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EP0897973A1 - Detergent and cleaning agents - Google Patents

Detergent and cleaning agents Download PDF

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Publication number
EP0897973A1
EP0897973A1 EP98114591A EP98114591A EP0897973A1 EP 0897973 A1 EP0897973 A1 EP 0897973A1 EP 98114591 A EP98114591 A EP 98114591A EP 98114591 A EP98114591 A EP 98114591A EP 0897973 A1 EP0897973 A1 EP 0897973A1
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EP
European Patent Office
Prior art keywords
weight
alkyl
detergent
surfactants
contain
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.)
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Application number
EP98114591A
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German (de)
French (fr)
Inventor
Werner Dr. Antwerpen
Ulrike Reploeg
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Publication of EP0897973A1 publication Critical patent/EP0897973A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/384—Animal products

Definitions

  • WO 94/09100 from Procter and Gamble describes the use of polyhydroxy fatty acid amides as a readily biodegradable nonionic surfactant with very good fat dispersibility and based on renewable raw materials in dishwashing detergents.
  • DE 44 30 085 from Henkel describes the use of fatty acid N-alkylpolyhydroxyalkylamides and alkyl and / or alkenyl (ether) phosphates in surface-active cleaning agents.
  • EP 0 569 376 describes a liquid detergent which contains alkyl polyglycoside and fatty alcohol sulfate.
  • sweet whey powder the main constituent of which is lactose monohydrate and the minor constituents of which are essentially minerals and proteins, in combination with all the usual surfactants and surfactant mixtures has excellent skin compatibility and very good emulsifying effects, which prevent deposits of oils and fats .
  • An improvement in the solubilizing capacity can also be achieved by adding sweet whey. Foaming is not impaired by the addition of whey, even when exposed to fat. A good drainage effect is significant, especially for glass and porcelain.
  • sweet whey powder into liquid all-purpose cleaners, an improvement of the whole, in particular of plastic surfaces and in mild detergents, a caring and softening effect, in particular for wool, was achieved.
  • the invention thus relates to detergents and cleaning agents with a Sweet whey content.
  • a sweet whey in powder form is used as sweet whey spray-dried ultrafiltration permeate powder.
  • Such a product contains 50 to 100, preferably 70 to 95, in particular 83 to 90% by weight of lactose monohydrate. Minor components are minerals (approx. 6 to 10% by weight), proteins (approx. 3 to 5 % By weight) and water (up to 3% by weight).
  • This sweet whey can be used in all common solid and liquid washing and Detergents can be incorporated by methods known per se.
  • the sweet whey is preferably used for the production of Hand dishwashing liquid, liquid all-purpose cleaner or liquid Delicates, as these formulations are excellent Skin compatibility of sweet whey is particularly important.
  • the detergents and cleaning agents according to the invention can contain the sweet whey in Amounts from 0.1 to 15, preferably from 2 to 7, in particular from 4 to 6% by weight contain.
  • these detergents and cleaning agents also contain those for these products common and typical ingredients such as surfactants and auxiliary and Additives.
  • the surfactants contained in the washing and cleaning agents according to the invention can be anionic, cationic, zwitterionic (amphoteric) or non-ionic Be nature.
  • Suitable anionic surfactants are alkyl sulfates, sulfonates, carboxylates, -phosphates and mixtures of the compounds mentioned. In the following should some of the types of anionic surfactants in question to be discribed.
  • Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie fatty acids) which are sulfonated by SO 3 , as described in "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials are natural fat derivatives, such as tallow or palm oil fatty acid.
  • Preferred alkyl ester sulfonates, especially for detergent applications are compounds of the formula wherein R 3 is a C 8 -C 20 hydrocarbon radical, preferably alkyl or a mixture of alkyl radicals, R 4 is a C 1 -C 6 hydrocarbon radical, preferably alkyl or a mixture of alkyl radicals.
  • M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate.
  • Suitable cations are metals such as sodium, hardly any, lithium or substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine.
  • R 3 is C 10 -C 16 alkyl and R 4 is methyl, ethyl or isopropyl.
  • Methyl ester sulfonates in which R 3 is C 10 -C 16 alkyl are particularly preferred.
  • Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 alkyl or Represents hydroxyalkyl.
  • R is preferably a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 alkyl or Represents hydroxyalkyl.
  • M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
  • Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with C 16 -C 18 are preferred for higher washing temperatures (eg above approx. 50 ° C).
  • the alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) SO 3 M, in which R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl radical having 10 to 24 C atoms, preferably a C 12 -C 20 alkyl or Hydroxyalkyl radical, particularly preferably a C 12 -C 18 alkyl or hydroxyalkyl radical.
  • A is an ethoxy or propoxy unit
  • m is a number greater than 0, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
  • M is a hydrogen atom or a cation such as e.g. a metal cation (e.g.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like.
  • Examples include C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, (C 12 -C 18 E (1.0) M), C 12 -C 18 alkyl polyethoxylate (2.25 ) sulfate (C 12 -C 18 E (2.25) M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate, (C 12 -C 18 E (3.0) M), C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, (C 12 -C 18 E (4.0) M), where M is sodium or potassium.
  • alkylbenzenesulfonate Another suitable anionic surfactant that can be used according to the invention is alkylbenzenesulfonate.
  • the alkyl group can be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
  • the preferred alkylbenzenesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably 10 to 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Magnesium is preferred as the cation for mild surfactant systems, while sodium is preferred for standard washing applications.
  • the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted.
  • the sulfo group is statistically distributed over the entire C chain, with the primary methyl groups at the beginning and end of the chain none Wear sulfonate groups.
  • the preferred secondary alkanesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably from 10 to 20 Carbon atoms and particularly preferably 13 to 17 carbon atoms.
  • the Cation is sodium, hardly, ammonium, mono-, di- or triethanolammonium, Calcium or magnesium and mixtures thereof. Sodium as the cation is preferred.
  • carboxylates e.g. Fatty acid soaps and comparable surfactants.
  • the soaps can be saturated or unsaturated and can have various substituents, such as hydroxyl groups or alpha sulfonate groups contain.
  • Linear saturated or unsaturated are preferred Hydrocarbon residues as a hydrophobic component in the soaps.
  • contain the hydrophobic components 6 to 30 carbon atoms, preferably 10 up to 18 carbon atoms.
  • the cation (M) of the carboxylate surfactants can be a Alkali metal, e.g. Sodium or potassium, an alkaline earth metal, e.g. Calcium or Magnesium, ammonium or substituted ammonium including mono-, di- and Be triethanolammonium. Mixtures of the cations can be advantageous be.
  • anionic surfactants are the salts of acylaminocarboxylic acids, by the reaction of fatty acid chlorides with sodium sarcosinate in alkaline Medium arise (acyl sarcosinate) or fatty acid-protein condensation products which are obtained by reacting fatty acid chlorides with oligopeptides, as well as the salts of alkylsulfamidocarboxylic acids and the salts of alkyl and Alkylaryl ether carboxylic acids.
  • anionic surfactants for use in detergents and cleaning agents are C 8 -C 24 -olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfate sulfates, alkylphenol parolate, primary phenolate sulfates Alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and uns
  • Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents” (Vol. I and II, Schwartz, Perry and Berch).
  • anionic surfactants are alkylbenzenesulfonates, Alkane sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, Sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, Hydroxy mixed ether sulfates, fatty acid amide (ether) sulfates, mono- and Dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinates, sulfotriglycerides, Amide soaps, alkyl oligoglucoside sulfates, alkyl amino sugar sulfates and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they have a conventional or narrow homolog distribution.
  • the ratio of anionic surfactants to sweet whey powder can be between 99: 1 and 1:99 vary.
  • Typical examples of cationic surfactants in the context of the present invention are quaternary ammonium salts and ester quats, especially quaternized ones Fatty acid alkanolamine ester salts and trialkylaminopropylamine ester salts.
  • the quaternary ammonium salts are preferably those of the type RN (CH 3 ) 3 Cl and R 2 N (CH 3 ) 2 Cl with an alkyl radical R whose chain length is between 8 and 24 C atoms, preferably between 10 and 18 C. -Atoms lies.
  • amphoteric surfactants which are suitable for the formulations of the present invention are, above all, those which can be described very generally as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and one of the aliphatic substituents contains between 8 and 18 carbon atoms and which contain an anionic, water-soluble group such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
  • Amphoteric surfactants are, for example, imidazolium surfactants of the following formula: wherein R 1 is a C 8 -C 22 alkyl or alkenyl radical, preferably C 12 -C 16 , R 2 is hydrogen or CH 2 CO 2 M, R 3 is CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, Z is CO 2 M or CH 2 CO 2 M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal , Alkaline earth metal, ammonia or alkanolammonium.
  • R 1 is a C 8 -C 22 alkyl or alkenyl radical, preferably C 12 -C 16
  • R 2 is hydrogen or CH 2 CO 2 M
  • R 3 is CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM
  • R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 OCH
  • Preferred amphoteric surfactants of the above formula are monocarboxylates and Dicarboxylates. Examples of these compounds are cocoamphocarboxypropionate, Cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also as Cocoamphodiacetate) and Cocoamphoacetat.
  • amphoteric surfactants are alkyldimethylbetaines, Alkyl amido betaines and alkyl dipolyethoxy betaines with an alkyl radical having 8 to 22, preferably with 8 to 18 carbon atoms. These connections are e.g. of the Hoechst AG is marketed under the trade name ®Genagen CAB.
  • Suitable nonionic surfactants are described in US 3,929,678. A Selection is given below.
  • Polyethylene, polypropylene and polybutylene oxide adducts of alkylphenols are preferred here.
  • This Compounds include the condensation products of alkylphenols with one Alkyl group of 6 to 12 carbon atoms, which are either linear or branched can, with alkene oxides. These compounds preferably contain ethylene oxide in a ratio of about 5 to about 25 moles per mole of alkylphenol.
  • Commercially Available surfactants of this type are e.g. Igepal TM CO-630 (GAF Corporation), Triton TM X-45, X-114, X-100 and X102 (Rohm and Haas) and the Arkopal TM N brands (Clariant GmbH). These surfactants are called alkylphenol alkoxylates, e.g. Alkylphenol ethoxylates.
  • the alkyl chain of the aliphatic alcohols can be linear or branched, primary or be secondary, and generally contains from 8 to 22 carbon atoms.
  • the condensation products of alcohols are particularly preferred Contain alkyl chain of 10 to 20 carbons, with 2 to 18 mol ethylene oxide per moles of alcohol.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates can have a narrow homolog distribution of the ethylene oxide ("Narrow Range Ethoxilates") or a broad homolog distribution of the Have ethylene oxides ("Broad Range Ethoxylates").
  • nonionic surfactants of this type are Teritol TM 15-S-9 (Condensation product of a C11-C15 linear secondary alcohol with 9 mol Ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a C12-C14 linear primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution).
  • Teritol TM 15-S-9 Condensation product of a C11-C15 linear secondary alcohol with 9 mol Ethylene oxide
  • Tergitol TM 24-L-NMW condensation product of a C12-C14 linear primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution.
  • Genapol TM brands from Clariant GmbH fall under this product class.
  • the hydrophobic part of these compounds preferably has a molecular weight between about 1500 and 1800 and is water-insoluble.
  • the attachment of Polyoxyethylene units on this hydrophobic part leads to an improvement the water solubility of the entire molecule.
  • the product is liquid up to one Polyoxyethylene content of approx. 50% of the total weight of the Condensation product, which is a condensation with up to about 40 mol of ethylene oxide corresponds.
  • Commercially available examples of this product class are the Pluronic TM brands from BASF and Genapol TM PF brands from Clariant GmbH.
  • the hydrophobic unit of these compounds consists of the reaction product of ethylenediamine and excess propylene oxide and generally has Molecular weight from about 2500 to 3000. This hydrophobic unit is ready condensed with ethylene oxide until the condensation product is approximately 40% by weight to approximately Contains 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000 having.
  • Commercially available examples of this class of compounds are Tetronic TM brands from BASF and the Genapol TM PN brands from Clariant GmbH.
  • This special category of nonionic compounds includes water-soluble amine oxides, phosphine oxides and sulfoxides which contain an alkyl radical with 10 to 18 carbon atoms and one or two alkyl groups or hydroxyalkyl groups with 1 to 3 carbon atoms.
  • This type of surfactant also includes amine oxides of the formula one in which R 3 represents an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof with a chain length of 8 to 22 carbon atoms, R is an alkylene or hydroxyalkylene group with 2 to 3 carbon atoms or mixtures thereof, each radical R 5 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units.
  • the R 5 groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring.
  • Amine oxides of this type are especially C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxyethyl dihydroxyethyl amine oxides.
  • Fatty acid amides have the formula R 6 -CON (R 7 ) 2 wherein R 6 is an alkyl group with 7 to 21, preferably with 9 to 17 carbon atoms and each radical R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and (C 2 H 4 O) x H, where x varies from 1 to 3.
  • R 6 is an alkyl group with 7 to 21, preferably with 9 to 17 carbon atoms and each radical R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and (C 2 H 4 O) x H, where x varies from 1 to 3.
  • C 8 -C 20 amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.
  • nonionic surfactants are Fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, Fatty acid N-alkylglucamides and protein hydrolyzates (especially vegetable Soy-based products).
  • the weight ratio between non-ionic surfactants and sweet whey can fluctuate within very wide limits.
  • Suitable nonionic surfactants are very generally described in US 3,929,678 described. A selection is given below.
  • polyethylene oxide condensates are preferred here.
  • This Compounds include the condensation products of alkylphenols with one Alkyl group of 6 to 12 carbon atoms, which are either linear or branched can, with alkene oxides. These compounds preferably contain ethylene oxide in a ratio of about 5 to about 25 moles per mole of alkylphenol.
  • Commercially Available surfactants of this type are e.g. Igepal TM CO-630, Triton TM X-45, X-114, X-100 and X-102.
  • the formulations according to the invention contain in addition to the surfactants mentioned, the specific auxiliaries and Additives, for example builders, foam inhibitors, salts, bleaches, Bleach activators, optical brighteners, graying inhibitors, solubilizers, Enzymes, thickeners, preservatives, fragrances and dyes, Pearlescent agents, emulsifiers, superfatting agents, biogenic agents (Plant extracts and vitamin complexes), sequestering agents.
  • the specific auxiliaries and Additives for example builders, foam inhibitors, salts, bleaches, Bleach activators, optical brighteners, graying inhibitors, solubilizers, Enzymes, thickeners, preservatives, fragrances and dyes, Pearlescent agents, emulsifiers, superfatting agents, biogenic agents (Plant extracts and vitamin complexes), sequestering agents.
  • Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which can precipitate or bind calcium ions in a complex manner.
  • Suitable and in particular ecologically harmless builder substances are 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.
  • Layered silicates are preferably used in non-aqueous systems. Zeolites and layered silicates can be contained in an amount of up to 20% by weight.
  • Usable organic builders are, for example, the percarboxylic acids preferably used in the form of their sodium salts, such as citric acid, nitriloacetate (NTA), ethylenediaminetetraacetic acid.
  • polymeric carboxylates and their salts can also be used. These include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 10% maleic acid and also polyvinylpyrrolidone and urethanes.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a sugar polyallyl ether and which have a relative molecular weight above one million are also particularly suitable.
  • the crosslinked polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.
  • These framework substances can be used in amounts of up to 5% by weight.
  • the agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanated silica.
  • foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanated silica.
  • foam inhibitors can also be used advantageously, e.g. those made of silicone oil, paraffin oil or waxes.
  • Liquid detergents can be optical brighteners, for example derivatives of Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in let the dispersion work in.
  • the maximum amount of brighteners in the Agents according to the invention is 0.5 wt .-%, preferably amounts of 0.02 to 0.25 wt .-% used.
  • the desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
  • organic solvents all monohydric or polyhydric alcohols are suitable as organic solvents.
  • Alcohols with 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used.
  • Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000.
  • polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred.
  • An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, it being possible for liquid detergents according to the invention to contain 8 to 12% by weight of such a mixture.
  • suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
  • Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, as well as higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates , Polyvinyl alcohol and polyvinyl pyrrolidone and electrolytes such as table salt and ammonium chloride are used.
  • Proteases, lipases, amylases or mixtures thereof come in as enzymes Question. Their proportion can be 0.2 to 1% by weight.
  • the enzymes can Carrier substances are adsorbed and / or embedded in coating substances.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP Diethylenetriaminepentamethylenephosphonic acid
  • Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentadiol or sorbic acid.
  • pearlescent agents examples include glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.
  • Suitable salts or adjusting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass).
  • Typical individual examples for further additives are sodium borate, starch, sucrose, polydextrose, TAED, stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, soaps and silicones.
  • sweet whey powder according to the invention in detergents and cleaning agents, in particular in household cleaning agents, such as hand dishwashing detergents, liquid all-purpose cleaners and mild detergents, particularly skin-friendly, environmentally friendly and powerful cleaning agents can be produced on the basis of a natural product.
  • household cleaning agents such as hand dishwashing detergents, liquid all-purpose cleaners and mild detergents, particularly skin-friendly, environmentally friendly and powerful cleaning agents can be produced on the basis of a natural product.
  • a Genapol DU 80 6.00% by weight Fatty acid mixture (Prifac 7949: palm kernel oil / oleic acid) 5.00% by weight Potassium hydroxide (w 85%) 0.80% by weight Triethanolamine 0.69% by weight B E-water (approx. 50 ° C) C. Hostapur SAS 60 5.10% by weight tri sodium citrate 2 hydrate 5.00% by weight D Ethanol 2.00% by weight Citric acid 1 hydrate 0.20% by weight Serusweet 83 6.00% by weight E Acticide SPX- (L) 0.20% by weight

