Die folgenden Beispiele sollen die Erfindung erläutem, ohne sie zu beschränken. Grundseife Gew.-% Natriumtallowat 68,00 Natriumcocoat 17,00 Aqua 12,00 NaCI 0,45 EDTA 0,20 Natriumetidronat 0,09 Glycerin 2,50 Natrium-Palmkemfettsäuresalze ad 100,00 Farbslurry Gew.-% Wollwachsalkohol 2,00 Paraffinum liquidum 33,00 Prunus dulcis 7,00 Disteardimoniumhectorit 1,00 TiO2 13,00 Wasser ad 100,00 Beispiel 1 Gew.-% Farbslurry 3,00 Grundseife 87,00 Paraffin 2,00 Polyethylenglycol-150 2,00 Talkum 6,00 Parfum 1,00 Na2S2O3 0,40 Octyldodecanol 0,50 Wasser ad 100,00 The following examples are intended to illustrate the invention without limiting it. basic soaps Wt .-% sodium tallowate 68,00 sodium cocoate 17.00 Aqua 12,00 NaCl 0.45 EDTA 0.20 Natriumetidronat 0.09 glycerin 2.50 Sodium Palmkemfettsäuresalze ad 100.00 color slurry Wt .-% Wool alcohol 2.00 Paraffinum liquidum 33,00 Prunus dulcis 7.00 Disteardimoniumhectorit 1.00 TiO 2 13,00 water ad 100.00 example 1 Wt .-% color slurry 3.00 basic soaps 87,00 paraffin 2.00 Polyethylene glycol-150 2.00 talc 6.00 Perfume 1.00 Na 2 S 2 O 3 0.40 octyldodecanol 0.50 water ad 100.00

    Die Grundseifennudeln werden mit dem Farbslurry und den übrigen Komponenten in einen üblichen Seifenmischer (Schneckenmischer mit Lochsieb) dosiert, durch mehrmaliges Vermischen homogenisiert, über eine Strangpresse ausgetragen, geschnitten und in üblicher Weise zu Stücken verarbeitet. Beispiel 2 Gew.-% Farbslurry 3,00 Grundseife 85,00 Paraffin 1,00 Talkum 7,00 Parfum 1,00 Na2S2O3 0,40 Octyldodecanol 0,50 Wasser ad 100,00 The ground soap noodles are dosed with the color slurry and the other components in a conventional soap mixer (screw mixer with perforated screen), homogenized by repeated mixing, discharged via an extruder, cut and processed in the usual way to pieces. Example 2 Wt .-% color slurry 3.00 basic soaps 85,00 paraffin 1.00 talc 7.00 Perfume 1.00 Na 2 S 2 O 3 0.40 octyldodecanol 0.50 water ad 100.00

    Die Grundseifennudeln werden mit dem Farbslurry und den übrigen Komponenten in einen üblichen Seifenmischer (Schneckenmischer mit Lochsieb) dosiert, durch mehrmaliges Vermischen homogenisiert, über eine Strangpresse ausgetragen, geschnitten und in üblicher Weise zu Stücken verarbeitet. Beispiel 3 Gew.-% Farbslurry 3,00 Grundseife 81,80 Paraffin 1,00 Talkum 9,00 Parfum 1,00 Na2S2O3 0,40 Octyldodecanol 0,50 Wasser ad 100,00 The ground soap noodles are dosed with the color slurry and the other components in a conventional soap mixer (screw mixer with perforated screen), homogenized by repeated mixing, discharged via an extruder, cut and processed in the usual way to pieces. Example 3 Wt .-% color slurry 3.00 basic soaps 81.80 paraffin 1.00 talc 9.00 Perfume 1.00 Na 2 S 2 O 3 0.40 octyldodecanol 0.50 water ad 100.00

