WO1991015564A1 - Tenside mixture for use in washing and cleaning agents - Google Patents

Tenside mixture for use in washing and cleaning agents Download PDF

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Publication number
WO1991015564A1
WO1991015564A1 PCT/EP1991/000628 EP9100628W WO9115564A1 WO 1991015564 A1 WO1991015564 A1 WO 1991015564A1 EP 9100628 W EP9100628 W EP 9100628W WO 9115564 A1 WO9115564 A1 WO 9115564A1
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WO
WIPO (PCT)
Prior art keywords
polyglucose
surfactants
weight
anionic
surfactant mixture
Prior art date
Application number
PCT/EP1991/000628
Other languages
German (de)
French (fr)
Inventor
Brigitte Giesen
Karlheinz Hill
Andreas Syldath
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to JP91506834A priority Critical patent/JPH05505843A/en
Priority to BR919106329A priority patent/BR9106329A/en
Publication of WO1991015564A1 publication Critical patent/WO1991015564A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017Mixtures of compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017Mixtures of compounds
    • C09K23/018Mixtures of two or more different organic oxygen-containing compounds

Definitions

  • the invention relates to surfactant mixtures and detergents and cleaning agents containing carbohydrate derivatives, and to a method for producing the mixtures and agents.
  • the detergents and cleaning agents form a group of technical products that are constantly produced and consumed in large quantities and then get into the waste water in this way.
  • detergent chemistry has been increasingly concerned with the development of active ingredients based on renewable raw materials.
  • surfactants which can be produced on the basis of oleochemicals, substances based on carbohydrates, in particular those based on glucose and starch, have also gained interest.
  • Typical representatives are the fatty acid sugar esters and especially the fatty alkyl glucosides.
  • European patent application 300 070 discloses a foam-forming component for fire extinguishing foam compositions which contain an alkyl polyglycoside in combination with a polysaccharide, for example starch, glycogen or cellulose.
  • European patent application 74 264 describes liquid hair detergents which, in addition to surfactants, which are usually used in shampoos, and conditioning agents, contain 10 to 70% by weight of mono-, di- or polysaccharides as stabilizers.
  • German patent application 16 28 642 discloses rinse aid for washing dishes containing water-soluble starch degradation products or sugars, which prevent both limescale deposits and signs of corrosion and act as a foam inhibitor.
  • French patent application 1 576613 discloses surfactant components and foaming agents containing them Improvement in foaming power mono- and di-saccharides were added.
  • the object of the present invention is to provide new active substance combinations for use in detergents and cleaners.
  • these combinations should contain a further constituent which is obtainable from native, that is to say renewable, raw materials.
  • the invention relates in a first embodiment to a surfactant mixture which contains one or more surfactants from the group of anionic and nonionic surfactants and polyglucose with an average relative molecular weight between 500 and 70,000.
  • the invention relates to a washing and cleaning agent which contains a surfactant mixture of one or more surfactants from the group of anionic and nonionic surfactants and polyglucose with an average molecular weight of between 500 and 70,000.
  • Preferred carbohydrate derivatives are polyglucoses with an average molecular weight between 800 and 50,000.
  • Polyglucoses which are obtainable chemically or bacterially by polymerizing glucose (dextrans) or which are starch degradation products are particularly suitable, the latter being diluted with incomplete hydrolysis Acids or alkaline solutions, by thermal action or by enzymatic Degradation occur (dextrins).
  • the polyglucoses according to the invention consist of a mixture of different polysaccharides, so that a molecular weight can only be given in the form of an average molecular weight.
  • dextrans obtainable by polymerization and the dextrins obtainable by degrading starch do not differ significantly in their effect when using comparable molecular weights, so that the use of dextrans and dextrins is equally preferred.
  • the use of polyglucoses which have a relative molecular mass between 1,000 and 45,000 and in particular between 1,500 and 40,000 and which are essentially soluble in water is particularly advantageous. "Essentially soluble in water” means that in a 10% by weight solution of polyglucose in softened water (0 ° d) not more than 10% by weight and in particular not more than 5% by weight, based on the amount of polyglucose used, remains as an undissolved sediment.
  • the surfactant mixtures according to the invention can preferably contain up to 50% by weight of polyglucose, based on the sum of surfactants and polyglucose.
  • surfactant mixtures are preferred which contain between 1 and 20% by weight and particularly advantageously between 1 and 12% by weight of polyglucose, based on the sum of surfactants and polyglucose.
  • the surfactant mixtures according to the invention furthermore contain conventional anionic surfactants and / or nonionic surfactants.
  • Suitable anionic surfactants are, for example, surfactants from the class of the sulfonates and sulfates.
  • Preferred surfactants of the sulfonate type are C9-Ci3-alkylbenzenesulfonates and sulfonates based on oleochemistry, such as the esters of ⁇ -sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration.
  • Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, that is, from fatty alcohols, such as. B.
  • coconut fatty alcohols Taigfett ⁇ alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C ⁇ o-C2 ⁇ -oxo alcohols, as well as the sulfuric acid monoesters of secondary alcohol of this chain length
  • the sulfuric acid monoesters of the primary alcohols based on fatty chemicals are preferred.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as linear C 1 -C 8-fatty alcohols or 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide.
  • the sulfates and sulfonates can be present individually or in a mixture.
  • Preferred surfactant mixtures contain alkylbenzenesulfonates and / or fatty alcohol ether sulfates, the use of mixtures of alkylbenzenesulfonate and fatty alcohol ether sulfate in a weight ratio between 1: 1 and 6: 1, in particular between 2: 1 and 5: 1, a particularly advantageous effect is achieved.
  • surfactant mixtures which contain a mixture of alkane sulfonate and fatty alcohol ether sulfate, in particular in a weight ratio of 1: 1 to 4: 1, as the anionic component.
  • Soaps from natural or synthetic, preferably saturated fatty acids can also be used as anionic surfactants. Suitable are in particular from natural fatty acids, e.g. B. coconut, palm kernel or taig fatty acids derived soap mixtures. Preference is given to those composed of 50 to 100% saturated C12-C1 fatty acid soaps and 0 to 50% oleic acid soap are.
  • the soap content in the mixtures according to the invention is between 0 and 15% by weight. However, preferred mixtures are soap-free.
  • anionic constituents of the surfactant mixtures according to the invention are disalts of the fatty acids sulfonated in the ⁇ -position, which are obtained by reacting saturated fatty acids based predominantly on natural raw materials by reaction with sulfur trioxide and subsequent conversion into the alkali metal, alkaline earth metal or Ammonium or organic amine salts are obtained. Disalts are likewise obtained in the production of sulfo fatty acid ester mono salts by partial saponification of the ester group. In such mixtures with oc-sulfofatty acid ester mono salts, the disalt can have a proportion of 10% by weight to 50% by weight.
  • disalts in the surfactant mixtures according to the invention is not restricted to a combination with ⁇ -sulfofatty acid ester mono salts. Disalze can be used alone or with any other anionic or nonionic surfactant. Preferred disalts are derived from fatty acids or fatty acid mixtures, in particular of natural origin, which have a C chain length between 8 and 18 and preferably between 12 and 18.
  • Suitable nonionic surfactants are, for example, customary ethoxylated fatty alcohols, in particular adducts of 2 to 7 mol of ethylene oxide (EO) with linear primary alcohols, such as, for. B. on coconut, tallow or oleyl alcohol, or on 2-position methyl branched primary alcohols (oxo alcohols).
  • EO ethylene oxide
  • linear primary alcohols such as, for. B. on coconut, tallow or oleyl alcohol, or on 2-position methyl branched primary alcohols (oxo alcohols).
  • Particularly preferred nonionic surfactants are fatty alkyl glycosides, in particular fatty alkyl glucosides, of the general formula R0 (G) x , where R is a fatty alkyl radical with CQ to (-22 atoms, preferably with essentially (2 to Ci8 atoms, G is a conventional glycose unit and in particular a glucose unit and x is a number between 1 and 10.
  • fatty alkyl glucosides Both ⁇ - and ß-configured glucosides, the fatty alkyl radical of which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions which preferably contain saturated alcohols, are particularly suitable Alkyl glucosides are used whose alkyl radical contains 50 to 70% by weight of C12 and 18 to 30% by weight (44.
  • the index number x is any number between 1 and 10; it gives the degree of oligomerization, ie the distribution of monoglucosides and oligoglucosides ..
  • x must always be an integer in a given compound, and above all the values x can be 1 to 6, the value x is an analytically determined re for a special product chemical size, which usually represents a broken number.
  • the average degree of oligomerization x preferably has a value of 1.1 to 3.0 and in particular of significantly less than 1.5. A degree of oligomerization between 1.1 and 1.4 is particularly preferred.
  • Alkyl glycosides or alkyl glucosides of the type described above can already contain polyglycoses or polyglucoses. The latter are formed in a side reaction in the production of alkyl glycosides by condensation of the glycose molecules with one another. These polyglycoses and in particular the polyglucoses are to be regarded as constituents of the nonionic surfactant "alkylglycoside / alkylglucoside" and are not among the carbohydrate derivatives to be used in accordance with the invention.