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Abstract

New laundry and cleaning detergents contain fresh whey.

Description

An moderne Haushaltsreinigungsmittel werden nicht nur hohe Ansprüche an das Reinigungsvermögen gegenüber Schmutz und Fett sondern auch in gleichem Maß an die Umweltverträglichkeit und an die pflegenden Eigenschaffen gestellt. Zunehmende Hautunverträglichkeiten und allergische Reaktionen erfordern die Entwicklung neuer Tenside oder Tensidgemische oder den Einsatz alternativer Substanzen, insbesondere für Reinigungsmittel, die täglich eingesetzt werden und mit der Haut in Kontakt kommen.Modern household cleaning products are not just demanding Cleanability against dirt and grease but also to the same extent in terms of environmental compatibility and the caring properties. Increasing skin intolerance and allergic reactions require that Development of new surfactants or surfactant mixtures or the use of alternative ones Substances, especially for cleaning agents, which are used daily and come into contact with the skin.

In WO 94/09100 von Procter und Gamble wird der Einsatz von Polyhydroxyfettsäureamiden als biologisch gut abbaubares nicht-ionisches Tensid mit sehr guter Fettdispergierbarkeit und auf Basis nachwachsender Rohstoffe in Geschirrspülmitteln beschrieben.
DE 44 30 085 von Henkel beschreibt den Einsatz von Fettsäure-N-alkylpolyhydroxyalkylamiden und Alkyl- und/oder Alkenyl(ether)phosphaten in oberflächenaktiven Reinigungsmitteln.
EP 0 569 376 beschreibt ein Flüssigwaschmittel, das Alkylpolyglycosid und Fettalkoholsulfat enthält.
Milde Detergenzgemische mit verbessertem Schaumvermögen und gesteigerter hautkosmetischer Verträglichkeit, enthaltend Monoglycerid(ether)sulfide und Fettsäureisethionate, Fettsäuretaurate und/oder Fettsäuresarcosinate werden in DE 44 32 366 vorgeschlagen.
Analoge Eigenschatten weisen Detergenzgemische auf, enthaltend Monoglycerid(ether)sulfide und Sorbitanester und/oder Polysorbate wie in DE 44 32 130 beschrieben.WO 94/09100 from Procter and Gamble describes the use of polyhydroxy fatty acid amides as a readily biodegradable nonionic surfactant with very good fat dispersibility and based on renewable raw materials in dishwashing detergents.
DE 44 30 085 from Henkel describes the use of fatty acid N-alkylpolyhydroxyalkylamides and alkyl and / or alkenyl (ether) phosphates in surface-active cleaning agents.
EP 0 569 376 describes a liquid detergent which contains alkyl polyglycoside and fatty alcohol sulfate.
Mild detergent mixtures with improved foaming power and increased skin cosmetic compatibility, containing monoglyceride (ether) sulfides and fatty acid isethionates, fatty acid taurates and / or fatty acid sarcosinates are proposed in DE 44 32 366.
Analogous properties have detergent mixtures containing monoglyceride (ether) sulfides and sorbitan esters and / or polysorbates as described in DE 44 32 130.

