WO2001027231A1 - Detergents - Google Patents

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Publication number
WO2001027231A1
WO2001027231A1 PCT/EP2000/009547 EP0009547W WO0127231A1 WO 2001027231 A1 WO2001027231 A1 WO 2001027231A1 EP 0009547 W EP0009547 W EP 0009547W WO 0127231 A1 WO0127231 A1 WO 0127231A1
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Prior art keywords
acid
alkyl
alcohol
weight
detergent according
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PCT/EP2000/009547
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German (de)
English (en)
Inventor
Manfred Weuthen
Ditmar Kischkel
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Cognis Deutschland Gmbh
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Publication of WO2001027231A1 publication Critical patent/WO2001027231A1/fr

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the invention is in the field of detergents and relates to preparations with an advanced surfactant system.
  • Detergents are available on the market that not only clean the laundry, but also give it a soft feel.
  • Such preparations which are often referred to as soft detergents, generally contain cationic surfactants of the tetraalkylammonium compound type, usually together with layered silicates, as finishing agents. Since the detergents are usually based on anionic surfactants, undesirable salt formation easily occurs in the presence of cationic surfactants, which leads to the deactivation of some of the detergent-active components and also to deposits on the fibers.
  • the manufacturer of soft dergents to maintain a balance and only use as much cationic surfactant in the formulation as is possible without significant salt formation. As a rule, this amount is still less than 0.5% by weight. With such low application concentrations, it is of course immediately clear why the soft detergents of the market have so far been unsuccessful and have not been able to displace conventional liquid fabric softeners that are only added in the rinse cycle, i.e. after the actual washing has been completed.
  • the object of the present invention was to provide new detergents, preferably in the form of powders, granules, extrudates or agglomerates, in which the problem of salt formation between anionic and cationic surfactants is solved, so that they can be used together with high washing performance larger amounts of cationic surfactants is possible and thus better fiber finish is achieved.
  • the invention relates to detergents containing
  • component (b) is present in amounts of 1 to 20, preferably 2 to 15, in particular 3 to 10 and particularly preferably 5 to 8% by weight.
  • the detergents according to the invention excellently meet the requirements mentioned at the outset.
  • the tetraalkylammonium compounds not only have an improved soft feel, at the same time the tendency to form salts with anionic surfactants is reduced, which makes it possible to produce detergents which have a higher cationic surfactant content than the prior art.
  • zeolites as builders which is further enhanced by the addition of layered silicates and / or the use of an anionic surfactant-free surfactant system based on nonionic and / or amphoteric surfactants, especially alk (en) yl oligoglycosides and / or betaines can be improved.
  • anionic surfactants which can be used as component (a1) are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerolethersulfonates, ⁇ -methyl estersulfonates, sulfofatty acids, alkylsulfates, fatty alcohol ether sulfates, glyceryl ether sulfates, hydroxyl amide ether sulfates, fatty acid amide sulfates, hydroxyl amide ether sulfates, fatty acid (OH) ether sulfates, hydroxyl amine ether sulfates, fatty acid (OH) ether sulfates, (ether) ether sulfates, (ether) ether sulfates, (ether) ether sulfates, (ether) ether sulfates, (ether) ether sulfates,
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Alkyl benzene sulfonates, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are preferably used.
  • Preferred alkylbenzenesulfonates preferably follow the formula (I)
  • R stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph for a phenyl radical
  • X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • dodecyibenzene sulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II)
  • R 2 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
  • Alkyl sulfates based on Ci6 / 18 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.
  • these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-olefins using the shop method.
  • Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
  • oxo alcohols such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins.
  • These alcohol mixtures are a mixture of strongly branched alcohols.
  • Such alcohol mixtures are commercially available under the trade name Lial®.
  • Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
  • soaps are to be understood as meaning fatty acid salts of the formula (III)
  • R 3 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, petol acid Linolenic acid, elaleostearic acid, arachic acid, gadoic acid, behenic acid and erucic acid and their technical mixtures.
  • coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.
  • nonionic surfactants which can be considered as component (a2) are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoyl amide glyglyol glycoside, fatty acid polyglycol ethers (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides are preferably used.
  • R 4 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 5 represents hydrogen or methyl
  • n represents numbers from 1 to 20.
  • Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol , Elaidyl Alcohol, Petroselinyl Alcohol, Linolyl Alcohol, Li ⁇ olenyl Alcohol, E-Laeostearyl Alcohol, Arachyl Alcohol, Gadoleyl Alcohol, Behenyl Alcohol, Erucyl Alcohol and Brassidyl Alcohol hol and their technical mixtures. Addition products of 3, 5 or are particularly preferred
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)
  • R 6 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms
  • R 7 is hydrogen or methyl
  • R 8 is a linear or branched alkyl radical having 1 to 4 carbon atoms
  • m is a number from 1 to 20 stands.
  • Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid , 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid and behenic acid and behenic acid, behenic acid.
  • the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VI),
  • R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G represents a sugar radical having 5 or 6 carbon atoms
  • p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglucosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1, 2 and 1, 4 lies.
  • the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 9 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above.
  • Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.
  • Amphoteric surfactants that can be used as component (a3) are often equated with the term betaines. These are known surfactants which are predominantly prepared by carboxyalkylation, preferably carboxymethylation, of aminic compounds.
  • the starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid is also possible.
  • alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines, which follow the formula (VII), 11
  • R12 in which R 10 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 11 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 12 for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and Y for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, Ci2 / ⁇ 4 -Kokosal- kyldimethylamin, Myristyldimet ylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl- amine, oleyl dimethyl amine, Ci6 / 18 tallow alkyl dimethyl amine, and their technical mixtures.
  • R 13 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • m represents numbers from 1 to 3
  • R 1 , R 12 , n and Y have the meanings given above.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-
  • Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
  • polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again Ci2 / i4 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the detergents can contain the surfactants which form the components (a) in amounts of 1 to 50, preferably 5 to 25 and in particular 10 to 20% by weight, based on the detergents.
  • tetraalkylammonium tetraalkylammonium
  • Tetraalkylammonium compounds used as component (b) are to be understood as cationic surfactants in which the quaternary nitrogen is substituted by 4 alkyl radicals.
  • the alkyl radicals can in turn also carry substituents, e.g. Hydroxy groups or phenyl radicals.
  • the quaternary nitrogen can also be part of a naphthenic ring system.
  • Tetraalkylammonium compounds which are suitable for the purposes of the invention preferably follow the formula (IX),
  • R 14 for a linear or branched, optionally hydroxy-substituted alkyl radical having 6 to 22 carbon atoms or a benzyl radical
  • R 15 and R 16 independently of one another for an optionally hydroxy-substituted alkyl radical with 1 to 22 carbon atoms
  • R 17 for an optionally hydroxy-substituted alkyl radical with 1 to 4 carbon atoms
  • Z represents halide, alkyl sulfate or alkyl phosphate.
  • the tetraalkylammonium compounds have one or two long-chain and two or three short-chain substituents, as is the case, for example, with dimethyl-distearylammonium chloride.
  • Other particularly suitable compounds are cetyltrimethylammonium chloride (Dehyquart® A, Cognis Deutschland GmbH / Duesseldorf) and in particular hydroxycetyl hydroxyethyl dimonium chloride (Dehyquart® E, Cognis Deutschland GmbH / Duesseldorf).
  • the detergents according to the invention can contain zeolites as builders (component c).
  • the fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent fluid is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P and Y are also suitable.
  • zeolite X and mixtures of A, X and / or P and Y are also suitable.
  • zeolite X and mixtures of A, X and / or P and Y are also suitable.
  • zeolite X and mixtures of A, X and / or P and Y are also suitable.
  • VEGOBOND AX ® commercial product from Condea Augusta SpA
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • these may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups, C ⁇ 2 -C 4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 microns (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • the zeolites are contained in the final preparations preferably in amounts of 10 to 60, in particular 20 to 40% by weight, based on the composition.
  • Further preferred ingredients of the detergents according to the invention are additional inorganic and organic builder substances, crystalline phyllosilicates and amorphous silicates with builder properties being used primarily as inorganic builder substances, and, where permissible, phosphates such as tripolyphosphates are also used.
  • the amount of co-builder is to be counted against the preferred amounts of zeolites.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2x + ryH2 ⁇ , where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and is preferred Values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na2Si2 ⁇ 5-yH2 ⁇ are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171.
  • Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1. Their usability is not limited to a special composition or structural formula.
  • smectites, in particular bentonites are preferred here.
  • Suitable layered silicates, which belong to the group of water-swellable smectites are, for example, those of the general form
  • the layered silicates can also contain hydrogen, alkali and alkaline earth ions, in particular Na and Ca 2+ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1.