  • mixtures which contain alkyl glucosides and additionally used polyglucose in a weight ratio of 99: 1 to 50:50 as active substance have no significant reduction in performance with regard to their textile washing ability and their dishwashing ability, and in particular mixtures who have favourited Alkyl Glucosides and Additionally include polyglucose used in a weight ratio of 95: 5 to 85:15, may even have an increase in performance compared to mixtures which contain only alkyl glucosides as active substance.
  • Preferred surfactant mixtures contain anionic and nonionic surfactants in a weight ratio of 5: 1 to 1: 3 and in particular 2: 1 to 1: 2.
  • preferred detergents and cleaning agents according to the invention contain anionic and / or nonionic surfactants, polyglucoses with an average relative molecular weight between 800 and 50,000 and further usual constituents of detergents and cleaning agents.
  • Detergents and cleaning agents which contain between 5 and 40% by weight, preferably 8 to 25% by weight, of the mixtures according to the invention are advantageously used.
  • Detergents and cleaning agents which contain surfactant mixtures with a content of 1 to 12% by weight, based on the sum of surfactants and polyglucoses, of dextrins and / or dextranes are used with particular advantage.
  • Detergents and cleaning agents which contain the surfactant mixtures according to the invention with up to 50% by weight of polyglucoses, based on the sum of surfactants and polyglucoses, have no significant reduction in performance. On the contrary, in some cases they can even perform better than agents which contain surfactant mixtures in the same amounts, which consist only of surfactants and in which the surfactants are not partially replaced by polyglucose.
  • washing and cleaning agents which contain the surfactant mixtures according to the invention with 1 to 20% by weight polyglucose, based on the sum of surfactants and polyglucoses.
  • the washing and cleaning agents according to the invention can be in solid, liquid or pasty form.
  • the agents can include both inorganic and organic builders, polymers, salts known as "washing alkalis", graying inhibitors, foam inhibitors, bleaching agents and bleach activators as well as optical brighteners, enzymes, fabric softening agents, dyes and fragrances, neutral salts, contain organic solvents and water.
  • Weakly acidic, neutral or alkaline-reacting salts are suitable as organic and inorganic builders, in particular alkali salts, which can precipitate or bind calcium ions in a complex manner.
  • Suitable and, in particular, ecologically harmless builder substances such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12837) are used with preference .
  • Their average particle size is usually in the range from 1 to 10 ⁇ .
  • Their content is generally 0 to 40, preferably 10 to 30% by weight, based on the anhydrous substance.
  • polymeric polycarboxylates such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the The acidity is at least 50%.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, as well as polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation by means of alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units are.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons.
  • NTA nitrilotriacetate
  • phosphates can also be used, in particular pentasodium tri-phosphate, optionally also pyrophosphates, which, owing to their solubility properties, can be used in liquid detergents, and orthophosphates, which are primarily used as precipitants for lime salts Act.
  • the phosphate content based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used.
  • Suitable organic, non-complexing salts are the bicarbonates, carbonates, borates or silicates of the alkalis - also referred to as "washing alkalis"; Of the alkali silicates, especially the sodium silicates with a Na2 ⁇ : Si ⁇ 2 ratio of 1: 1 to 1: 3.5 can be used.
  • Carboxymethyl cellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used as graying inhibitors.
  • graying inhibitors such as polyvinylpyrrolidone can also be used.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Bisacylamides derived from Ci2-C20-Al ylamines and C2-Co-dicarboxylic acids can also be used.
  • Mixtures of various foam inhibitors are also advantageously used, eg. B. from silicone and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • sodium perborate tetrahydrate NaB02 • H2O2 • 3 H2O
  • sodium perborate monohydrate NaBÜ2 • H2O2
  • Other bleaching agents are, for example, peroxycarbonate (Na2CO3 • 1.5 H2O2), citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxaphthalates or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, furthermore carboxylic anhydrides and esters of polyols such as glucose pentaacetate.
  • the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • B salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which Instead of the morpholino group, wear a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • B the compound 4,4-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded on coating substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids such as l-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP) are suitable as stabilizers, in particular for per compounds and enzymes.
  • HEDP l-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • the lower alcohols, ether alcohols and glycols with 1 to 6 carbon atoms are particularly suitable as water-soluble organic solvents.
  • detergents and cleaning agents contain 8-25% by weight of surfactant mixtures with a content of 1-20% by weight and in particular 1-12% by weight of polyglucose, based on the sum of polyglucoses and surfactants , 10-30% by weight of fluoride substances, 10-25% by weight of bleaching agents, 0-5% by weight of polymers and 2-15% by weight of alkali silicates and / or alkali metal carbonates.
  • detergents and cleaning agents of the above composition are preferred, in which the surfactant mixtures are alkylbenzenesulfonate and / or fatty alcohol ether sulfate as an anionic surfactant component.
  • detergents and cleaning agents of the above composition are preferred which contain 1 to 15% by weight of alkyl glucosides.
  • Manual dishwashing detergents containing 5-30% by weight of anionic surfactants, such as alkylbenzenesulfonate, fatty alcohol ether sulfate, secondary alkanesulfonate, ⁇ -sulfofatty acid disalt or mixtures thereof, and 1-5% by weight of polyglucose, such as dextrans and / or dextrins.
  • anionic surfactants such as alkylbenzenesulfonate, fatty alcohol ether sulfate, secondary alkanesulfonate, ⁇ -sulfofatty acid disalt or mixtures thereof, and 1-5% by weight of polyglucose, such as dextrans and / or dextrins.
  • manual dishwashing detergents which contain 5-20% by weight of anionic surfactants from the group given above, 1-15% by weight of nonionic surfactants, preferably alkyl glucosides, and 1-5% by weight of dextrans and / or dextrins.
  • Both the surfactant mixtures according to the invention and the washing and cleaning agents according to the invention can be prepared in a manner which is conventional per se, for example by mixing, granulating and / or by spray drying. In the case of detergents and cleaning agents, separately prepared surfactant mixtures can be used. It is also possible to incorporate the surfactant components and the polyglucose individually into the compositions in a manner which is customary per se and in any order.
  • the binary or ternary surfactant mixture in question was dissolved as a cleaning agent in a concentration of 0.15 g of the mixture in 1 liter of the 45 ° C. warm water. Cleaning liquors with different water hardnesses of 16 ° d, 3 ° d and 0 ° d were produced. Beef tallow (approx. 1.7 g per plate) was used as standard soiling (see H.-J. Lehmann, "Fette, Seifen, Anstrichstoff 1, pages 163 to 165, 1972). A difference in the washing capacity of 2 plates and more can be seen as significant.
  • C12-C14-APG alkyl glucoside of the Ci2-Ci4 fatty alcohol mixture, produced by the method of transacetalization with butanol
  • ABS dodecylbenzenesulfonate, sodium salt
  • disalt ⁇ -sulfo-Ci6 / 18 ⁇ fatty acid .
  • Na disalt SAS Hostapur SAS 30 (sales product of Hoechst AG), secondary alkane sulfonate
  • Dextran 17200 polyglucose
  • M r (molecular weight) 17 200 dextran 9000 polyglucose
  • M r 9000 dextrin type I polyglucose
  • Dextrin type IV polyglucose, M r 13750

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Abstract

Polyglucoses with an average relative molecular mass of between 500 and 70,000, which themselves have no surface-active properties, when in combination with one or more tensides from the group of anionic and non-ionic tensides, intensify the washing and cleaning action of these tensides and/or make it possible to replace part of the tensides without reducing the washing and cleaning action. Preferred tenside mixtures may contain up to 50 % wt. polyglucoses in relation to the sum of tensides and polyglucoses.

Description

"Tensid ischung für die Verwendung in Wasch- und Reinigungsmitteln" "Surfactant for use in detergents and cleaning agents"
Die Erfindung betrifft Tensidmischungen und Wasch- und Reinigungs¬ mittel mit einem Gehalt an Kohlenhydrat-Derivaten sowie ein Ver¬ fahren zur Herstellung der Mischungen und Mittel.The invention relates to surfactant mixtures and detergents and cleaning agents containing carbohydrate derivatives, and to a method for producing the mixtures and agents.