    Die Grundseifennudeln werden mit dem Farbslurry und den übrigen Komponenten in einen üblichen Seifenmischer (Schneckenmischer mit Lochsieb) dosiert, durch mehrmaliges Vermischen homogenisiert, über eine Strangpresse ausgetragen, geschnitten und in üblicher Weise zu Stücken verarbeitet. Beispiel 4 Gew.-% Farbslurry 3,00 Grundseife 78,90 Paraffin 1,00 Talkum 12,00 Parfum 1,00 Na2S2O3 0,40 Octyldodecanol 0,50 Wasser ad 100,00 The ground soap noodles are dosed with the color slurry and the other components in a conventional soap mixer (screw mixer with perforated screen), homogenized by repeated mixing, discharged via an extruder, cut and processed in the usual way to pieces. Example 4 Wt .-% color slurry 3.00 basic soaps 78,90 paraffin 1.00 talc 12,00 Perfume 1.00 Na 2 S 2 O 3 0.40 octyldodecanol 0.50 water ad 100.00

    Die Grundseifennudeln werden mit dem Farbslurry und den übrigen Komponenten in einen üblichen Seifenmischer (Schneckenmischer mit Lochsieb) dosiert, durch mehrmaliges Vermischen homogenisiert, über eine Strangpresse ausgetragen, geschnitten und in üblicher Weise zu Stücken verarbeitet.The basic soap noodles become with the color slurry and the remaining components in one usual soap mixer (screw mixer with perforated sieve) dosed, by repeated mixing Homogenized, discharged via an extruder, cut and in the usual Way to pieces processed.

    Claims (9)

    1. Shaped cosmetic soap product comprising
      talc, whose particle diameter is in the range from 0.5-50 µm,
      one or more fatty acids having 12-22 carbon atoms in the form of their alkali soaps and
      one or more refatting substances,
         where the soap product comprises less than 1 % by weight of alkyl (oligo) glycosides.
    2. Soap product according to Claim 1, characterized in that talc grades are chosen which comprise not more than 5% by weight of particles below 1 µm and not more than 5% by weight of particles above 50 µm in size.
    3. Soap product according to Claim 1, characterized in that talc grades are chosen in which the fraction of particles greater than 40 µm in diameter (sieve residue) is at most 2% by weight.
    4. Soap product according to Claim 1, characterized in that talc grades are chosen in which the average particle diameter (D50) is 5-15 µm.
    5. Soap product according to Claim 1, characterized in that it comprises 1-30% by weight of refatting substances, preferably chosen from the group of long-chain alcohols, e.g. lanolin, cetyl alcohol, of mono- and diglycerides or the corresponding glycol esters, of mono-, di-, triglycerides of vegetable origin, e.g. almond oil, of hydrogenated fats, Vaseline, of waxes and of Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, of esters of linear C6-C20-fatty acids with linear C6-C20-fatty alcohols, of esters of branched C6-C13-carboxylic acids with linear C6-C20-fatty alcohols, of esters of linear C6-C18-fatty acids with branched alcohols, in particular 2-ethylhexanol, of esters of linear and/or branched fatty acids with polyhydric alcohols (such as e.g. dimerdiol or trimerdiol) and/or of Guerbet alcohols, of triglycerides based on C6-C10-fatty acids, of branched primary alcohols, of substituted cyclohexanes, of Guerbet carbonates, of dialkyl ethers and/or of aliphatic or naphthenic hydrocarbons.
    6. Soap product according to Claim 1, characterized in that it comprises 1 - 99% by weight of fatty acids having 12-22 carbon atoms, in the form of their alkali soaps, in particular a base soap, for example one whose soap constituents are composed of sodium tallowate, sodium cocoate and sodium palm kernel fatty acid salt.
    7. Soap product according to Claim 1, characterized in that the fatty acids are composed of 50-80% by weight of C16-C18-fatty acids and of 20-50% by weight of C12-C14-fatty acids.
    8. Soap product according to Claim 1, characterized in that 1-10% by weight of free fatty acids having 12-22 carbon atoms are additionally present therein.
    9. Soap product according to Claim 1, characterized in that it comprises water in an amount of from 5-35% by weight.
    EP01115784A 2000-07-20 2001-07-11 Soap bar comprising talc, alkali fatty acid and emollient, but not comprising alkyl oligoglycosides Revoked EP1174493B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE10035213A DE10035213A1 (en) 2000-07-20 2000-07-20 Shaped soap product containing talc, one or more fatty acids in the form of their alkali soaps and one or more lipid-replenishing substances in the absence of alkyl (oligo) glycosides
    DE10035213 2000-07-20