In der kanadischen Patentschrift CA 21 01 622 wird der Einsatz von Milchsäure aus Molke in biologisch leicht abbaubaren, phosphatfreien Kosmetika, dargelegt. In der belgischen Patentschrift BE 10 03 561 wird die Emulgierwirkung von Molke, ein Abfallprodukt der Käseherstellung und ihre hautfreundliche Wirkung in Haushaltsreinigungsmittel beschrieben. Ein hohes Reinigungsvermögen zeigen Detergenzgemische, enthaltend Milcheiweißenzyme, gelöst in Borsäure-Puffer, gemäß der Patentschrift JP 62 19 696.In Canadian patent specification CA 21 01 622 the use of lactic acid is out Whey presented in easily biodegradable, phosphate-free cosmetics. Belgian patent BE 10 03 561 describes the emulsifying effect of whey, a waste product of cheese making and its skin-friendly effect in Household cleaning agents described. Show high cleaning ability Detergent mixtures containing milk protein enzymes, dissolved in boric acid buffer, according to the patent specification JP 62 19 696.

In den beschriebenen Rezepturen für Haushaltsreinigungsmittel ist es nicht gelungen, allen Anforderungen an ein modernes Reinigungsmittel, wie Hautverträglichkeit, gute biologische Abbaubarkeit, gute Reinigungswirkung und pflegende Wirkung gleichermaßen in befriedigender Weise gerecht zu werden.It is not in the recipes for household cleaning products described managed to meet all the requirements of a modern cleaning agent, such as Skin compatibility, good biodegradability, good cleaning effect and nurturing effect equally satisfactorily.

Überraschenderweise wurde gefunden, daß Süßmolke-Pulver, dessen Hauptbestandteil Lactose-Monohydrat und dessen Nebenbestandteile im wesentlichen Mineralstoffe und Proteine sind, in Kombination mit allen gängigen Tensiden und Tensidmischungen eine hervorragende Hautverträglichkeit und sehr gute Emulgiereffekte, die eine Ablagerung von Ölen und Fetten verhindert, bewirkt. Auch läßt sich eine Verbesserung des Solubilisiervermögens durch Zugabe von Süßmolke erreichen. Das Schaumvermögen auch bei Fettbelastung wird durch Zugabe von Molke nicht beeinträchtigt.
Signifikant ist ein guter Ablaufeffekt, insbesondere für Glas und Porzellan. Desweiteren wurde bei Einarbeitung von Süßmolke-Pulver in flüssige Allzweckreiniger eine Verbesserung des Ganzes, insbesondere von Kunststoffoberflächen und in Feinwaschmitteln ein pflegender und weichmachender Effekt, insbesondere für Wolle, erzielt.Surprisingly, it was found that sweet whey powder, the main constituent of which is lactose monohydrate and the minor constituents of which are essentially minerals and proteins, in combination with all the usual surfactants and surfactant mixtures has excellent skin compatibility and very good emulsifying effects, which prevent deposits of oils and fats . An improvement in the solubilizing capacity can also be achieved by adding sweet whey. Foaming is not impaired by the addition of whey, even when exposed to fat.
A good drainage effect is significant, especially for glass and porcelain. Furthermore, with the incorporation of sweet whey powder into liquid all-purpose cleaners, an improvement of the whole, in particular of plastic surfaces and in mild detergents, a caring and softening effect, in particular for wool, was achieved.

Gegenstand der Erfindung sind somit Wasch- und Reinigungsmittel mit einem Gehalt an Süßmolke.The invention thus relates to detergents and cleaning agents with a Sweet whey content.

Als Süßmolke nimmt man eine pulverförmige Süßmolke, beispielsweise ein sprühgetrocknetes Ultrafiltration-Permeat Pulver. Ein solches Produkt enthält 50 bis 100, vorzugsweise 70 bis 95, insbesondere 83 bis 90 Gew.-% Lactosemonohydrat. Nebenbestandteile sind Mineralstoffe (ca. 6 bis 10 Gew.-%), Proteine (ca. 3 bis 5 Gew.-%) und Wasser (bis zu 3 Gew.-%).For example, a sweet whey in powder form is used as sweet whey spray-dried ultrafiltration permeate powder. Such a product contains 50 to 100, preferably 70 to 95, in particular 83 to 90% by weight of lactose monohydrate. Minor components are minerals (approx. 6 to 10% by weight), proteins (approx. 3 to 5 % By weight) and water (up to 3% by weight).

Diese Süßmolke kann in alle üblichen festen und flüssigen Wasch- und Reinigungsmittel durch an sich bekannte Verfahren eingearbeitet werden. Vorzugsweise nimmt man die Süßmolke für die Herstellung von Handgeschirrspülmitteln, flüssigen Allzweckreinigern oder flüssigen Feinwaschmitteln, da bei diesen Formulierungen die ausgezeichnete Hautverträglichkeit der Süßmolke besonders von Bedeutung ist.This sweet whey can be used in all common solid and liquid washing and Detergents can be incorporated by methods known per se. The sweet whey is preferably used for the production of Hand dishwashing liquid, liquid all-purpose cleaner or liquid Delicates, as these formulations are excellent Skin compatibility of sweet whey is particularly important.

Die erfindungsgemäßen Wasch- und Reinigungsmittel können die Süßmolke in Mengen von 0,1 bis 15, vorzugsweise von 2 bis 7, insbesondere von 4 bis 6 Gew.-% enthalten. Darüberhinaus enthalten diese Wasch- und Reinigungsmittel noch die für diese Produkte üblichen und typischen Bestandteile wie Tenside und Hilfs- und Zusatzstoffe.The detergents and cleaning agents according to the invention can contain the sweet whey in Amounts from 0.1 to 15, preferably from 2 to 7, in particular from 4 to 6% by weight contain. In addition, these detergents and cleaning agents also contain those for these products common and typical ingredients such as surfactants and auxiliary and Additives.

Die in den erfindungsgemäßen Wasch- und Reinigungsmitteln enthaltenen Tenside können anionischer, kationischer, zwitterionischer (amphotärer) oder nicht-ionischer Natur sein.The surfactants contained in the washing and cleaning agents according to the invention can be anionic, cationic, zwitterionic (amphoteric) or non-ionic Be nature.

Als anionische Tenside kommen in Betracht Alkylsulfate, -sulfonate, -carboxylate, -phosphate und Mischungen aus den genannten Verbindungen. Im folgenden sollen einige der in Frage kommenden Typen von anionischen Tensiden näher beschrieben werden.Suitable anionic surfactants are alkyl sulfates, sulfonates, carboxylates, -phosphates and mixtures of the compounds mentioned. In the following should some of the types of anionic surfactants in question to be discribed.

AlkylestersulfonateAlkyl ester sulfonates

Alkylestersulfonate stellen lineare Ester von C8-C20-Carboxylsäuren (d.h. Fettsäuren) dar, die durch SO3 sulfoniert werden, wie in "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329 beschrieben. Geeignete Ausgangsmaterialien sind natürliche Fettderivate, wie z.B. Talg- oder Palmölfettsäure. Bevorzugte Alkylestersulfonate, speziell für Waschmittelanwendungen, sind Verbindungen der Formel

Figure 00040001
worin R3 einen C8-C20-Kohlenwasserstoffrest, bevorzugt Alkyl oder eine Mischung von Alkylresten, R4 einen C1-C6-Kohlenwasserstoffrest, bevorzugt Alkyl oder eine Mischung von Alkylresten darstellt. M steht für ein Kation, das ein wasserlösliches Salz mit dem Alkylestersulfonat bildet. Geeignete Kationen sind Metalle wie Natrium, Kaum, Lithium oder substituierte oder nicht substituierte Ammoniumkationen wie Monoethanolamin, Diethanolamin und Triethanolamin. Bevorzugt sind R3 C10-C16-Alkyl und R4 Methyl, Ethyl oder Isopropyl. Besonders bevorzugt sind Methylestersulfonate, in denen R3 C10-C16-Alkyl ist.Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie fatty acids) which are sulfonated by SO 3 , as described in "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials are natural fat derivatives, such as tallow or palm oil fatty acid. Preferred alkyl ester sulfonates, especially for detergent applications, are compounds of the formula
Figure 00040001
wherein R 3 is a C 8 -C 20 hydrocarbon radical, preferably alkyl or a mixture of alkyl radicals, R 4 is a C 1 -C 6 hydrocarbon radical, preferably alkyl or a mixture of alkyl radicals. M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are metals such as sodium, hardly any, lithium or substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. R 3 is C 10 -C 16 alkyl and R 4 is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R 3 is C 10 -C 16 alkyl are particularly preferred.