Die Wasch- und Reinigungsmittel bilden eine Gruppe von technischen Produkten, die ständig in großen Mengen produziert und verbraucht werden und dann auf diese Weise in die Abwässer gelangen. Nachdem große und schließlich erfolgreiche Anstrengungen unternommen wor¬ den sind, die Waschmittel-Phosphate durch andere, die Umwelt we¬ niger belastende Buildersubstanzen zu ersetzen, und nachdem es außerdem gelungen ist, die biologische Abbaubarkeit der tensidi- schen Bestandteile in den Wasch- und Reinigungsmitteln stark zu verbessern, hat sich in neuerer Zeit die Waschmittel-Chemie ver¬ stärkt mit der Entwicklung von Wirkstoffen auf der Basis von nach¬ wachsenden Rohstoffen beschäftigt. Neben den auf fettchemischer Basis herstellbaren Tensiden haben auch Substanzen auf Kohlenhy¬ drat-Basis, insbesondere auf Basis Glucose und Stärke an Interesse gewonnen. Typische Vertreter sind die Fettsäure-Zuckerester und insbesondere die Fettalkylglucoside. Es hat in der Vergangenheit auch nicht an Versuchen gefehlt, Verbindungen auf reiner Kohlen¬ hydrat-Basis als Bestandteile von Wasch- und Reinigungsmitteln zu verwenden, zumal die Rohstoffe Stärke, Saccharose und Glucose vom günstigen Preis her als industrielle Ausgangsmaterialien inter¬ essant erschienen. So gehört heute die Verwendung von Mono-, Di- und/oder Polysac- chariden als Bindemittel (US-Amerikanische Patentschrift 3803285, Deutsche Patentanmeldung 20 00 069), Haftmittel (Euro¬ päische Patentanmeldung 145 438), Verdickungsmittel (US-Amerika¬ nische Patentschrift 4 435 300), Emulsionsstabilisatoren (Bri¬ tische Patentschrift 2 148 926), und als Enzymstabilisatoren (US-Amerikanische Patentschrift 3773674) zum Stand der Technik.The detergents and cleaning agents form a group of technical products that are constantly produced and consumed in large quantities and then get into the waste water in this way. After great and finally successful efforts have been made to replace the detergent phosphates with other, less polluting builder substances, and after the biodegradability of the surfactant components in the detergents and cleaning agents has also been achieved In recent years, detergent chemistry has been increasingly concerned with the development of active ingredients based on renewable raw materials. In addition to the surfactants which can be produced on the basis of oleochemicals, substances based on carbohydrates, in particular those based on glucose and starch, have also gained interest. Typical representatives are the fatty acid sugar esters and especially the fatty alkyl glucosides. In the past there has been no lack of attempts to use pure carbohydrate-based compounds as constituents of detergents and cleaning agents, especially since the raw materials starch, sucrose and glucose have appeared to be of reasonable price as industrial starting materials. Today, the use of mono-, di- and / or polysaccharides as binders (US Pat. No. 3803285, German patent application 20 00 069), adhesives (European patent application 145 438), thickeners (US-American niche Patent 4,435,300), emulsion stabilizers (British Patent 2,148,926), and as enzyme stabilizers (US Pat. No. 3,773,674) to the prior art.
In der Europäischen Patentanmeldung 300 070 wird eine schaumbil¬ dende Komponente für Feuerlöschschaummittel offenbart, die ein Alkylpolyglykosid in Kombination mit einem Polysaccharid, bei¬ spielsweise Stärke, Glykogen oder Cellulose, enthalten.European patent application 300 070 discloses a foam-forming component for fire extinguishing foam compositions which contain an alkyl polyglycoside in combination with a polysaccharide, for example starch, glycogen or cellulose.
Weiterhin ist aus der Europäischen Patentanmeldung 215 637 be¬ kannt, daß sprühgetrocknete Waschmittel, die nicht phosphathaltige Buildersubstanzen beinhalten, eine zufriedenstellende Dispergier- barkeit in Wasser zeigen, wenn Mono-, Di- oder Polysaccharide, deren Derivate oder wasserlösliche Stärkeabbauprodukte in Mengen von 1 bis 20 Gew.-%, bezogen auf das sprühgetrocknete Produkt, als Strukturierungsmittel eingesetzt werden.Furthermore, it is known from European Patent Application 215 637 that spray-dried detergents which do not contain builder substances containing phosphate show satisfactory dispersibility in water when mono-, di- or polysaccharides, their derivatives or water-soluble starch degradation products in amounts of 1 to 20% by weight, based on the spray-dried product, can be used as structuring agent.
Die Europäische Patentanmeldung 74 264 beschreibt flüssige Haar¬ waschmittel, die außer Tensiden, die üblicherweise in Haarwasch¬ mitteln eingesetzt werden, und Konditionierungsmitteln 10 bis 70 Gew.-% Mono-, Di- oder Polysaccharide als Stabilisatoren enthal¬ ten.European patent application 74 264 describes liquid hair detergents which, in addition to surfactants, which are usually used in shampoos, and conditioning agents, contain 10 to 70% by weight of mono-, di- or polysaccharides as stabilizers.
Die Deutsche Patentanmeldung 16 28 642 offenbart Klarspülmittel zur Geschirreinigung mit einem Gehalt an wasserlöslichen Stärke¬ abbauprodukten oder Zuckern, die sowohl Kalkablagerungen wie auch Korrosionserscheinungen verhindern und als Schauminhibitor wirken.German patent application 16 28 642 discloses rinse aid for washing dishes containing water-soluble starch degradation products or sugars, which prevent both limescale deposits and signs of corrosion and act as a foam inhibitor.
Aus der Französischen Patentanmeldung 1 576613 sind Tensidkompo- nenten und diese enthaltende, schäumende Mittel bekannt, denen zur Verbesserung der Schaumkraft Mono- und Di-Saccharide zugesetzt wurden.French patent application 1 576613 discloses surfactant components and foaming agents containing them Improvement in foaming power mono- and di-saccharides were added.
Der vorliegenden Erfindung liegt die Aufgabe zu Grunde, neue Wirk¬ stoffkombinationen für die Verwendung in Wasch- und Reinigungs¬ mitteln bereitzustellen. Diese Kombinationen sollen neben herkömm¬ lichen bekannten Tensiden einen weiteren Bestandteil enthalten, der aus nativen, also nachwachsenden Rohstoffen erhältlich ist.The object of the present invention is to provide new active substance combinations for use in detergents and cleaners. In addition to conventionally known surfactants, these combinations should contain a further constituent which is obtainable from native, that is to say renewable, raw materials.
Es wurde nun gefunden, daß bestimmte Kohlenhydrat-Derivate, die selber keine oberflächenaktiven Eigenschaften besitzen, in Ver¬ bindung mit an sich üblichen Tensiden deren Wasch- und Reinigungs¬ wirkung verstärken und/oder einen Teil der Tenside zu ersetzen vermögen, ohne daß die Wasch- und Reinigungswirkung vermindert wird.It has now been found that certain carbohydrate derivatives, which themselves have no surface-active properties, in conjunction with conventional surfactants, enhance their washing and cleaning action and / or can replace some of the surfactants without the washing - And cleaning effect is reduced.
Gegenstand der Erfindung ist dementsprechend in einer ersten Aus¬ führungsform eine Tensidmischung, die ein oder mehrere Tenside aus der Gruppe der anionischen und nichtionischen Tenside sowie Poly¬ glucose mit einer durchschnittlichen relativen Molekülmasse zwi¬ schen 500 und 70000 enthält.Accordingly, the invention relates in a first embodiment to a surfactant mixture which contains one or more surfactants from the group of anionic and nonionic surfactants and polyglucose with an average relative molecular weight between 500 and 70,000.
Gegenstand der Erfindung ist in einer weiteren Ausführungsform ein Wasch- und Reinigungsmittel, das eine Tensidmischung aus einem oder mehreren Tensiden aus der Gruppe der anionischen und nicht¬ ionischen Tenside und Polyglucose mit einer durchschnittlichen relativen Molekülmasse zwischen 500 und 70000 enthält.In a further embodiment, the invention relates to a washing and cleaning agent which contains a surfactant mixture of one or more surfactants from the group of anionic and nonionic surfactants and polyglucose with an average molecular weight of between 500 and 70,000.
Bevorzugte Kohlenhydrat-Derivate sind Polyglucosen mit einer durchschnittlichen relativen Molekülmasse zwischen 800 und 50 000 Insbesondere sind Polyglucosen geeignet, die chemisch oder bakte¬ riell durch Polymerisation von Glucose (Dextrane) erhältlich sind oder die Abbauprodukte der Stärke darstellen, wobei diese durch unvollständige Hydrolyse mit verdünnten Säuren oder alkalischen Lösungen, durch thermische Einwirkung oder durch enzymatischen Abbau entstehen (Dextrine). Die erfindungsgemäßen Polyglucosen bestehen je nach ihrer Herstellungsart aus einem Gemisch von verschiedenen Polysacchariden, so daß die Angabe eines Moleku¬ largewichts nur in Form eines durchschnittlichen Molekulargewichts erfolgen kann.Preferred carbohydrate derivatives are polyglucoses with an average molecular weight between 800 and 50,000. Polyglucoses which are obtainable chemically or bacterially by polymerizing glucose (dextrans) or which are starch degradation products are particularly suitable, the latter being diluted with incomplete hydrolysis Acids or alkaline solutions, by thermal action or by enzymatic Degradation occur (dextrins). Depending on the type of preparation, the polyglucoses according to the invention consist of a mixture of different polysaccharides, so that a molecular weight can only be given in the form of an average molecular weight.