    Publications (2)

    Publication Number Publication Date
    EP1174493A1 EP1174493A1 (en) 2002-01-23
    EP1174493B1 true EP1174493B1 (en) 2005-01-26

    Family

    ID=7649527

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP01115784A Revoked EP1174493B1 (en) 2000-07-20 2001-07-11 Soap bar comprising talc, alkali fatty acid and emollient, but not comprising alkyl oligoglycosides

    Country Status (6)

    Country Link
    US (1) US6589923B2 (en)
    EP (1) EP1174493B1 (en)
    JP (1) JP2002097496A (en)
    AT (1) ATE287943T1 (en)
    DE (2) DE10035213A1 (en)
    ES (1) ES2234736T3 (en)

    Families Citing this family (25)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE10221812A1 (en) * 2002-05-16 2003-11-27 Beiersdorf Ag Aqueous cosmetic composition useful as a shaving or cleansing agent contains fatty acids or salts, emulsifiers, complexers, waxes and talc
    US6706675B1 (en) * 2002-08-30 2004-03-16 The Dial Corporation Translucent soap bar composition and method of making the same
    DE10318325A1 (en) * 2003-04-19 2004-10-28 Beiersdorf Ag A cleansing soap bar contains a combination of surfactants with elastomeric polymers, especially dimethicone/vinyldimethicone cross polymers
    PE20060468A1 (en) * 2004-04-26 2006-07-06 Cp Kelco Aps DERMOPROTECTIVE COMPOSITION TO CONTROL SKIN ALKALINITY, INCLUDING CARBOXYLIC ACID POLYSACCHARIDS
    US6949493B1 (en) 2004-05-19 2005-09-27 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Soap bars comprising synergestically high levels of both free fatty acid and filler
    US20070042919A1 (en) * 2005-08-19 2007-02-22 Catherine Schmit Personal cleansing bar having enhanced skin feel attributes
    US20080153728A1 (en) * 2005-08-19 2008-06-26 The Dial Corporation Cleansing compositions having improved fragrance characteristics and methods for the formulation thereof
    US8017567B2 (en) * 2005-08-19 2011-09-13 The Dial Corporation Personal cleansing bar with free fatty acid and quaternary surfactant synergism
    US20080125340A1 (en) * 2005-08-19 2008-05-29 The Dial Corporation Personal cleansing composition with enhanced skin feel characteristics
    DE102005049834A1 (en) * 2005-10-14 2007-04-19 Beiersdorf Ag Solid soaps with reduced cracking
    US20070098870A1 (en) * 2005-10-27 2007-05-03 Trudsoe Jens E Composition containing alkylene oxide derivative of pectin
    US20080045438A1 (en) * 2006-08-21 2008-02-21 D/B/A Unilever, A Corporation Of New York Softening laundry detergent
    SG182157A1 (en) 2007-06-01 2012-07-30 Solazyme Inc Production of oil in microorganisms
    EP2265724A4 (en) * 2008-04-09 2013-01-23 Solazyme Inc Direct chemical modification of microbial biomass and microbial oils
    CN102712858B (en) 2008-11-28 2015-08-12 索拉兹米公司 Tailor-made oil is prepared in restructuring heterotroph microorganism
    CA2785507C (en) 2009-12-23 2014-10-21 Colgate-Palmolive Company Cleansing bar
    CN103124499B (en) 2010-05-28 2016-09-28 泰拉瑞亚控股公司 Comprise the food compositions of tailor-made oil
    MX340844B (en) 2010-12-09 2016-07-27 Colgate Palmolive Co Cleansing composition.
    EP2817403B1 (en) 2012-02-24 2017-04-05 Colgate-Palmolive Company Soap bar
    US11499123B2 (en) * 2016-08-17 2022-11-15 Zobele Holding S.P.A. Water soluble pellet and method for manufacturing said water soluble pellet
    CA3236000A1 (en) * 2022-08-12 2024-02-15 Matthew Lawrence Lynch Low-water compositions
    US20240052260A1 (en) * 2022-08-12 2024-02-15 The Procter & Gamble Company Low-water compositions
    WO2024036117A1 (en) * 2022-08-12 2024-02-15 The Procter & Gamble Company Low-water compositions
    CA3236224A1 (en) * 2022-08-12 2024-02-15 Matthew Lawrence Lynch Low-water compositions
    WO2024036125A1 (en) * 2022-08-12 2024-02-15 The Procter & Gamble Company Low-water compositions