AlkylsulfateAlkyl sulfates

Alkylsulfate sind wasserlösliche Salze oder Säuren der Formel ROSO3M, worin R bevorzugt einen C10-C24-Kohlenwasserstoffrest, bevorzugt einen Alkyl- oder Hydroxyalkylrest mit 10 bis 20 C-Atomen, besonders bevorzugt einen C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. M ist Wasserstoff oder ein Kation, z.B. ein Alkalimetallkation (z.B. Natrium, Kalium, Lithium) oder Ammonium oder substituiertes Ammonium, z.B. ein Methyl-, Dimethyl- und Trimethylammoniumkation oder ein quaternäres Ammoniumkation, wie Tetramethylammonium- und Dimethylpiperidiniumkation und quatäre Ammoniumkationen, abgeleitet von Alkylaminen wie Ethylamin, Diethylamin, Triethylamin und deren Mischungen. Alkylketten mit C12-C16 sind dabei bevorzugt für niedrige Waschtemperaturen (z.B. unter ca. 50°C) und Alkylketten mit C16-C18 bevorzugt für höhere Waschtemperaturen (z.B. oberhalb ca. 50°C).Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 alkyl or Represents hydroxyalkyl. M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with C 16 -C 18 are preferred for higher washing temperatures (eg above approx. 50 ° C).

AlkylethersulfateAlkyl ether sulfates

Die Alkylethersulfate sind wasserlösliche Salze oder Säuren der Formel RO(A) SO3M, worin R einen unsubstituierten C10-C24-Alkyl- oder Hydroxyalkylrest mit 10 bis 24 C-Atomen, bevorzugt einen C12-C20-Alkyl- oder Hydroxyalkylrest, besonders bevorzugt einen C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. A ist eine Ethoxy- oder Propoxyeinheit, m ist eine Zahl von größer als 0, typischerweise zwischen ca. 0,5 und ca. 6, besonders bevorzugt zwischen ca. 0,5 und ca. 3 und M ist ein Wasserstoffatom oder ein Kation wie z.B. ein Metallkation (z.B. Natrium, Kalium, Lithium, Calcium, Magnesium, etc.), Ammonium oder ein substituiertes Ammoniumkation. Beispiele für substituierte Ammoniumkationen sind Methyl-, Dimethyl-, Trimethylammonium- und quaternäre Ammoniumkationen wie Tetramethylammonium und Dimethylpiperidiniumkationen, sowie solche, die von Alkylaminen, wie Ethylamin, Diethylamin, Triethylamin, Mischungen davon und ähnliche, abgeleitet sind. Als Beispiele seien genannt C12-C18-Alkyl-polyethoxylat-(1,0)-sulfat, (C12-C18E(1,0)M), C12-C18-Alkyl-polyethoxylat (2,25)sulfat (C12-C18E (2,25)M), C12-C18-Alkyl-polyethoxylat (3,0)sulfat, (C12-C18E (3,0)M), C12-C18-Alkyl-polyethoxylat (4,0)sulfat, (C12-C18E (4,0)M), wobei M Natrium oder Kalium ist.The alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) SO 3 M, in which R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl radical having 10 to 24 C atoms, preferably a C 12 -C 20 alkyl or Hydroxyalkyl radical, particularly preferably a C 12 -C 18 alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy unit, m is a number greater than 0, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as e.g. a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples include C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, (C 12 -C 18 E (1.0) M), C 12 -C 18 alkyl polyethoxylate (2.25 ) sulfate (C 12 -C 18 E (2.25) M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate, (C 12 -C 18 E (3.0) M), C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, (C 12 -C 18 E (4.0) M), where M is sodium or potassium.

AlkylbenzolsulfonateAlkylbenzenesulfonates

Ein weiteres geeignetes anionisches Tensid, das erfindungsgemäß eingesetzt werden kann, ist Alkylbenzolsulfonat. Die Alkylgruppe kann dabei entweder gesättigt oder ungesättigt, verzweigt oder linear und gegebenenfalls mit einer Hydroxylgruppe substituiert sein.
Die bevorzugten Alkylbenzolsulfonate enthalten lineare Alkylketten mit 9 bis 25 Kohlenstoffatomen, bevorzugt 10 bis 13 Kohlenstoffatomen, das Kation ist Natrium, Kalium, Ammonium, Mono-, Di- oder Triethanolammonium, Calcium oder Magnesium und Mischungen davon. Für milde Tensidsysteme ist Magnesium als Kation bevorzugt, für Standardwaschanwendungen dagegen Natrium.Another suitable anionic surfactant that can be used according to the invention is alkylbenzenesulfonate. The alkyl group can be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
The preferred alkylbenzenesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably 10 to 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Magnesium is preferred as the cation for mild surfactant systems, while sodium is preferred for standard washing applications.

Sekundäre AlkansulfonateSecondary alkane sulfonates

In sekundären Alkansulfonaten kann die Alkylgruppe entweder gesättigt oder ungesättigt, verzweigt oder linear und gegebenenfalls mit einer Hydroxylgruppe substituiert sein. Die Sulfogruppe ist statistisch über die gesamte C-Kette verteilt, wobei die primären Methylgruppen am Kettenanfang und Kettenende keine Sulfonatgruppen tragen. Die bevorzugten sekundären Alkansulfonate enthalten lineare Alkylketten mit 9 bis 25 Kohlenstoffatomen, bevorzugt von 10 bis 20 Kohlenstoffatomen und besonders bevorzugt 13 bis 17 Kohlenstoffatome. Das Kation ist Natrium, Kaum, Ammonium, Mono-, Di- oder Triethanolammonium, Calcium oder Magnesium und Mischungen davon. Natrium als Kation ist bevorzugt.In secondary alkane sulfonates, the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted. The sulfo group is statistically distributed over the entire C chain, with the primary methyl groups at the beginning and end of the chain none Wear sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably from 10 to 20 Carbon atoms and particularly preferably 13 to 17 carbon atoms. The Cation is sodium, hardly, ammonium, mono-, di- or triethanolammonium, Calcium or magnesium and mixtures thereof. Sodium as the cation is preferred.

SeifenSoap

Weitere bevorzugte Tenside sind Carboxylate, z.B. Fettsäureseifen und vergleichbare Tenside. Die Seifen können gesättigt oder ungesättigt sein und können verschiedene Substituenten, wie Hydroxylgruppen oder Alpha-Sulfonatgruppen enthalten. Bevorzugt sind lineare gesättigte oder ungesättigte Kohlenwasserstoffreste als hydrophobe Komponente in den Seifen. Üblicherweise enthalten die hydrophoben Komponenten 6 bis 30 Kohlenstoffatome, bevorzugt 10 bis 18 Kohlenstoffatome. Das Kation (M) der Carboxylattenside kann ein Alkalimetall, z.B. Natrium oder Kalium, ein Erdalkalimetall, z.B. Calcium oder Magnesium, Ammonium oder substituiertes Ammonium einschließlich Mono-, Di- und Triethanolammonium sein. Mischungen der Kationen können dabei von Vorteil sein.Other preferred surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants. The soaps can be saturated or unsaturated and can have various substituents, such as hydroxyl groups or alpha sulfonate groups contain. Linear saturated or unsaturated are preferred Hydrocarbon residues as a hydrophobic component in the soaps. Usually contain the hydrophobic components 6 to 30 carbon atoms, preferably 10 up to 18 carbon atoms. The cation (M) of the carboxylate surfactants can be a Alkali metal, e.g. Sodium or potassium, an alkaline earth metal, e.g. Calcium or Magnesium, ammonium or substituted ammonium including mono-, di- and Be triethanolammonium. Mixtures of the cations can be advantageous be.

Weitere mögliche anionische Tenside sind die Salze von Acylaminocarbonsäuren, die durch Umsetzung von Fettsäurenchloriden mit Natriumsarkosinat im alkalischen Medium entstehen (Acylsarcosinate) oder Fettsäure-Eiweiß-Kondensationsprodukte die durch Umsetzung von Fettsäurechloriden mit Oligopeptiden erhalten werden, sowie die Salze von Alkylsulfamidocarbonsäuren und die Salze von Alkyl- und Alkylarylethercarbonsäuren.Other possible anionic surfactants are the salts of acylaminocarboxylic acids, by the reaction of fatty acid chlorides with sodium sarcosinate in alkaline Medium arise (acyl sarcosinate) or fatty acid-protein condensation products which are obtained by reacting fatty acid chlorides with oligopeptides, as well as the salts of alkylsulfamidocarboxylic acids and the salts of alkyl and Alkylaryl ether carboxylic acids.

Andere anionische Tenside für den Einsatz in Wasch- und Reinigungsmitteln sind C8-C24-Olefinsulfonate, sulfonierte Polycarboxylsäuren, hergestellt durch Sulfonierung der Pyrrolyseprodukte von Erdalkalimetallcitraten, wie z.B. beschrieben in GB 1,082,179, Alkylglycerinsulfate, Fettacylglycerinsulfate, Oleylglycerinsulfate, Alkylphenolethersulfate, primäre Paraffinsulfonate, Alkylphosphate, Alkyletherphosphate, Isethionate, wie Acylisethionate, N-Acyltauride, Alkylsuccinamate, Sulfosuccinate, Monoester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Monoester) und Diester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Diester), Acylsarcosinate, Sulfate von Alkylpolysacchariden wie Sulfate von Alkylpolyglycosiden, verzweigte primäre Alkylsulfate und Alkylpolyethoxycarboxylate der Formel RO(CH2CH2)kCH2COOM worin R C8-C22-Alkyl, k eine Zahl von 0 bis 10 und M ein ein lösliches Salz bildendes Kation ist. Harzsäuren oder hydrierte Harzsäuren, wie Rosin oder hydriertes Rosin oder Tallölharze und Tallölharzsäuren sind ebenfalls einsetzbar. Weitere Beispiele sind in "Surface Active Agents and Detergents" (Vol. I und II, Schwartz, Perry und Berch) beschrieben.Other anionic surfactants for use in detergents and cleaning agents are C 8 -C 24 -olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfate sulfates, alkylphenol parolate, primary phenolate sulfates Alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 diesters), Acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxy carboxylates of the formula RO (CH 2 CH 2 ) k CH 2 COOM wherein RC 8 -C 22 alkyl, k is a number from 0 to 10 and M a is a soluble salt is forming cation. Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch).