Die durch Polymerisation erhältlichen Dextrane und die durch Abbau von Stärke erhältlichen Dextrine unterscheiden sich bei der Zu¬ grundelegung vergleichbarer Molekülmasse nicht wesentlich in ihrer Wirkung, so daß der Einsatz von Dextranen und Dextrinen gleicher¬ maßen bevorzugt ist. Besonders vorteilhaft ist der Einsatz von Polyglucosen, die eine relative Molekülmasse zwischen 1 000 und 45000 und insbesondere zwischen 1 500 und 40 000 aufweisen und die im wesentlichen in Wasser löslich sind. Dabei bedeutet "im wesentlichen in Wasser löslich", daß in einer 10-Gew.-%igen Lösung von Polyglucose in enthärtetem Wasser (0° d) nicht mehr als 10 Gew.-% und insbesondere nicht mehr als 5 Gew.-%, bezogen auf die Menge der eingesetzten Polyglucose, als Bodensatz ungelöst zurück bleibt.The dextrans obtainable by polymerization and the dextrins obtainable by degrading starch do not differ significantly in their effect when using comparable molecular weights, so that the use of dextrans and dextrins is equally preferred. The use of polyglucoses which have a relative molecular mass between 1,000 and 45,000 and in particular between 1,500 and 40,000 and which are essentially soluble in water is particularly advantageous. "Essentially soluble in water" means that in a 10% by weight solution of polyglucose in softened water (0 ° d) not more than 10% by weight and in particular not more than 5% by weight, based on the amount of polyglucose used, remains as an undissolved sediment.
Die erfindungsgemäßen Tensidmischungen können vorzugsweise bis zu 50 Gew.-% Polyglucose, bezogen auf die Summe aus Tensiden und Polyglucose, enthalten. Insbesondere sind Tensidmischungen bevor¬ zugt, die zwischen 1 und 20 Gew.-% und mit besonderem Vorteil zwischen 1 und 12 Gew.-% Polyglucose, bezogen auf die Summe aus Tensiden und Polyglucose, enthalten.The surfactant mixtures according to the invention can preferably contain up to 50% by weight of polyglucose, based on the sum of surfactants and polyglucose. In particular, surfactant mixtures are preferred which contain between 1 and 20% by weight and particularly advantageously between 1 and 12% by weight of polyglucose, based on the sum of surfactants and polyglucose.
Die erfindungsgemäßen Tensidmischungen beinhalten weiterhin üb¬ liche anionische Tenside und/oder nichtionische Tenside. Geeignete anionische Tenside sind beispielsweise Tenside aus der Klasse der Sulfonate und Sulfate. Als Tenside vom Sulfonattyp kommen vorzugs¬ weise C9-Ci3-Alkylbenzolsulfonate und Sulfonate auf fettchemischer Basis, wie die Ester von α-Sulfofettsäuren, wobei die Sulfogruppe in ihrer Salz-Form vorliegt (Monosalz), z. B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren in Betracht. Geeignet sind außerdem auch die biologisch gut ab¬ baubaren Alkansulfonate, die aus Ci2-Ci8-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hy¬ drolyse bzw. Neutralisation gewonnen werden. Die Sulfonatgruppe ist über die gesamte Kohlenstoffkette statistisch verteilt, wobei die sekundären Alkansulfonate überwiegen. Geeignete Tenside vom Sulfattyp sind beispielsweise die Schwefelsäuremonoester aus pri¬ mären Alkoholen natürlichen und synthetischen Ursprungs, daß heißt, aus Fettalkoholen, wie z. B. Kokosfettalkoholen, Taigfett¬ alkoholen, Oleylalkohol, Lauryl-, Myristyl-, Palmityl- oder Stea- rylalkohol, oder den Cιo-C2θ-Oxoalkoholen, sowie die Schwefel¬ säuremonoester sekundärer Alkohol dieser Kettenlänge, wobei die Schwefelsäuremonoester der primären Alkohole auf fettchemischer Basis bevorzugt sind. Ebenfalls bevorzugt sind die Schwefelsäure¬ monoester der mit 1 bis 6 mol Ethylenoxid ethoxylierten Alkohole, wie lineare Ci2-Ci8-Fettalkohole oder 2-Methyl-verzweigte Cg-Cn-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid.The surfactant mixtures according to the invention furthermore contain conventional anionic surfactants and / or nonionic surfactants. Suitable anionic surfactants are, for example, surfactants from the class of the sulfonates and sulfates. Preferred surfactants of the sulfonate type are C9-Ci3-alkylbenzenesulfonates and sulfonates based on oleochemistry, such as the esters of α-sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration. Also suitable are the readily biodegradable alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating. Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, that is, from fatty alcohols, such as. B. coconut fatty alcohols, Taigfett¬ alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the Cιo-C2θ-oxo alcohols, as well as the sulfuric acid monoesters of secondary alcohol of this chain length, the sulfuric acid monoesters of the primary alcohols based on fatty chemicals are preferred. Also preferred are the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as linear C 1 -C 8-fatty alcohols or 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide.
Die Sulfate und Sulfonate können einzeln oder im Gemisch vorlie¬ gen. Bevorzugte Tensidmischungen enthalten Alkylbenzolsulfonate und/oder Fettalkoholethersulfate, wobei durch den Einsatz von Mi¬ schungen aus Alkylbenzolsulfonat und Fettalkoholethersulfat in einem Gewichtsverhältnis zwischen 1 : 1 und 6 : 1, insbesondere zwischen 2 : 1 und 5 : 1, eine besonders vorteilhafte Wirkung er¬ zielt wird. Ebenso sind Tensidmischungen bevorzugt, die als anio¬ nische Komponente eine Mischung aus Alkansulfonat und Fettalko¬ holethersulfat insbesondere in einem Gewichtsverhältnis von 1 : 1 bis 4 : 1 enthalten.The sulfates and sulfonates can be present individually or in a mixture. Preferred surfactant mixtures contain alkylbenzenesulfonates and / or fatty alcohol ether sulfates, the use of mixtures of alkylbenzenesulfonate and fatty alcohol ether sulfate in a weight ratio between 1: 1 and 6: 1, in particular between 2: 1 and 5: 1, a particularly advantageous effect is achieved. Likewise preferred are surfactant mixtures which contain a mixture of alkane sulfonate and fatty alcohol ether sulfate, in particular in a weight ratio of 1: 1 to 4: 1, as the anionic component.
Als anionische Tenside sind auch Seifen aus natürlichen oder syn¬ thetischen, vorzugsweise gesättigten Fettsäuren brauchbar. Geeig¬ net sind insbesondere aus natürlichen Fettsäuren, z. B. Kokos-, Palmkern- oder Taigfettsäuren abgeleitete Seifengemische. Bevor¬ zugt sind solche, die zu 50 bis 100 % aus gesättigten C12-C1 - Fettsäureseifen und zu 0 bis 50 % aus ölsäureseife zusammengesetzt sind. Der Gehalt an Seife in den erfindungsgemäßen Mischungen liegt zwischen 0 und 15 Gew.-%. Bevorzugte Mischungen sind jedoch frei von Seife.Soaps from natural or synthetic, preferably saturated fatty acids can also be used as anionic surfactants. Suitable are in particular from natural fatty acids, e.g. B. coconut, palm kernel or taig fatty acids derived soap mixtures. Preference is given to those composed of 50 to 100% saturated C12-C1 fatty acid soaps and 0 to 50% oleic acid soap are. The soap content in the mixtures according to the invention is between 0 and 15% by weight. However, preferred mixtures are soap-free.
Als weitere anionische Bestandteile der erfindungsgemäßen Tensid¬ mischungen kommen Disalze der in α-Stellung sulfonierten Fettsäu¬ ren, welche durch Umsetzung von gesättigten, vorwiegend auf na¬ türlichen Rohstoffen basierenden Fettsäuren durch Umsetzung mit Schwefeltrioxid und anschließende Überführung in die Alkali-, Erdalkali- oder Ammonium- bzw. organischen Aminsalze erhalten werden. Disalze werden ebenfalls bei der Herstellung von -Sulfo- fettsäureester-Monosalzen durch partielle Verseifung der Ester¬ gruppe erhalten. Das Disalz kann in solchen Gemischen mit oc-Sul- fofettsäureester-Monosalzen einen Anteil von 10 Gew.-% bis 50 Gew.-% aufweisen. Die Verwendung von Disalzen in den erfindungs¬ gemäßen Tensidmischungen ist jedoch nicht auf eine Kombination mit α-Sulfofettsäureester-Monosalzen beschränkt. Disalze können allein oder mit jedem anderen anionischen oder nichtionischen Tensid eingesetzt werden. Bevorzugte Disalze leiten sich von Fettsäuren bzw. Fettsäuregemischen insbesondere natürlichen Ursprungs ab, die eine C-Kettenlänge zwischen 8 und 18 und vorzugsweise zwischen 12 und 18 aufweisen.Other anionic constituents of the surfactant mixtures according to the invention are disalts of the fatty acids sulfonated in the α-position, which are obtained by reacting saturated fatty acids based predominantly on natural raw materials by reaction with sulfur trioxide and subsequent conversion into the alkali metal, alkaline earth metal or Ammonium or organic amine salts are obtained. Disalts are likewise obtained in the production of sulfo fatty acid ester mono salts by partial saponification of the ester group. In such mixtures with oc-sulfofatty acid ester mono salts, the disalt can have a proportion of 10% by weight to 50% by weight. However, the use of disalts in the surfactant mixtures according to the invention is not restricted to a combination with α-sulfofatty acid ester mono salts. Disalze can be used alone or with any other anionic or nonionic surfactant. Preferred disalts are derived from fatty acids or fatty acid mixtures, in particular of natural origin, which have a C chain length between 8 and 18 and preferably between 12 and 18.