    Family Cites Families (11)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE6922806U (en) 1969-06-06 1969-11-20 Severin & Co Gmbh Fa A TABLE LAMP
    US5064555A (en) 1985-12-02 1991-11-12 The Procter & Gamble Company Mild skin cleansing soap bar with hydrated cationic polymer skin conditioner
    EP0308190B1 (en) 1987-09-17 1994-04-06 The Procter & Gamble Company Ultra mild skin cleansing toilet bar with selected mixed polymers
    US5154849A (en) 1990-11-16 1992-10-13 The Procter & Gamble Company Mild skin cleansing toilet bar with silicone skin mildness/moisturizing aid
    US5264145A (en) 1991-06-18 1993-11-23 The Procter & Gamble Company Personal cleansing freezer bar with selected fatty acid soaps and synthetic surfactant for reduced bathtub ring, improved mildness, and good lather
    US5294363A (en) * 1991-09-23 1994-03-15 The Procter & Gamble Company Mild personal cleansing bar composition with balanced surfactants, fatty acids, and paraffin wax
    US5703026A (en) * 1995-06-01 1997-12-30 The Procter & Gamble Company Skin cleansing bar soap compositions comprising particles of absorbent gellant materials
    GB2316088A (en) 1996-08-06 1998-02-18 Cussons Int Ltd Lotion Bar
    GB9617552D0 (en) 1996-08-21 1996-10-02 Cussons Int Ltd Personal cleansing bar
    DE19649896A1 (en) 1996-12-02 1998-06-04 Henkel Kgaa Shaped soap products
    US6218348B1 (en) 2000-04-26 2001-04-17 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Process of making soap bar with enhanced skin benefits comprising adding salts of specific protic acid

    Also Published As

    Publication number Publication date
    ES2234736T3 (en) 2005-07-01
    DE10035213A1 (en) 2002-01-31
    US20020045555A1 (en) 2002-04-18
    JP2002097496A (en) 2002-04-02
    EP1174493A1 (en) 2002-01-23
    ATE287943T1 (en) 2005-02-15
    DE50105171D1 (en) 2005-03-03
    US6589923B2 (en) 2003-07-08