Typische Beispiele für anionische Tenside sind Alkylbenzolsulfonate, Alkansulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Fettsäureamid-(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinate, Sulfotriglyceride, Amidseifen, Alkyloligoglucosidsulfate, Alkylaminozuckersulfate und Alkyl-(ether)-phosphate. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können sie eine konventionelle oder auch eingeengte Homologenverteilung aufweisen.Typical examples of anionic surfactants are alkylbenzenesulfonates, Alkane sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, Sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, Hydroxy mixed ether sulfates, fatty acid amide (ether) sulfates, mono- and Dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinates, sulfotriglycerides, Amide soaps, alkyl oligoglucoside sulfates, alkyl amino sugar sulfates and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they have a conventional or narrow homolog distribution.

Das Verhältnis von anionischen Tensiden zu Süßmolke-Pulver kann zwischen 99:1 und 1:99 variieren.The ratio of anionic surfactants to sweet whey powder can be between 99: 1 and 1:99 vary.

Typische Beispiele für kationische Tenside im Rahmen der vorliegenden Erfindung sind quartäre Ammoniumsalze und Esterquats, insbesondere quaternierte Fettsäurealkanolaminester-Salze und Trialkylaminopropylaminester-Salze.Typical examples of cationic surfactants in the context of the present invention are quaternary ammonium salts and ester quats, especially quaternized ones Fatty acid alkanolamine ester salts and trialkylaminopropylamine ester salts.

Bei den quartären Ammoniumsalzen handelt es sich vorzugsweise um solche des Typs RN(CH3)3Cl und R2N(CH3)2Cl mit einem Alkylrest R, dessen Kettenlänge zwischen 8 und 24 C-Atomen, bevorzugt zwischen 10 und 18 C-Atomen liegt.The quaternary ammonium salts are preferably those of the type RN (CH 3 ) 3 Cl and R 2 N (CH 3 ) 2 Cl with an alkyl radical R whose chain length is between 8 and 24 C atoms, preferably between 10 and 18 C. -Atoms lies.

Beispiele für amphotere Tenside, die für die Formulierungen der vorliegenden Erfindung geeignet sind, sind vor allem solche, die ganz allgemein als Derivate von aliphatischen sekundären und tertiären Aminen beschrieben werden können, in denen der aliphatische Rest linear oder verzweigt sein kann und einer der aliphatischen Substituenten zwischen 8 und 18 Kohlenstoffatome enthält und die eine anionische, wasserlösliche Gruppe wie z.B. Carboxy, Sulfonat, Sulfat, Phosphat oder Phosphonat enthalten. Amphotere Tenside sind beispielsweise Imidazolium-Tenside der nachfolgenden Formel:

Figure 00080001
worin R1 einen C8-C22-Alkyl- oder Alkenylrest, bevorzugt C12-C16, darstellt, R2 ist Wasserstoff oder CH2CO2M, R3 ist CH2CH2OH oder CH2CH2OCH2CHCOOM, R4 ist Wasserstoff, CH2CH2OH oder CH2CH2OCH2CHCOOM, Z ist CO2M oder CH2CO2M, n ist 2 oder 3, bevorzugt 2, M ist Wasserstoff oder ein Kation wie Alkalimetall, Erdalkalimetall, Ammoniak oder Alkanolammonium.Examples of amphoteric surfactants which are suitable for the formulations of the present invention are, above all, those which can be described very generally as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and one of the aliphatic substituents contains between 8 and 18 carbon atoms and which contain an anionic, water-soluble group such as carboxy, sulfonate, sulfate, phosphate or phosphonate. Amphoteric surfactants are, for example, imidazolium surfactants of the following formula:
Figure 00080001
wherein R 1 is a C 8 -C 22 alkyl or alkenyl radical, preferably C 12 -C 16 , R 2 is hydrogen or CH 2 CO 2 M, R 3 is CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, Z is CO 2 M or CH 2 CO 2 M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal , Alkaline earth metal, ammonia or alkanolammonium.

Bevorzugte amphotere Tenside der obigen Formel sind Monocarboxylate und Dicarboxylate. Beispiele für diese Verbindungen sind Cocoamphocarboxypropionat, Cocoamidocarboxypropionsäure, Cocoamphocarboxyglycinat (oder auch als Cocoamphodiacetat bezeichnet) und Cocoamphoacetat.Preferred amphoteric surfactants of the above formula are monocarboxylates and Dicarboxylates. Examples of these compounds are cocoamphocarboxypropionate, Cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also as Cocoamphodiacetate) and Cocoamphoacetat.

Weitere bevorzugte amphotere Tenside sind Alkyldimethylbetaine, Alkylamidobetaine und Alkyldipolyethoxybetaine mit einem Alkylrest mit 8 bis 22, bevorzugt mit 8 bis 18 Kohlenstoffatomen. Diese Verbindungen werden z.B. von der Hoechst AG unter dem Handelsnamen ®Genagen CAB vermarktet. Further preferred amphoteric surfactants are alkyldimethylbetaines, Alkyl amido betaines and alkyl dipolyethoxy betaines with an alkyl radical having 8 to 22, preferably with 8 to 18 carbon atoms. These connections are e.g. of the Hoechst AG is marketed under the trade name ®Genagen CAB.

Geeignete nichtionische Tenside werden in US 3,929,678 beschrieben. Eine Auswahl wird nachfolgend gegeben.Suitable nonionic surfactants are described in US 3,929,678. A Selection is given below.

Polyethylen-, Polypropylen- und Polybutylenoxidaddukte von Alkylphenolen: Allgemein werden hier die Polyethylenoxidkondensate bevorzugt. Diese Verbindungen umfassen die Kondensationsprodukte von Alkylphenolen mit einer Alkylgruppe von 6 bis 12 Kohlenstoffatome, die entweder linear oder verzweigt sein kann, mit Alkenoxiden. Bevorzugt enthalten diese Verbindungen Ethylenoxid in einem Verhältnis von ca. 5 bis ca. 25 mol pro mol Alkylphenol. Kommerziell erhältliche Tenside diesen Typs sind z.B. Igepal™ CO-630 (GAF Corporation), Triton™ X-45, X-114, X-100 und X102 (Rohm und Haas) und die Arkopal™ N-Marken (Clariant GmbH). Diese Tenside werden als Alkylphenolalkoxilate, z.B. Alkylphenolethoxilate, bezeichnet.Polyethylene, polypropylene and polybutylene oxide adducts of alkylphenols: In general, the polyethylene oxide condensates are preferred here. This Compounds include the condensation products of alkylphenols with one Alkyl group of 6 to 12 carbon atoms, which are either linear or branched can, with alkene oxides. These compounds preferably contain ethylene oxide in a ratio of about 5 to about 25 moles per mole of alkylphenol. Commercially Available surfactants of this type are e.g. Igepal ™ CO-630 (GAF Corporation), Triton ™ X-45, X-114, X-100 and X102 (Rohm and Haas) and the Arkopal ™ N brands (Clariant GmbH). These surfactants are called alkylphenol alkoxylates, e.g. Alkylphenol ethoxylates.

Additionsprodukte von aliphatischen Alkoholen mit ca. 1 bis ca. 25 mol Ethylenoxid Die Alkylkette der aliphatischen Alkohole kann linear oder verzweigt, primär oder sekundär sein, und enthält im allgemeinen von 8 bis 22 Kohlenstoffatome. Besonders bevorzugt sind die Kondensationsprodukte von Alkoholen, die eine Alkylkette von 10 bis 20 Kohlenstoffen enthalten, mit 2 bis 18 mol Ethylenoxid pro mol Alkohol. Die Alkylkette kann gesättigt oder auch ungesättigt sein. Ebenso können die Alkoholethoxylate eine enge Homologenverteilung des Ethylenoxides ("Narrow Range Ethoxilates") oder eine breite Homologenverteilung des Ethylenoxides ("Broad Range Ethoxylates") aufweisen. Beispiele von kommerziell erhältlichen nichtionischen Tensiden dieses Types sind Teritol™ 15-S-9 (Kondensationsprodukt eines C11-C15 linearen sekundären Alkohols mit 9 mol Ethylenoxid), Tergitol™ 24-L-NMW (Kondensationsprodukt eines C12-C14 linearen primären Alkohols mit 6 mol Ethylenoxid mit enger Molgewichtsverteilung). Ebenfalls unter diese Produktklasse fallen die Genapol™ -Marken der Clariant GmbH.Addition products of aliphatic alcohols with approx. 1 to approx. 25 mol ethylene oxide The alkyl chain of the aliphatic alcohols can be linear or branched, primary or be secondary, and generally contains from 8 to 22 carbon atoms. The condensation products of alcohols are particularly preferred Contain alkyl chain of 10 to 20 carbons, with 2 to 18 mol ethylene oxide per moles of alcohol. The alkyl chain can be saturated or unsaturated. As well the alcohol ethoxylates can have a narrow homolog distribution of the ethylene oxide ("Narrow Range Ethoxilates") or a broad homolog distribution of the Have ethylene oxides ("Broad Range Ethoxylates"). Examples of commercial available nonionic surfactants of this type are Teritol ™ 15-S-9 (Condensation product of a C11-C15 linear secondary alcohol with 9 mol Ethylene oxide), Tergitol ™ 24-L-NMW (condensation product of a C12-C14 linear primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution). Likewise The Genapol ™ brands from Clariant GmbH fall under this product class.