Geeignete nichtionische Tenside sind beispielsweise übliche eth- oxylierte Fettalkohole, insbesondere Anlagerungsprodukte von 2 bis 7 mol Ethylenoxid (EO) an lineare primäre Alkohole, wie z. B. an Kokos-, Taigfett- oder Oleylalkohol, oder an in 2-Stellung methyl¬ verzweigte primäre Alkohole (Oxoalkohole). Insbesondere werden Cl2"Cl4-Alkohole mit 3 EO oder 4 EO, Ci3-Cχ5-Alkohole mit 3, 5 oder 7 EO, Ci2-Ci8-Alkohole mit 3, 5 oder 7 EO und Mischungen aus diesen, wie Mischungen aus Ci2~Ci4-Alkohol mit 3 EO und Ci2-Cl8~ Alkohole mit 5 EO eingesetzt.Suitable nonionic surfactants are, for example, customary ethoxylated fatty alcohols, in particular adducts of 2 to 7 mol of ethylene oxide (EO) with linear primary alcohols, such as, for. B. on coconut, tallow or oleyl alcohol, or on 2-position methyl branched primary alcohols (oxo alcohols). In particular, Cl2 "Cl4 alcohols with 3 EO or 4 EO, Ci3-Cχ5 alcohols with 3, 5 or 7 EO, Ci2-Ci8 alcohols with 3, 5 or 7 EO and mixtures of these, such as mixtures of Ci2 ~ Ci4 -Alcohol with 3 EO and Ci2-Cl8 ~ alcohols with 5 EO used.
Besonders bevorzugte nichtionische Tenside sind Fettalkyglykoside, insbesondere Fettalkylglucoside, der allgemeinen Formel R0(G)x, wobei R einen Fettalkylrest mit CQ- bis (-22-Atomen, vorzugsweise mit im wesentlichen ( 2- bis Ci8~Atomen, G eine übliche Glykose- einheit und insbesondere eine Glucoseeinheit und x eine Zahl zwi¬ schen 1 und 10 darstellt. Als Fettalkylglucoside eignen sich ins¬ besondere sowohl α- als auch ß-konfigurierte Glucoside, deren Fettalkylrest sich von Lauryl-, Myristyl-, Cetyl- und Stearylal- kohol sowie von technischen Fraktionen, die vorzugsweise gesät¬ tigte Alkohole enthalten, ableitet. Mit besonderer Bevorzugung werden Alkylglucoside eingesetzt, deren Alkylrest zu 50 bis 70 Gew.-% C12 und 18 bis 30 Gew.-% (44 enthält. Die Indexzahl x ist eine beliebige Zahl zwischen 1 und 10; sie gibt den Oligomerisie- rungsgrad, d. h. die Verteilung von Monoglucosiden und Oligoglu- cosiden an. Während x in einer gegebenen Verbindung immer eine ganze Zahl sein muß, und hier vor allem die Werte x gleich 1 bis 6 annehmen kann, ist der Wert x für ein spezielles Produkt eine analytisch ermittelte rechnerische Größe, die meistens eine ge¬ brochene Zahl darstellt. Vorzugsweise hat der mittlere Oligomeri- sierungsgrad x einen Wert von 1,1 bis 3,0 und insbesondere von deutlich kleiner als 1,5. Besonders bevorzugt ist ein Oligomeri- sierungsgrad zwischen 1,1 und 1,4.Particularly preferred nonionic surfactants are fatty alkyl glycosides, in particular fatty alkyl glucosides, of the general formula R0 (G) x , where R is a fatty alkyl radical with CQ to (-22 atoms, preferably with essentially (2 to Ci8 atoms, G is a conventional glycose unit and in particular a glucose unit and x is a number between 1 and 10. As fatty alkyl glucosides Both α- and ß-configured glucosides, the fatty alkyl radical of which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions which preferably contain saturated alcohols, are particularly suitable Alkyl glucosides are used whose alkyl radical contains 50 to 70% by weight of C12 and 18 to 30% by weight (44. The index number x is any number between 1 and 10; it gives the degree of oligomerization, ie the distribution of monoglucosides and oligoglucosides .. While x must always be an integer in a given compound, and above all the values x can be 1 to 6, the value x is an analytically determined re for a special product chemical size, which usually represents a broken number. The average degree of oligomerization x preferably has a value of 1.1 to 3.0 and in particular of significantly less than 1.5. A degree of oligomerization between 1.1 and 1.4 is particularly preferred.
Alkylglykoside bzw. Alkylglucoside der oben beschriebenen Art können bereits Polyglykosen bzw. Polyglucosen enthalten. Letztere werden bei der Herstellung von Alkylglykosiden in einer Nebenre¬ aktion durch Kondensation der Glykosemoleküle untereinander ge¬ bildet. Diese Polyglykosen und insbesondere die Polyglucosen sind als Bestandteile des nichtionischen Tensids "Alkylglykosid/Alkyl- glucosid" anzusehen und zählen nicht zu den erfindungsgemäß ein¬ zusetzenden, zusätzlich zuzusetzenden Kohlenhydrat-Derivaten. Vielmehr wurde überraschenderweise gefunden, daß Mischungen, die als Aktivsubstanz Alkylglucoside und zusätzlich eingesetzte Poly¬ glucose in einem Gewichtsverhältnis von 99 : 1 bis 50 : 50 bein¬ halten, hinsichtlich ihres TextilWaschvermögens und ihres Ge¬ schirrspülVermögens keine signifikante Leistungsminderung aufwei¬ sen und insbesondere Mischungen, die Alkylglucoside und zusätzlich eingesetzte Polyglucose in einem Gewichtsverhältnis von 95 : 5 bis 85 : 15 beinhalten, sogar eine Leistungssteigerung gegenüber Mi¬ schungen aufweisen können, die nur Alkylglucoside als Aktivsub¬ stanz beinhalten.Alkyl glycosides or alkyl glucosides of the type described above can already contain polyglycoses or polyglucoses. The latter are formed in a side reaction in the production of alkyl glycosides by condensation of the glycose molecules with one another. These polyglycoses and in particular the polyglucoses are to be regarded as constituents of the nonionic surfactant "alkylglycoside / alkylglucoside" and are not among the carbohydrate derivatives to be used in accordance with the invention. Rather, it has surprisingly been found that mixtures which contain alkyl glucosides and additionally used polyglucose in a weight ratio of 99: 1 to 50:50 as active substance have no significant reduction in performance with regard to their textile washing ability and their dishwashing ability, and in particular mixtures who have favourited Alkyl Glucosides and Additionally include polyglucose used in a weight ratio of 95: 5 to 85:15, may even have an increase in performance compared to mixtures which contain only alkyl glucosides as active substance.
Bevorzugte Tensidmischungen enthalten anionische und nichtionische Tenside in einem Gewichtsverhältnis von 5 : 1 bis 1 : 3 und ins¬ besondere von 2 : 1 bis 1 : 2.Preferred surfactant mixtures contain anionic and nonionic surfactants in a weight ratio of 5: 1 to 1: 3 and in particular 2: 1 to 1: 2.
In einer weiteren Ausführungsform enthalten bevorzugte erfin¬ dungsgemäße Wasch- und Reinigungsmittel anionische und/oder nichtionische Tenside, Polyglucosen mit einer durchschnittlichen relativen Molekülmasse zwischen 800 und 50000 sowie weitere üb¬ liche Bestandteile von Wasch- und Reinigungsmitteln. Besonders bevorzugt sind Mittel, die die erfindungsgemäßen Tensidmischungen mit bis zu 50 Gew.-% und vorzugsweise 1 - 20 Gew.-% Polyglucose, bezogen auf die Summe aus Tensiden und Polyglucosen, enthalten. Vorteilhafterweise werden dabei Wasch- und Reinigungsmittel ein¬ gesetzt, die zwischen 5 und 40 Gew.-%, vorzugsweise 8 bis 25 Gew.-% der erfindungsgemäßen Mischungen enthalten. Mit besonderem Vorteil werden Wasch- und Reinigungsmittel eingesetzt, die Ten¬ sidmischungen mit einem Gehalt von 1 - 12 Gew.-%, bezogen auf die Summe aus Tensiden und Polyglucosen, an Dextrinen und/oder Dex- tranen enthalten. Dabei weisen Wasch- und Reinigungsmittel, die die erfindungsgemäßen Tensidmischungen mit bis zu 50 Gew.-% an Polyglucosen, bezogen auf die Summe aus Tensiden und Polyglucosen, enthalten, keine signifikante Leistungsminderung auf. Im Gegen¬ teil, sie können sogar in einigen Fällen eine höhere Leistung als solche Mittel erbringen, die in denselben Mengen Tensidmischungen beinhalten, die nur aus Tensiden bestehen und in denen die Tenside nicht teilweise durch Polyglucose ersetzt sind. Dies gilt insbe¬ sondere für Wasch- und Reinigunsmittel, die die erfindungsgemäßen Tensidmischungen mit 1 - 20 Gew.-% Polyglucose, bezogen auf die Summe aus Tensiden und Polyglucosen, enthalten. Die erfindungsgemäßen Wasch- und Reinigungsmittel können in fester, flüssiger oder pastöser Form vorliegen.In a further embodiment, preferred detergents and cleaning agents according to the invention contain anionic and / or nonionic surfactants, polyglucoses with an average relative molecular weight between 800 and 50,000 and further usual constituents of detergents and cleaning agents. Agents which contain the surfactant mixtures according to the invention with up to 50% by weight and preferably 1 to 20% by weight of polyglucose, based on the sum of surfactants and polyglucoses, are particularly preferred. Detergents and cleaning agents which contain between 5 and 40% by weight, preferably 8 to 25% by weight, of the mixtures according to the invention are advantageously used. Detergents and cleaning agents which contain surfactant mixtures with a content of 1 to 12% by weight, based on the sum of surfactants and polyglucoses, of dextrins and / or dextranes are used with particular advantage. Detergents and cleaning agents which contain the surfactant mixtures according to the invention with up to 50% by weight of polyglucoses, based on the sum of surfactants and polyglucoses, have no significant reduction in performance. On the contrary, in some cases they can even perform better than agents which contain surfactant mixtures in the same amounts, which consist only of surfactants and in which the surfactants are not partially replaced by polyglucose. This applies in particular to detergents and cleaning agents which contain the surfactant mixtures according to the invention with 1 to 20% by weight polyglucose, based on the sum of surfactants and polyglucoses. The washing and cleaning agents according to the invention can be in solid, liquid or pasty form.