    Similar Documents

    Publication Publication Date Title
    EP1174493B1 (en) Soap bar comprising talc, alkali fatty acid and emollient, but not comprising alkyl oligoglycosides
    EP1174495B1 (en) Soap bar comprising talc, alkali fatty acid and nonionic surfactant, but not comprising alkyl oligoglycosides
    DE60104333T2 (en) SKIN CLEANING PIECE WITH HIGH COMPONENTS OF LIQUID SOFTWARE
    DE3330113A1 (en) TRANSPARENT SOAP BARS AND METHOD FOR THE PRODUCTION THEREOF
    EP1174123B1 (en) Shaped soap product comprising talc, one or more alkali salts of fatty acids and one or more amphoteric surfactants free of alkyl-(oligo)-glucosides
    DE60206387T2 (en) PARTICULAR SKIN CLEANING AGENT WITH HIGH STABILITY AGAINST MATCHING
    EP0702711B1 (en) Pourable liquid aqueous cleaning-agent concentrates (ii)
    EP1174494B1 (en) Soap bar comprising talc, alkali fatty acid and anionic surfactant, but not comprising alkyl oligoglycosides
    DE2525775A1 (en) FOAMING AND CONDITIONING AGENT
    DE212015000054U1 (en) Cleaning compositions containing stable silver
    EP0720644B1 (en) Detergent mixtures and washing or cleaning agents with improved solvent properties
    EP1174492B1 (en) Soap bar comprising talc, alkali fatty acid and cationic surfactant, but not comprising alkyl oligoglycosides
    DE60206484T2 (en) SOAP PIECE COMPOSITIONS CONTAINING ANIONIC SURFACE, SOAP, SALT OF HYDROXYANIC ACID AND FILLING MATERIAL
    DE69929833T2 (en) A non-liquid process for producing a particulate detergent containing acyl isethionate, soap and optionally fillers
    EP0941300B1 (en) Shaped soap products
    DE602004010831T2 (en) METHOD FOR PRODUCING SOAPS WITH LOW SODIUM AND HIGH SUGAR CONTENT
    DE19545136C1 (en) Syndet soap bars with little or no free fatty acid content
    EP1497406B1 (en) Molded soap product containing one or several pregelatinized, cross-linked starch derivatives
    DE19641277C2 (en) Syndet soaps
    DE10318325A1 (en) A cleansing soap bar contains a combination of surfactants with elastomeric polymers, especially dimethicone/vinyldimethicone cross polymers
    EP1775338B1 (en) Solid soap with reduced cracking
    DE10216507A1 (en) Shaped detergent products, e.g. &#39;syndet&#39; bars, contain anionic surfactants, pre-gelatinized crosslinked starch derivatives and 12-22C fatty acids as alkali(ne earth) soaps
    DE102010043896A1 (en) Use of in situ prepared zinc soap as pearlescent donor agents in liquid, paste, gel-form to cut-resistant agent, preferably detergents or cleaning agents

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    17P Request for examination filed

    Effective date: 20020206

    17Q First examination report despatched

    Effective date: 20020502

    AKX Designation fees paid

    Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050126

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050126

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: GERMAN

    REF Corresponds to:

    Ref document number: 50105171

    Country of ref document: DE

    Date of ref document: 20050303

    Kind code of ref document: P

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20050317

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050426

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050426

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050426

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2234736

    Country of ref document: ES

    Kind code of ref document: T3

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050711

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050711

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050711

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    PLBI Opposition filed

    Free format text: ORIGINAL CODE: 0009260

    PLAX Notice of opposition and request to file observation + time limit sent

    Free format text: ORIGINAL CODE: EPIDOSNOBS2

    26 Opposition filed

    Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

    Effective date: 20051024

    ET Fr: translation filed
    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

    Free format text: ORIGINAL CODE: EPIDOSCOBS2

    PLBB Reply of patent proprietor to notice(s) of opposition received

    Free format text: ORIGINAL CODE: EPIDOSNOBS3

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IE

    Payment date: 20070720

    Year of fee payment: 7

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20070727

    Year of fee payment: 7

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20070731

    Year of fee payment: 7

    RDAF Communication despatched that patent is revoked

    Free format text: ORIGINAL CODE: EPIDOSNREV1

    BERE Be: lapsed

    Owner name: BEIERSDORF A.G.

    Effective date: 20050731

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050626

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20070720

    Year of fee payment: 7

    RDAG Patent revoked

    Free format text: ORIGINAL CODE: 0009271

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: PATENT REVOKED

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20070710

    Year of fee payment: 7

    27W Patent revoked

    Effective date: 20071127

    GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

    Effective date: 20071127

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: TR

    Payment date: 20080620

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20080723

    Year of fee payment: 8