Additionsprodukte von Ethylenoxid mit einer hydrophoben Base, gebildet aus der Kondensation von Propylenoxid mit PropylenglykolAddition products of ethylene oxide with a hydrophobic base formed from the Condensation of propylene oxide with propylene glycol

Der hydrophobe Teil dieser Verbindungen hat bevorzugt ein Molekulargewicht zwischen ca. 1500 und 1800 auf und ist wasserunlöslich. Die Anlagerung von Polyoxyethyleneinheiten an diesem hydrophoben Teil führt zu einer Verbesserung der Wasserlöslichkeit des gesamten Moleküls. Das Produkt ist flüssig bis zu einem Polyoxyethylengehalt von ca. 50 % des Gesamtgewichtes des Kondensationsproduktes, was einer Kondensation mit bis zu ca. 40 mol Ethylenoxid entspricht. Kommerziell erhältliche Beispiele dieser Produktklasse sind die Pluronic™-Marken der BASF und die Genapol™ PF-Marken der Clariant GmbH.The hydrophobic part of these compounds preferably has a molecular weight between about 1500 and 1800 and is water-insoluble. The attachment of Polyoxyethylene units on this hydrophobic part leads to an improvement the water solubility of the entire molecule. The product is liquid up to one Polyoxyethylene content of approx. 50% of the total weight of the Condensation product, which is a condensation with up to about 40 mol of ethylene oxide corresponds. Commercially available examples of this product class are the Pluronic ™ brands from BASF and Genapol ™ PF brands from Clariant GmbH.

Additionsprodukte von Ethylenoxid mit einem Reaktionsprodukt von Propylenoxid und Ethylendiamin.Addition products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

Die hydrophobe Einheit dieser Verbindungen besteht aus dem Reaktionsprodukt von Ethylendiamin und überschüssigem Propylenoxid und weist im allgemeinen ein Molekulargewicht von ca. 2500 bis 3000 auf. Diese hydrophobe Einheit wird soweit mit Ethylenoxid kondensiert, bis das Kondensationsprodukt ca. 40 Gew.-% bis ca. 80 Gew.-% Polyoxyethylen enthält und ein Molekulargewicht von ca. 5000 bis 11000 aufweist. Kommerziell erhältliche Beispiele dieser Verbindungsklasse sind die Tetronic™-Marken der BASF und die Genapol™ PN-Marken der Clariant GmbH.The hydrophobic unit of these compounds consists of the reaction product of ethylenediamine and excess propylene oxide and generally has Molecular weight from about 2500 to 3000. This hydrophobic unit is ready condensed with ethylene oxide until the condensation product is approximately 40% by weight to approximately Contains 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000 having. Commercially available examples of this class of compounds are Tetronic ™ brands from BASF and the Genapol ™ PN brands from Clariant GmbH.

Semipolare nichtionische TensideSemipolar nonionic surfactants

Diese spezielle Kategorie von nichtionischen Verbindungen umfaßt wasserlösliche Aminoxide, Phosphinoxide und Sulfoxide, die einen Alkylrest mit 10 bis 18 Kohlenstoffatome und ein bzw. zwei Alkylgruppen oder Hydroxyalkylgruppen mit 1 bis 3 Kohlenstoffatomen enthalten. Zu dieser Art von Tensiden gehören auch Aminoxide der Formel

Figure 00100001
ein, worin R3 eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe oder Mischungen hiervon darstellt mit einer Kettenlänge von 8 bis 22 Kohlenstoffatome, R ist eine Alkylen- oder Hydroxyalkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, jeder Rest R5 ist eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxideinheiten. Die R5-Gruppen können miteinander über ein Sauerstoff oder Stickstoffatom verbunden sein und somit einen Ring bilden. Aminoxide dieser Art sind besonders C10-C18-Alkyldimethylaminoxide und C8-C12-Alkoxyethyl-dihydroxyethylaminoxide.This special category of nonionic compounds includes water-soluble amine oxides, phosphine oxides and sulfoxides which contain an alkyl radical with 10 to 18 carbon atoms and one or two alkyl groups or hydroxyalkyl groups with 1 to 3 carbon atoms. This type of surfactant also includes amine oxides of the formula
Figure 00100001
one in which R 3 represents an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof with a chain length of 8 to 22 carbon atoms, R is an alkylene or hydroxyalkylene group with 2 to 3 carbon atoms or mixtures thereof, each radical R 5 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units. The R 5 groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring. Amine oxides of this type are especially C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxyethyl dihydroxyethyl amine oxides.

FettsäureamideFatty acid amides

Fettsäureamide besitzen die Formel R6-CON(R7)2 worin R6 eine Alkylgruppe mit 7 bis 21, bevorzugt mit 9 bis 17 Kohlenstoffatomen ist und jeder Rest R Wasserstoff, C1-C4-Alkyl, C1-C4-Hydroxyalkyl und (C2H4O)xH ist, wobei x von 1 bis 3 variiert. Bevorzugt sind C8-C20-Amide, -monoethanolamide, -diethanolamide und -isopropanolamide.Fatty acid amides have the formula R 6 -CON (R 7 ) 2 wherein R 6 is an alkyl group with 7 to 21, preferably with 9 to 17 carbon atoms and each radical R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and (C 2 H 4 O) x H, where x varies from 1 to 3. C 8 -C 20 amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.

Nichtionischen TensideNonionic surfactants

Typische Beispiele für weitere geeignete nichtionische Tenside sind Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, Alk(en)yloligoglycoside, Fettsäure-N-alkylglucamide und Proteinhydrolysate (insbesondere pflanzliche Produkte auf Sojabasis). Das Gewichtsverhältnis zwischen nicht ionischen Tenside und Süßmolke kann in sehr weiten Grenzen schwanken. Vorteilhaft ist ein Gewichtsverhältnis von nichtionischem Tensid zu Süßmolke von 1:25.Typical examples of other suitable nonionic surfactants are Fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, Fatty acid N-alkylglucamides and protein hydrolyzates (especially vegetable Soy-based products). The weight ratio between non-ionic surfactants and sweet whey can fluctuate within very wide limits. One is advantageous Weight ratio of nonionic surfactant to sweet whey of 1:25.

Geeignete nichtionische Tenside werden ganz allgemein in US 3,929,678 beschrieben. Eine Auswahl wird nachfolgend gegeben.Suitable nonionic surfactants are very generally described in US 3,929,678 described. A selection is given below.

Polyethylen-, Polypropylen- und Polybutylenoxidaddukte von AlkylphenolenPolyethylene, polypropylene and polybutylene oxide adducts of alkylphenols

Allgemein werden hier die Polyethylenoxidkondensate bevorzugt. Diese Verbindungen umfassen die Kondensationsprodukte von Alkylphenolen mit einer Alkylgruppe von 6 bis 12 Kohlenstoffatomen, die entweder linear oder verzweigt sein kann, mit Alkenoxiden. Bevorzugt enthalten diese Verbindungen Ethylenoxid in einem Verhältnis von ca. 5 bis ca. 25 mol pro mol Alkylphenol. Kommerziell erhältliche Tenside diesen Typs sind z.B. Igepal™ CO-630, Triton™ X-45, X-114, X-100 und X-102.In general, the polyethylene oxide condensates are preferred here. This Compounds include the condensation products of alkylphenols with one Alkyl group of 6 to 12 carbon atoms, which are either linear or branched can, with alkene oxides. These compounds preferably contain ethylene oxide in a ratio of about 5 to about 25 moles per mole of alkylphenol. Commercially Available surfactants of this type are e.g. Igepal ™ CO-630, Triton ™ X-45, X-114, X-100 and X-102.

Die erfindungsgemäßen Formulierungen enthalten, je nach Anwendungszweck, neben den genannten Tensiden noch die jeweils spezifischen Hilfs- und Zusatzstoffe beispielsweise Gerüststoffe, Schauminhibitoren, Salze, Bleichmittel, Bleichaktivatoren, optische Aufheller, Vergrauungsinhibitoren, Lösungsvermittler, Enzyme, Verdickungsmittel, Konservierungsmittel, Duft- und Farbstoffe, Perlglanzmittel, Emulgatoren, Überfettungsmittel, biogene Wirkstoffe (Pflanzenextrakte und Vitaminkomplexe), Sequestriermittel.Depending on the intended use, the formulations according to the invention contain in addition to the surfactants mentioned, the specific auxiliaries and Additives, for example builders, foam inhibitors, salts, bleaches, Bleach activators, optical brighteners, graying inhibitors, solubilizers, Enzymes, thickeners, preservatives, fragrances and dyes, Pearlescent agents, emulsifiers, superfatting agents, biogenic agents (Plant extracts and vitamin complexes), sequestering agents.

Als organische und anorganische Gerüststoffe eignen sich neutral oder insbesondere alkalisch reagierende Salze, die Calciumionen auszufällen oder komplex zu binden vermögen. Geeignete und insbesondere ökologisch unbedenkliche Buildersubstanzen sind feinkristalline, synthetische wasserhaltige Zeolithe vom Typ NaA, die ein Calciumbindevermögen im Bereich von 100 bis 200 mg CaO/g aufweisen. In nicht wäßrigen Systemen werden bevorzugt Schichtsilikate eingesetzt. Zeolithe und Schichtsilikate können in einer Menge bis zu 20 Gew.-% im Mittel enthalten sein. Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Percarbonsäuren, wie Citronensäure, Nitriloacetat (NTA), Ethylendiamintetraessigsäure. Analog hierzu können auch polymere Carboxylate und deren Salze eingesetzt werden. Hierzu gehören beispielsweise die Salze homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure und auch Polyvinylpyrrolidon und Urethane. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100 000, die der Copolymeren zwischen 2000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Zuckerpolyallylethers quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispielsweise hierfür sind die unter den Namen Carbopol 940 und 941 erhältlichen Polymere. Die quervernetzten Polyacrylate werden in Mengen nicht über 1 Gew.-%, vorzugsweise in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt.
Diese Gerüstsubstanzen können in Mengen bis zu 5 Gew-.% eingesetzt werden.Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which can precipitate or bind calcium ions in a complex manner. Suitable and in particular ecologically harmless builder substances are 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. Layered silicates are preferably used in non-aqueous systems. Zeolites and layered silicates can be contained in an amount of up to 20% by weight. Usable organic builders are, for example, the percarboxylic acids preferably used in the form of their sodium salts, such as citric acid, nitriloacetate (NTA), ethylenediaminetetraacetic acid. Analogously, polymeric carboxylates and their salts can also be used. These include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 10% maleic acid and also polyvinylpyrrolidone and urethanes. The relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a sugar polyallyl ether and which have a relative molecular weight above one million are also particularly suitable. Examples of these are the polymers available under the names Carbopol 940 and 941. The crosslinked polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.
These framework substances can be used in amounts of up to 5% by weight.