Als weitere übliche Bestandteile können die Mittel sowohl anorga¬ nische als auch organische Gerüstsubstanzen, Polymere, als "Waschalkalien" bezeichnete Salze, Vergrauungsinhibitoren, Schauminhibitoren, Bleichmittel und Bleichaktivatoren sowie op¬ tische Aufheller, Enzyme, textilweichmachende Stoffe, Färb- und Duftstoffe, Neutralsalze, organische Lösungsmittel und Wasser ent¬ halten.As further conventional constituents, the agents can include both inorganic and organic builders, polymers, salts known as "washing alkalis", graying inhibitors, foam inhibitors, bleaching agents and bleach activators as well as optical brighteners, enzymes, fabric softening agents, dyes and fragrances, neutral salts, contain organic solvents and water.
Als organische und anorganische Gerüstsubstanzen eignen sich schwach sauer, neutral oder alkalisch reagierende Salze, insbe¬ sondere Alkalisalze, die Calciumionen auszufällen oder komplex zu binden vermögen. Geeignete und insbesondere ökologisch unbedenk¬ liche Buildersubstanzen, wie feinkristalline, synthetische was¬ serhaltige Zeolithe vom Typ NaA, die ein Calciumbindever ögen im Bereich von 100 bis 200 mg CaO/g (gemäß den Angaben in DE 24 12837) aufweisen, finden eine bevorzugte Verwendung. Ihre mittlere Teilchengröße liegt üblicherweise im Bereich von 1 bis 10 μ . Ihr Gehalt beträgt im allgemeinen 0 bis 40, vorzugsweise 10 bis 30 Gew.-%, bezogen auf wasserfreie Substanz.Weakly acidic, neutral or alkaline-reacting salts are suitable as organic and inorganic builders, in particular alkali salts, which can precipitate or bind calcium ions in a complex manner. Suitable and, in particular, ecologically harmless builder substances, such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12837) are used with preference . Their average particle size is usually in the range from 1 to 10 μ. Their content is generally 0 to 40, preferably 10 to 30% by weight, based on the anhydrous substance.
Als weitere Bestandteile, die insbesondere zusammen mit den Zeo- lithen eingesetzt werden, kommen (co-)poly ere Polycarboxylate in Betracht, wie Polyacrylate, Polymethacrylate und insbesondere Co- polymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure. Die relative Molekülmasse der Ho opoly- meren liegt im allgemeinen zwischen 1 000 und 100 000, das der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 50 000 bis 120000, bezogen auf freie Säure. Ein besonders bevorzugtes Acryl- säure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50 000 bis 100000 auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copoly ere der Acrylsäure oder Methacrylsäure mit Vinylethe n, wie Vinylmethylether, in denen der Anteil der Säure mindestens 50 % beträgt. Brauchbar sind ferner Polyacetalcarbonsäuren, wie sie beispielsweise in den US-Patent¬ schriften 4 144226 und 4 146 495 beschrieben sind sowie polymere Säuren, die durch Polymerisation von Acrolein und anschließene Disproportionierung mittels Alkalien erhalten werden und aus Acrylsäureeinheiten und Vinylalkoholeinheiten bzw. Acroleinein- heiten aufgebaut sind.Other constituents which are used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the The acidity is at least 50%. Also useful are polyacetal carboxylic acids, as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, as well as polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation by means of alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units are.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäu- ren, wie Citronensäure, und Nitrilotriacetat (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist.Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons.
In Fällen, in denen ein Phosphat-Gehalt toleriert wird, können auch Phosphate mitverwendet werden, insbesondere Pentanatriumtri- phosphat, gegebenenfalls auch Pyrophosphate, die aufgrund ihrer Löslichkeitseigenschaften in Flüssigwaschmitteln eingesetzt werden können, sowie Orthophosphate, die in erster Linie als Fällungs- mittel für Kalksalze wirken. Der Gehalt an Phosphaten, bezogen auf Pentanatriumtriphosphat, liegt unter 30 Gew.-%. Es werden jedoch bevorzugt Mittel ohne Phophatgehalt eingesetzt.In cases where a phosphate content is tolerated, phosphates can also be used, in particular pentasodium tri-phosphate, optionally also pyrophosphates, which, owing to their solubility properties, can be used in liquid detergents, and orthophosphates, which are primarily used as precipitants for lime salts Act. The phosphate content, based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used.
Geeignete organische, nicht komplexbildende Salze sind die - auch als "Waschalkalien" bezeichneten - Bicarbonate, Carbonate, Borate oder Silikate der Alkalien; von den AlkaliSilikaten sind vor allem die Natriumsilikate mit einem Verhältnis Na2θ : Siθ2 wie 1 : 1 bis 1 : 3,5 brauchbar.Suitable organic, non-complexing salts are the bicarbonates, carbonates, borates or silicates of the alkalis - also referred to as "washing alkalis"; Of the alkali silicates, especially the sodium silicates with a Na2θ: Siθ2 ratio of 1: 1 to 1: 3.5 can be used.
Als Vergrauungsinhibitoren werden bevorzugt Carboxymethylcellulose (Na-Salz), Methylcellulose, Methylhydroxyethylcellulose und deren Mischungen eingesetzt. Doch sind auch andere Vergrauungsinhibi¬ toren wie Polyvinylpyrrolidon brauchbar. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenen¬ falls silanierter Kieselsäure, Paraffine, Wachse, Mikrokristal¬ linwachse und deren Gemische mit silanierter Kieselsäure. Auch von Ci2-C20-Al ylaminen und C2-Cö-Dicarbonsäuren abgeleitete Bisacyl- amide sind brauchbar. Mit Vorteil werden auch Gemische verschie¬ dener Schauminhibitoren verwendet, z. B. solche aus Silikonen und Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren an eine granuläre, in Wasser lösliche bzw. dispergierbare Träger¬ substanz gebunden.Carboxymethyl cellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used as graying inhibitors. However, other graying inhibitors such as polyvinylpyrrolidone can also be used. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bisacylamides derived from Ci2-C20-Al ylamines and C2-Co-dicarboxylic acids can also be used. Mixtures of various foam inhibitors are also advantageously used, eg. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborat-tetrahydrat (NaB02 H2O2 3 H2O) und das Natriumperborat-monohydrat (NaBÜ2 H2O2) besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxycarbonat (Na2Cθ3 1,5 H2O2), Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxa- phthalate oder Diperdodecandisäure.Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate (NaB02 H2O2 3 H2O) and sodium perborate monohydrate (NaBÜ2 H2O2) are of particular importance. Other bleaching agents that can be used are, for example, peroxycarbonate (Na2CO3 1.5 H2O2), citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxaphthalates or diperdodecanedioic acid.
Um beim Waschen bei Temperaturen von 60 °C und darunter eine ver¬ besserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden. Beispiele hierfür sind mit H2O2 organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbin- dungen, vorzugsweise N,N'-tetraacylierte Diamine, wie N,N,N',N'- Tetraacetylethylendiamin, ferner Carbonsäureanhydride und Ester von Polyolen, wie Glucosepentaacetat.In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, furthermore carboxylic anhydrides and esters of polyols such as glucose pentaacetate.