Die erfindungsgemäßen Mittel können als Schauminhibitoren Fettsäurealkylesteralkoxylate, Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure, enthalten. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z.B. solche aus Silikonöl, Paraffinöl oder Wachsen. Vorzugsweise sind Schauminhibitoren an eine granulare, in Wasser lösliche oder dispergierbare Trägersubstanz gebunden.The agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanated silica. With Mixtures of different foam inhibitors can also be used advantageously, e.g. those made of silicone oil, paraffin oil or waxes. Are preferred Foam inhibitors to a granular, water soluble or dispersible Carrier bound.

Flüssigwaschmittel können optische Aufheller beispielsweise Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten, die sich gut in die Dispersion einarbeiten lassen. Der maximale Gehalt an Aufhellern in den erfindungsgemäßen Mitteln beträgt 0,5 Gew.-%, vorzugsweise werden Mengen von 0,02 bis 0,25 Gew.-% eingesetzt.Liquid detergents can be optical brighteners, for example derivatives of Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in let the dispersion work in. The maximum amount of brighteners in the Agents according to the invention is 0.5 wt .-%, preferably amounts of 0.02 to 0.25 wt .-% used.

Die gewünschte Viskosität der Mittel kann durch Zugabe von Wasser und/oder organischen Lösungsmitteln oder durch Zugabe einer Kombination aus organischen Lösungsmitteln und Verdickungsmitteln eingestellt werden. Prinzipiell kommen als organische Lösungsmittel alle ein- oder mehrwertigen Alkohole in Betracht. Bevorzugt werden Alkohole mit 1 bis 4 Kohlenstoffatomen wie Methanol, Ethanol, Propanol, Isopropanol, geradkettiges und verzweigtes Butanol, Glycerin und Mischungen aus den genannten Alkoholen eingesetzt. Weitere bevorzugte Alkohole sind Polyethylenglykole mit einer relativen Molekülmasse unter 2000. Insbesondere ist ein Einsatz von Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 600 und in Mengen bis zu 45 Gew.-% und von Polyethylenglykol mit einer relativen Molekülmasse zwischen 400 und 600 in Mengen von 5 bis 25 Gew.-% bevorzugt. Eine vorteilhafte Mischung aus Lösungsmitteln besteht aus monomerem Alkohol, beispielsweise Ethanol und Polyethylenglykol im Verhältnis 0,5:1 bis 1,2:1, wobei erfindungsgemäße Flüssigwaschmittel 8 bis 12 Gew.-% einer solchen Mischung enthalten können. Weitere geeignete Lösungsmittel sind beispielsweise Triacetin (Glycerintriacetat) und 1-Methoxy-2-propanol.
Als Verdickungsmittel werden bevorzugt gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, die vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-, Kalium-, Aluminium-, Magnesium- und Titan-Stearate oder die Natrium und/oder Kaliumsalze der Behensäure, sowie Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethylcellulose, ferner höhermolekulare Polyethylenglycolmono- und -diester von Fettsäuren, Polyacrylate, Polyvinylalkohol und Polyvinylpyrrolidon sowie Elektrolyte wie Kochsalz und Ammoniumchlorid eingesetzt.The desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners. In principle, all monohydric or polyhydric alcohols are suitable as organic solvents. Alcohols with 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used. Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000. In particular, use of polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred. An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, it being possible for liquid detergents according to the invention to contain 8 to 12% by weight of such a mixture. Other suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, as well as higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates , Polyvinyl alcohol and polyvinyl pyrrolidone and electrolytes such as table salt and ammonium chloride are used.

Als Enzyme kommen Proteasen, Lipasen, Amylasen bzw. deren Gemische in Frage. Ihr Anteil kann 0,2 bis 1 Gew.-% betragen. Die Enzyme können an Trägersubstanzen adsorbiert werden und/oder in Hüllsubstanzen eingebettet sein.Proteases, lipases, amylases or mixtures thereof come in as enzymes Question. Their proportion can be 0.2 to 1% by weight. The enzymes can Carrier substances are adsorbed and / or embedded in coating substances.

Um Spuren von Schwermetallen zu binden, können die Salze von Polyphosphorsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und Diethylentriaminpentamethylenphosphonsäure (DTPMP) eingesetzt werden.In order to bind traces of heavy metals, the salts of Polyphosphoric acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and Diethylenetriaminepentamethylenephosphonic acid (DTPMP) can be used.

Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentadiol oder Sorbinsäure.Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentadiol or sorbic acid.

Als Perlglanzmittel kommen beispielsweise Glycoldistearinsäureester wie Ethylenglycoldistearat, aber auch Fettsäuremonoglycolester in Betracht.Examples of pearlescent agents are glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.

Als Salze bzw. Stellmittel kommen beispielsweise Natriumsulfat, Natriumcarbonat oder Natriumsilikat (Wasserglas) in Betracht.
Als typische Einzelbeispiele für weitere Zusatzstoffe sind Natriumborat, Stärke, Saccharose, Polydextrose, TAED, Stilbenverbindungen, Methylcellulose, Toluolsulfonat, Cumolsulfonat, Seifen und Silicone zu nennen.Suitable salts or adjusting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass).
Typical individual examples for further additives are sodium borate, starch, sucrose, polydextrose, TAED, stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, soaps and silicones.

Mit dem erfindungsgemäßen Einsatz von Süßmolke-Pulver in Wasch- und Reinigungsmitteln, insbesondere in Haushaltsreinigungsmitteln, wie Handgeschirrspülmittel, flüssige Allzweckreiniger und Feinwaschmitteln, lassen sich besonders hautschonende, umweltfreundliche und leistungsstarke Reinigungsmittel auf Basis eines Naturproduktes herstellen.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken.With the use of sweet whey powder according to the invention in detergents and cleaning agents, in particular in household cleaning agents, such as hand dishwashing detergents, liquid all-purpose cleaners and mild detergents, particularly skin-friendly, environmentally friendly and powerful cleaning agents can be produced on the basis of a natural product.
The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

BeispieleExamples HandgeschirrspülmittelHand dishwashing liquid Beispiel 1example 1

AA Hostapur SAS 60Hostapur SAS 60 8.00 Gew.-%8.00% by weight Genapol LRO flüssigGenapol LRO liquid 5.00 Gew.-%5.00% by weight Genagen LABGenagen LAB 2.00 Gew.-% 2.00% by weight Serusweet 83Serusweet 83 4.00 Gew.-%4.00% by weight BB Wasserwater CC. Acticide SPX-(L)Acticide SPX- (L) 0.20 Gew.-%0.20% by weight

Beispiel 2Example 2

AA Hostapur SAS 60Hostapur SAS 60 6.00 Gew.-%6.00% by weight Genapol LRO flüssigGenapol LRO liquid 7.20 Gew.-%7.20% by weight Genagen LABGenagen LAB 1.80 Gew.-%1.80% by weight Serusweet 83Serusweet 83 6.00 Gew.-%6.00% by weight BB Wasserwater CC. Acticide SPX-(L)Acticide SPX- (L) 0.20 Gew.-%0.20% by weight

Beispiel 3Example 3

AA Hostapur SAS 60Hostapur SAS 60 20.00 Gew.-%20.00% by weight Genapol LRO flüssigGenapol LRO liquid 4.50 Gew.-%4.50% by weight Genagen LABGenagen LAB 0.50 Gew.-%0.50% by weight Serusweet 83Serusweet 83 4.00 Gew.-%4.00% by weight BB Wasserwater CC. Acticide SPX-(L)Acticide SPX- (L) 0.20 Gew.-%0.20% by weight

Beispiel 4Example 4

AA Hostapur SAS 60Hostapur SAS 60 20.50 Gew.-% 20.50% by weight Genapol LRO flüssigGenapol LRO liquid 4.00 Gew.-%4.00% by weight Genagen LABGenagen LAB 0.50 Gew.-%0.50% by weight Serusweet 83Serusweet 83 6.00 Gew.-%6.00% by weight BB Wasserwater CC. Acticide SPX-(L)Acticide SPX- (L) 0.20 Gew.-%0.20% by weight

Herstellung:Manufacturing:

Alle Komponenten von A nacheinander in B einrühren. Abschließend C zugeben.Stir all components of A into B one after the other. Finally add C.

AllzweckreinigerAll-purpose cleaner Beispiel 1example 1

AA Hostapur SASHostapur SAS 7.80 Gew.-%7.80% by weight Genapol DU 080Genapol DU 080 2.00 Gew.-%2.00% by weight BB tri-Natriumcitrat-2-hydrattri sodium citrate 2 hydrate 5.00 Gew.-%5.00% by weight CC. Wasser (ca. 40 - 50°C)Water (approx. 40 - 50 ° C) DD Serusweet 83Serusweet 83 6.00 Gew.-%6.00% by weight Acticide SPC-(L)Acticide SPC- (L) 0.20 Gew.-%0.20% by weight

HerstellungManufacturing

Komponenten A miteinander vermischen. B in C lösen; diese Lösung in A einrühren. Danach die Komponenten D zufügen. Mix components A together. Solve B in C; stir this solution into A. Then add components D.

Beispiel 2Example 2

AA Genapol DU 080Genapol DU 080 10.00 Gew.-%10.00% by weight DiethylenglykolmonobutyletherDiethylene glycol monobutyl ether 4.95 Gew.-%4.95% by weight BB Wasserwater CC. Hostapur SAS 60Hostapur SAS 60 8.40 Gew.-%8.40% by weight Genapol ZROflüssigGenapol ZRO liquid 1.40 Gew.-%1.40% by weight Serusweet 83 (Fa. Diedrichs)Serusweet 83 (Diedrichs) 6.00 Gew.-%6.00% by weight DD Acticide SPC-(L)Acticide SPC- (L) 0.20 Gew.-%0.20% by weight

HerstellungManufacturing

Alle Komponenten von A nacheinander in B lösen, danach die Komponenten von C einrühren, abschließend D zugeben.Solve all components of A in succession in B, then the components of C stir in, finally add D.

Feinwaschmittel für HandwäscheDelicate detergent for hand washing Beispiel 1example 1

AA Genapol DU 80Genapol DU 80 6.00 Gew.-%6.00% by weight Fettsäuremischung (Prifac 7949: Palmkernöl-/Ölsäure)Fatty acid mixture (Prifac 7949: palm kernel oil / oleic acid) 5.00 Gew.-%5.00% by weight Kaliumhydroxid (w = 85 %)Potassium hydroxide (w = 85%) 0.80 Gew.-%0.80% by weight TriethanolaminTriethanolamine 0.69 Gew.-%0.69% by weight BB E-Wasser (ca. 50°C)E-water (approx. 50 ° C) CC. Hostapur SAS 60Hostapur SAS 60 5.10 Gew.-%5.10% by weight tri-Natriumcitrat-2-hydrattri sodium citrate 2 hydrate 5.00 Gew.-% 5.00% by weight DD EthanolEthanol 2.00 Gew.-%2.00% by weight Citronensäure-1-hydratCitric acid 1 hydrate 0.20 Gew.-%0.20% by weight Serusweet 83Serusweet 83 6.00 Gew.-%6.00% by weight EE Acticide SPX-(L)Acticide SPX- (L) 0.20 Gew.-%0.20% by weight

HerstellungManufacturing

Komponenten A vermischen, B dazugeben und gut lösen. Danach die Komponenten & einrühren und auf Raumtemperatur abkühlen lassen. Komponenten D nacheinander hinzufügen, abschließend E zufügen.Mix components A, add B and dissolve well. Then the components & stir in and allow to cool to room temperature. Components D add one after the other, finally add E.

Chemische Beschreibung der eingesetzten Handelsprodukte

Hostapur® SAS 60:
sekundäres Natriumalkansulfonat
Genapol® LRO flüssig:
C12/C14-Natriumalkyldiglycolethersulfat
Genagen® LAB:
C12/C14-Alkyldimethylbetain
Genapol® DU 080:
C11 Oxoalkoholpolyglykolether mit 8 Ethylenoxid
Genapol® ZRO flüssig
C12/C14 Natriumalkyltriglycolethersulfat
Chemical description of the commercial products used
Hostapur® SAS 60:
secondary sodium alkane sulfonate
Genapol® LRO liquid:
C12 / C14 sodium alkyl diglycol ether sulfate
Genagen® LAB:
C12 / C14 alkyl dimethyl betaine
Genapol® DU 080:
C11 oxo alcohol polyglycol ether with 8 ethylene oxide
Genapol® ZRO liquid
C12 / C14 sodium alkyl triglycol ether sulfate

Die oben genannten Produkte sind Handelsprodukte der Hoechst Aktiengesellschaft, Frankfurt/Main.

Serusweet®:
sprühgetrocknete Süßmolke, bestehend aus Laktose-Monohydrat (min. 83 %)
Mineralstoffe
8+/-2 %
Protein
4+/-1 %
Feuchtigkeit
max. 3 %
Handelsprodukt der Fa. F.H. Diedrichs GmbH, Mannheim
Acticid®:
Konservierungsmittel
Handelsprodukt der Fa. Thor Chemie GmbH, Speyer.The above products are commercial products from Hoechst Aktiengesellschaft, Frankfurt / Main.
Serusweet®:
spray-dried sweet whey, consisting of lactose monohydrate (min. 83%)
Minerals
8 +/- 2%
protein
4 +/- 1%
humidity
Max. 3%
Commercial product from FH Diedrichs GmbH, Mannheim
Acticid®:
Preservative
Commercial product from Thor Chemie GmbH, Speyer.

Claims (6)

Wasch- und Reinigungsmittel enthaltend Süßmolke.Detergent and cleaning agent containing sweet whey. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß sie 0,1 bis 15 Gew.-% Süßmolke enthalten.Detergent and cleaning agent according to claim 1, characterized in that they contain 0.1 to 15 wt .-% sweet whey. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß sie 2 bis 7 Gew.-% Süßmolke enthalten.Detergent and cleaning agent according to claim 1, characterized in that they contain 2 to 7 wt .-% sweet whey. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß es sich um Handgeschirrspülmittel, flüssige Allzweckreiniger oder flüssige Feinwaschmittel handelt.Detergent and cleaning agent according to claim 1, characterized in that it is hand dishwashing liquid, liquid all-purpose cleaner or liquid mild detergent. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß sie zusätzlich anionische, kationische, amphotere und/oder nichtionische Tenside und Zusatzstoffe enthalten.Detergent and cleaning agent according to claim 1, characterized in that they are additionally anionic, cationic, amphoteric and / or nonionic Contain surfactants and additives. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß sie eine Süßmolke enthalten, die 50 bis 100 Gew.-% Lactosemonohydrat, 6 bis 10 Gew.-% Mineralstoffe, 3 bis 5 Gew.-% Proteine und bis zu 3 Gew.-% Wasser enthält.Detergent and cleaning agent according to claim 1, characterized in that they contain a sweet whey, the 50 to 100 wt .-% Lactose monohydrate, 6 to 10% by weight minerals, 3 to 5% by weight proteins and contains up to 3% by weight of water.
EP98114591A 1997-08-18 1998-08-04 Detergent and cleaning agents Withdrawn EP0897973A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997135763 DE19735763A1 (en) 1997-08-18 1997-08-18 Detergents and cleaners
DE19735763 1997-08-18

Publications (1)

Publication Number Publication Date
EP0897973A1 true EP0897973A1 (en) 1999-02-24

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EP (1) EP0897973A1 (en)
JP (1) JPH11152495A (en)
DE (1) DE19735763A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001055290A1 (en) * 2000-01-27 2001-08-02 Henkel Kommanditgesellschaft Auf Aktien Surfactant combination
DE102005042603A1 (en) * 2005-09-07 2007-03-08 Henkel Kgaa Skin care hand dishwashing liquid
WO2007057080A1 (en) * 2005-11-18 2007-05-24 Henkel Ag & Co. Kgaa Textile treatment agent comprising a milk product
EP2770043A1 (en) * 2013-02-21 2014-08-27 Lina Line ® E.U. Detergent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2015367344A1 (en) 2014-12-19 2017-07-13 Clariant International Ltd Aqueous electrolyte-containing adjuvant compositions, active ingredient-containing compositions and the use thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB159083A (en) * 1920-01-07 1921-02-24 Charles Samuel Townsend Improvements in and relating to soap
DE2638089A1 (en) * 1976-08-24 1978-03-02 Degussa Stabilised lipase prepn(s). - contg. as stabiliser sweet whey powder consisting of lactose whey protein, milk fat, whey minerals and water
GB1551074A (en) * 1975-08-20 1979-08-22 Procter & Gamble Liquid dishwashing compositions
EP0245551A1 (en) * 1985-05-10 1987-11-19 Unilever N.V. Detergent granules
BE1003561A3 (en) * 1989-10-11 1992-04-21 Met Beperkte Aansprakelijkheid Liquid detergents
WO1993001269A1 (en) * 1991-07-01 1993-01-21 Unilever Plc Antifoam ingredient
WO1994019529A1 (en) * 1993-02-26 1994-09-01 Thomas Vollmond A process for providing localized variation in the colour density of fabrics
EP0635569A2 (en) * 1993-07-19 1995-01-25 Unilever N.V. Liquid cleaning products
CA2101622A1 (en) * 1993-07-29 1995-01-30 Herbert Gorge Production process for whey based detergents, soaps and cosmetics
WO1997014780A1 (en) * 1995-10-16 1997-04-24 Unilever N.V. Encapsulated bleach particles

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB159083A (en) * 1920-01-07 1921-02-24 Charles Samuel Townsend Improvements in and relating to soap
GB1551074A (en) * 1975-08-20 1979-08-22 Procter & Gamble Liquid dishwashing compositions
DE2638089A1 (en) * 1976-08-24 1978-03-02 Degussa Stabilised lipase prepn(s). - contg. as stabiliser sweet whey powder consisting of lactose whey protein, milk fat, whey minerals and water
EP0245551A1 (en) * 1985-05-10 1987-11-19 Unilever N.V. Detergent granules
BE1003561A3 (en) * 1989-10-11 1992-04-21 Met Beperkte Aansprakelijkheid Liquid detergents
WO1993001269A1 (en) * 1991-07-01 1993-01-21 Unilever Plc Antifoam ingredient
WO1994019529A1 (en) * 1993-02-26 1994-09-01 Thomas Vollmond A process for providing localized variation in the colour density of fabrics
EP0635569A2 (en) * 1993-07-19 1995-01-25 Unilever N.V. Liquid cleaning products
CA2101622A1 (en) * 1993-07-29 1995-01-30 Herbert Gorge Production process for whey based detergents, soaps and cosmetics
WO1997014780A1 (en) * 1995-10-16 1997-04-24 Unilever N.V. Encapsulated bleach particles

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001055290A1 (en) * 2000-01-27 2001-08-02 Henkel Kommanditgesellschaft Auf Aktien Surfactant combination
EP1564283A3 (en) * 2000-01-27 2006-06-07 Henkel Kommanditgesellschaft auf Aktien Surfactant combination
DE102005042603A1 (en) * 2005-09-07 2007-03-08 Henkel Kgaa Skin care hand dishwashing liquid
WO2007057080A1 (en) * 2005-11-18 2007-05-24 Henkel Ag & Co. Kgaa Textile treatment agent comprising a milk product
EP2770043A1 (en) * 2013-02-21 2014-08-27 Lina Line ® E.U. Detergent

Also Published As

Publication number Publication date
JPH11152495A (en) 1999-06-08
DE19735763A1 (en) 1999-02-25

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