Die Waschmittel können als optische Aufheller Derivate der Diami- nostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z. B. Salze der 4,4'-Bis(2-anilino-4-morpholino- l,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure oder gleich¬ artig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilino- gruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4'-Distyryl-di- phenyls anwesend sein; z. B. die Verbindung 4,4-Bis-(4-chlor- 3-sulfostyryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden.The detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which Instead of the morpholino group, wear a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-di- phenyls to be present; z. B. the compound 4,4-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen und Amylasen bzw. deren Gemische in Frage. Besonders geeignet sind aus Bakterienstä men oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Strepto yces griseus gewonnene enzymatische Wirkstoffe. Die Enzyme können an Trägerstoffen adsorbiert und/oder an Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zer¬ setzung zu schützen.Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded on coating substances in order to protect them against premature decomposition.
Als Stabilisatoren insbesondere für Perverbindungen und Enzyme kommen die Salze von Polyphosphonsäuren, wie l-Hydroxyethan-1,1- diphosphonsäure (HEDP) und Diethylentriaminpentamethylenphosphon- säure (DTPMP) in Betracht.The salts of polyphosphonic acids, such as l-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP) are suitable as stabilizers, in particular for per compounds and enzymes.
Als wasserlösliche organische Lösungsmittel eignen sich vor allem die niederen Alkohole, Etheralkohole und Glykole mit 1 bis 6 Koh- lenstoffato en, wie z. B. Methanol, Ethanol, Propanol, Isopropyl- alkohol, Ethylenglykol, Propylenglykol, Diethylenglykol, Methyl- glykol, Ethylglykol und Butylglykol.The lower alcohols, ether alcohols and glycols with 1 to 6 carbon atoms, such as, for example, are particularly suitable as water-soluble organic solvents. B. methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, methyl glycol, ethyl glycol and butyl glycol.
In einer bevorzugten Ausführungsform enthalten Wasch- und Reini¬ gungsmittel 8 - 25 Gew.-% an Tensidmischungen mit einem Gehalt von 1 - 20 Gew.-% und insbesondere 1 - 12 Gew.-% Polyglucose, bezogen auf die Summe aus Polyglucosen und Tensiden, 10 - 30 Gew.-% an Bu ldersubstanzen, 10 - 25 Gew.- an Bleichmitteln, 0 - 5 Gew.-% an Polymeren und 2 - 15 Gew.-% an Alkalisilikaten und/oder Alka¬ licarbonaten.In a preferred embodiment, detergents and cleaning agents contain 8-25% by weight of surfactant mixtures with a content of 1-20% by weight and in particular 1-12% by weight of polyglucose, based on the sum of polyglucoses and surfactants , 10-30% by weight of fluoride substances, 10-25% by weight of bleaching agents, 0-5% by weight of polymers and 2-15% by weight of alkali silicates and / or alkali metal carbonates.
Ebenso sind Wasch- und Reinigungsmittel obiger Zusammensetzung bevorzugt, in denen die Tensidmischungen Alkylbenzolsulfonat und/oder Fettalkoholethersulfat als anionischen Tensidbestandteil enthalten.Likewise, detergents and cleaning agents of the above composition are preferred, in which the surfactant mixtures are alkylbenzenesulfonate and / or fatty alcohol ether sulfate as an anionic surfactant component.
Weiterhin sind Wasch- und Reinigungsmittel der obigen Zusammen¬ setzung bevorzugt, die 1 bis 15 Gew.-% Alkylglucoside enthalten.Furthermore, detergents and cleaning agents of the above composition are preferred which contain 1 to 15% by weight of alkyl glucosides.
Besonders bevorzugt sind manuelle Geschirrspülmittel, die 5 - 30 Gew.-% anionische Tenside, wie Alkylbenzolsulfonat, Fettalkohol¬ ethersulfat, sekundäres Alkansulfonat, α-Sulfofettsäure-disalz oder Mischungen aus diesen, und 1 - 5 Gew.-% Polyglucose, wie Dextrane und/oder Dextrine, enthalten.Manual dishwashing detergents containing 5-30% by weight of anionic surfactants, such as alkylbenzenesulfonate, fatty alcohol ether sulfate, secondary alkanesulfonate, α-sulfofatty acid disalt or mixtures thereof, and 1-5% by weight of polyglucose, such as dextrans and / or dextrins.
Gleichermaßen bevorzugt sind manuelle Geschirrspülmittel, die 5 - 20 Gew.-% anionische Tenside aus der oben angegebenen Gruppe, 1 - 15 Gew.-% nichtionische Tenside, vorzugsweise Alkylglucoside, und 1 - 5 Gew.-% Dextrane und/oder Dextrine enthalten.Likewise preferred are manual dishwashing detergents which contain 5-20% by weight of anionic surfactants from the group given above, 1-15% by weight of nonionic surfactants, preferably alkyl glucosides, and 1-5% by weight of dextrans and / or dextrins.
Sowohl die erfindungsgemäßen Tensidmischungen als auch die erfin¬ dungsgemäßen Wasch- und Reinigungsmittel können in an sich übli¬ cher Weise, beispielsweise durch Mischen, Granulieren und/oder durch Sprühtrocknung hergestellt werden. Im Fall der Wasch- und Reinigungsmittel können dabei separat hergestellte Tensidmischun¬ gen verwendet werden. Ebenso ist es möglich, die tensidischen Be¬ standteile und die Polyglucose einzeln in an sich üblicher Weise und beliebiger Reihenfolge in die Mittel einzuarbeiten. Both the surfactant mixtures according to the invention and the washing and cleaning agents according to the invention can be prepared in a manner which is conventional per se, for example by mixing, granulating and / or by spray drying. In the case of detergents and cleaning agents, separately prepared surfactant mixtures can be used. It is also possible to incorporate the surfactant components and the polyglucose individually into the compositions in a manner which is customary per se and in any order.
B e i s p i e l eB e i s p i e l e
Beispiel 1 :Example 1 :
Zur Bestimmung des TellerspülVermögens wurde als Reinigungsmittel die betreffende binäre oder ternäre Tensidmischung in einer Kon¬ zentration von 0,15 g der Mischung in 1 Liter des 45° C warmen Wassers gelöst. Es wurden Reinigungsflotten mit den verschiedenen Wasserhärten 16°d, 3°d und 0°d hergestellt. Als Standardver¬ schmutzung wurde Rindertalg (ca. 1,7 g pro Teller) verwendet (siehe H.-J. Lehmann, "Fette, Seifen, Anstrichmittel 1 , Seiten 163 bis 165, 1972). Ein Unterschied im Spülvermögen von 2 Tellern und mehr ist als signifikant anzusehen.To determine the dishwashing capacity, the binary or ternary surfactant mixture in question was dissolved as a cleaning agent in a concentration of 0.15 g of the mixture in 1 liter of the 45 ° C. warm water. Cleaning liquors with different water hardnesses of 16 ° d, 3 ° d and 0 ° d were produced. Beef tallow (approx. 1.7 g per plate) was used as standard soiling (see H.-J. Lehmann, "Fette, Seifen, Anstrichmittel 1, pages 163 to 165, 1972). A difference in the washing capacity of 2 plates and more can be seen as significant.
Als Tenside und Polyglucosen wurden folgende Substanzen einge¬ setzt:The following substances were used as surfactants and polyglucoses:
C12-C14-APG: Alkylglucosid des Ci2-Ci4-Fettalkoholgemisches, hergestellt nach der Methode der Umacetalisierung mit ButanolC12-C14-APG: alkyl glucoside of the Ci2-Ci4 fatty alcohol mixture, produced by the method of transacetalization with butanol
Produktzusammensetzung (GC-Analyse) Monoglucosid 63 % Diglucosid 15 %Product composition (GC analysis) monoglucoside 63% diglucoside 15%
Triglucosid 6 %Triglucoside 6%
Tetra-Hexa-Glucosid ca. 3 % Butylglucosid 4 % Cχ2-Ci4-Fettalkohol 3 % Polyglucose 6 %Tetra-hexa-glucoside approx. 3% butyl glucoside 4% Cχ2-Ci4 fatty alcohol 3% polyglucose 6%
ABS: Dodecylbenzolsulfonat, Na-SalzABS: dodecylbenzenesulfonate, sodium salt
FAES: Cχ2-Ci4-Fettalkylsulfat 2 EO, Na-SalzFAES: Cχ2-Ci4-fatty alkyl sulfate 2 EO, Na salt
(EO bedeutet Ethylenoxid) Disalz: α-Sulfo-Ci6/18~Fettsäure. Na-Disalz SAS: Hostapur SAS 30 (Verkaufsprodukt der Hoechst AG), sekundäres Alkansulfonat(EO means ethylene oxide) disalt: α-sulfo-Ci6 / 18 ~ fatty acid . Na disalt SAS: Hostapur SAS 30 (sales product of Hoechst AG), secondary alkane sulfonate
Dextran 17200: Polyglucose, Mr (relative Molekülmasse) 17 200 Dextran 9000: Polyglucose, Mr 9000 Dextrin Typ I: Polyglucose, Mr 23800Dextran 17200: polyglucose, M r (molecular weight) 17 200 dextran 9000: polyglucose, M r 9000 dextrin type I: polyglucose, M r 23800
(Verkaufsprodukt der Firma Sigma)(Sales product from Sigma)
Dextrin Typ IV: Polyglucose, Mr 13750Dextrin type IV: polyglucose, M r 13750
(Verkaufsprodukt der Firma Sigma)(Sales product from Sigma)
Tabelle 1Table 1
Figure imgf000017_0001
Tabelle 2
Figure imgf000017_0001
Table 2
Figure imgf000018_0001
Figure imgf000018_0001
Tabelle 3Table 3
Figure imgf000018_0002
Tabelle 4
Figure imgf000018_0002
Table 4
Figure imgf000019_0001
Figure imgf000019_0001
Tabelle 5Table 5
Figure imgf000019_0002
Figure imgf000019_0002
Tabelle 6Table 6
Figure imgf000019_0003
Figure imgf000019_0003
Tabelle 7Table 7
Figure imgf000019_0004
Beispiel 2
Figure imgf000019_0004
Example 2
Waschmittel folgender Zusammensetzung wurden in einemDetergents of the following composition were in one
Laundero eter getestet:Laundero eter tested:
Tensidmischung 9 Gew.-%Surfactant mixture 9% by weight
Zeolith NaA 24 Gew.-%Zeolite NaA 24% by weight
Natriumperborat-tetrahydrat 18 Gew.-%Sodium perborate tetrahydrate 18% by weight
Natriumcarbonat 10 Gew.-%Sodium carbonate 10% by weight
Wasserglas (Na2θ : SiÖ2 = 3 Gew.-%Water glass (Na2θ: SiÖ2 = 3% by weight
1 : 3,3)1: 3.3)
Natriumsulfat 30 Gew.-%Sodium sulfate 30% by weight
Wasser, optischer Aufheller, Rest Farbstoff, Enzym, ParfümWater, optical brightener, remainder dye, enzyme, perfume
Waschbedingungen:Washing conditions:
Atlas-Laundero eterAtlas Laundero eter
Waschtemperatur 60° CWash temperature 60 ° C
Wasserhärte 16° d (160 mg CaO proWater hardness 16 ° d (160 mg CaO per
Liter)Liter)
Waschpulver 10 g/1 FlottenVerhältnis 1 : 30 Stahlkugeln 10Washing powder 10 g / 1 liquor ratio 1: 30 steel balls 10
3-fach Bestimmung Anschmutzungen SH-PBV (Staub-Hautfett auf Polyester/Baumwolle veredelt) LS-PBV (Lippenstift auf Poly¬ ester/Baumwolle ver¬ edeltTriple determination of soiling SH-PBV (dusty skin fat refined on polyester / cotton) LS-PBV (lipstick refined on polyester / cotton)
Die optische Auswertung der Waschergebnisse erfolgte mit einem Zeiß-Reflektometer bei 465 nm (Ausblendung des Aufheller-Effek¬ tes). Dabei können Remissionsunterschiede von 2 % und mehr direkt vom Verbraucher nachvollzogen werden. Tabel le 8 eingesetzte Polyglucose : Dextran 17200The optical evaluation of the washing results was carried out using a Zeiss reflectometer at 465 nm (suppression of the brightener effect). Remission differences of 2% and more can be directly understood by the consumer. Table 8 of the polyglucose used: dextran 17200
Figure imgf000021_0001
Figure imgf000021_0001
Tabelle 9 eingesetzte Polyglucose: Dextran 17200Table 9 used polyglucose: dextran 17200
Figure imgf000021_0002
Figure imgf000021_0002
Tabelle 10Table 10
Figure imgf000022_0001
Figure imgf000022_0001
Tabelle 11Table 11
Figure imgf000022_0002
Figure imgf000022_0002

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Tensidmischung, enthaltend ein oder mehrere Tenside aus der Gruppe der anionischen und nichtionischen Tenside sowie Poly¬ glucose mit einer durchschnittlichen relativen Molekülmasse zwischen 500 und 70000.1. surfactant mixture containing one or more surfactants from the group of anionic and nonionic surfactants and polyglucose with an average relative molecular weight between 500 and 70,000.
2. Tensidmischung nach Anspruch 1, dadurch gekennzeichnet, daß sie bis zu 50 Gew.-%, vorzugsweise 1 bis 20 Gew.-% Polyglu¬ cose, bezogen auf die Summe aus Tensiden und Polyglucose, enthält, wobei die eingesetzte Polyglucose eine relative Mole¬ külmasse zwischen 1 000 und 45000 aufweist.2. A surfactant mixture according to claim 1, characterized in that it contains up to 50% by weight, preferably 1 to 20% by weight, of polyglucose, based on the sum of surfactants and polyglucose, the polyglucose used being a relative mole ¬ cooling mass between 1 000 and 45 000.
3. Tensidmischung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie als anionische Komponente eine Mischung aus Alkylben¬ zolsulfonat und Fettalkoholethersulfat in einem Gewichtsver¬ hältnis zwischen 1 : 1 und 6 : 1 enthält.3. Surfactant mixture according to claim 1 or 2, characterized in that it contains, as the anionic component, a mixture of alkylbenzenesulfonate and fatty alcohol ether sulfate in a weight ratio between 1: 1 and 6: 1.
4. Tensidmischung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie als anionische Komponente eine Mischung aus Alkansul- fonat und Fettalkoholethersulfat in einem GewichtsVerhältnis von 1 : 1 bis 4 : 1 enthält.4. Surfactant mixture according to claim 1 or 2, characterized in that it contains, as the anionic component, a mixture of alkanesulfonate and fatty alcohol ether sulfate in a weight ratio of 1: 1 to 4: 1.
5. Tensidmischung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie als nichtionische Tenside Fettalkyl- glucoside der allgemeinen Formel R0(G)x enthält, wobei R einen Fettalkylrest mit Cβ~ bis C22-A-tomen, vorzugsweise mit im we¬ sentlichen Ci2-bis Ciβ-Ato en, G eine Glucoseinheit und x eine Zahl zwischen 1 und 10 darstellt.5. Surfactant mixture according to one of claims 1 to 4, characterized in that it contains fatty alkyl glucosides of the general formula R0 (G) x as nonionic surfactants, where R is a fatty alkyl radical with Cβ ~ to C22 atoms , preferably with im we¬ considerable Ci2 to Ciβ ato en, G represents a glucose unit and x represents a number between 1 and 10.
6. Tensidmischung gemäß Anspruch 5, dadurch gekennzeichnet, daß sie Alkylglucosid und zusätzlich eingesetzte Polyglucose in einem GewichtsVerhältnis von 95 : 5 bis 85 : 15 enthält. 6. A surfactant mixture according to claim 5, characterized in that it contains alkyl glucoside and additionally used polyglucose in a weight ratio of 95: 5 to 85:15.
7. Wasch- und Reinigungsmittel, enthaltend eine Tensidmischung aus einem oder mehreren Tensiden aus der Gruppe der anioni¬ schen und nichtionischen Tenside und Polyglucose mit einer durchschnittlichen relativen Molekülmasse zwischen 500 und7. washing and cleaning agents containing a surfactant mixture of one or more surfactants from the group of anionic and nonionic surfactants and polyglucose with an average relative molecular weight between 500 and
70000.70000.
8. Mittel gemäß Anspruch 7, dadurch gekennzeichnet, daß es zwischen 5 und 40 Gew.-% einer Tensidmischung mit 1 bis 20 Gew.-% Polyglucose, bezogen auf die Summe aus Tensiden und Polyglucose, enthält.8. Composition according to claim 7, characterized in that it contains between 5 and 40 wt .-% of a surfactant mixture with 1 to 20 wt .-% polyglucose, based on the sum of surfactants and polyglucose.
9. Verfahren zur Herstellung von Tensidmischungen, enthaltend ein oder mehrere Tenside aus der Gruppe der anionischen und nicht¬ ionischen Tenside sowie Polyglucose mit einer durchschnitt¬ lichen relativen Molekülmasse zwischen 500 und 70000, dadurch gekennzeichnet, daß sie in an sich üblicher Weise hergestellt werden.9. A process for the preparation of surfactant mixtures comprising one or more surfactants from the group of anionic and non-ionic surfactants and polyglucose with an average molecular weight between 500 and 70,000, characterized in that they are prepared in a conventional manner.
10. Verfahren zur Herstellung von Wasch- und Reinigungsmitteln, enthaltend eine Tensidmischung aus einem oder mehreren Ten¬ siden aus der Gruppe der anionischen und nichtionischen Ten¬ side und Polyglucose mit einer durchschnittlichen relativen Molekülmasse zwischen 500 und 70 000, dadurch gekennzeichnet, daß sie in an sich üblicher Weise hergestellt werden. 10. A process for the preparation of detergents and cleaning agents, comprising a surfactant mixture of one or more surfactants from the group of anionic and nonionic surfactants and polyglucose with an average molecular weight between 500 and 70,000, characterized in that they are in are produced in a conventional manner.
PCT/EP1991/000628 1990-04-09 1991-04-02 Tenside mixture for use in washing and cleaning agents WO1991015564A1 (en)

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DE4011487A1 (en) 1991-10-10
EP0524975A1 (en) 1993-02-03
BR9106329A (en) 1993-04-20
JPH05505843A (en) 1993-08-26

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