  • preferential Layered silicates are used that are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • the preferred builder substances also include amorphous sodium silicates with a Na ⁇ O: Si0 2 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “roentgenamo ⁇ h”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
  • This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1.
  • Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray-silicate silicates are particularly preferred.
  • phosphates As builders, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used.
  • a preferred dextrin is described in British patent application GB 9419091 A1 ,
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
  • An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable.
  • a product oxidized to C ⁇ of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates are also particularly preferred, as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0150930 A1 and Japanese Patent Application JP 93/339896.
  • Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • Suitable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium sets of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • Granular polymers are usually subsequently mixed into one or more basic granules.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids are also salts or their full-body substances. Polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na ⁇ O: Si0 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
  • the content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • the agents can contain other known additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, small amounts of neutral filler salts and colorants and fragrances and the like.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using boron monohydrate or percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable.
  • hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 19620411 A1, the manganese, copper and cobalt described in German patent application DE 4416438 A1.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydroiases can help maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microf
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amyiases, pululanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B 4 ⁇ 7).
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carbo- oxymethyl cellulose and mixtures thereof, and also polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-mo ⁇ holino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which replace the Mo ⁇ holino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyrene type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl , or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example 10 "6 to 10 " 3 wt .-%, preferably by 10- 5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
  • Suitable soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers are characterized by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20.
  • Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • Wax-like compounds can be used as defoamers.
  • Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C. are understood as “waxy”.
  • the waxy defoamer substances are practically insoluble in water, ie at 20 ° C. they have a solubility of less than 0.1% by weight in 100 g of water.
  • all wax-like defoamer substances known from the prior art can be present.
  • Suitable wax-like compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohol - len as well as paraffin waxes or mixtures thereof.
  • the silicone compounds known for this purpose can of course also be used.
  • Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420, and / or its solidification point , This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C.
  • paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.
  • the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Suitable bisamides as defoamers are those which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylene diamine, 1,3-propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, p-phenylene diamine and tolylene diamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoyiethylenediamine, bisstearoylethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol monostearate, ethylene glycol and rat sorbitan, sorbitan Sorbitanmonolau-, Sorbitandilaurat, sorbitan, sorbitan dioleate, and sorbitan mixed tallow alkyl and diesters.
  • Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
  • suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) 24COO (CH2) 27CH3 and CH 3 (CH 2 ) 26COO (CH2) 25CH 3
  • carnauba wax which is a mixture of Carnauba acid alkyl esters, often in combination with small amounts of free camamauba acid, other long-chain acids, high molecular weight alcohols and hydrocarbons.
  • Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, as are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
  • Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
  • Dialkyl ethers may also be present as defoamers.
  • the ethers can be asymmetrical or symmetrical, i.e. contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms.
  • Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.
  • Suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. For their production, one starts from, for example, carboxylic acid magnesium salts which are below at temperatures above 300 ° C. Elimination of carbon dioxide and water are pyrolyzed, for example according to the German laid-open specification DE 2553900 OS.
  • Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid.
  • Suitable defoamers are fatty acid polyethylene glycol esters, which are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids.
  • the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
  • alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds.
  • the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
  • the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
  • the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
  • the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
  • suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic see cellulose ethers in weight ratios of 80:20 to 40:60, in particular from 75:25 to 50:50.
  • native starch which is composed of amylose and amylopectin. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeotites are particularly suitable.
  • Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanated.
  • organopoysiloxanes are described, for example, in European patent application EP 0496510 A1.
  • Polydiorganosiloxanes which are known from the prior art are particularly preferred.
  • compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins.
  • the polydiorganosiloxanes contain finely divided silica, which can also be silanized.
  • Silica-containing dimethylpolysiloxanes are particularly suitable.
  • the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
  • the silicones are preferably applied to carrier materials. Suitable carrier materials have already been described in connection with the paraffins.
  • the carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl and benzylatepylpropionate, stylate propionate.
  • the ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, ⁇ -isomethylionone and methylcedrylke - clay, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the te ⁇ ene such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the final preparations can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
  • the detergents obtainable using the additives according to the invention can be produced or used in the form of powders, extrudates, granules or agglomerates. These can be both universal and delicates or color detergents, optionally in the form of compact or super-compact.
  • the corresponding methods known from the prior art are suitable for producing such agents.
  • the agents are preferably prepared by mixing different particulate components which contain detergent ingredients.
  • the particulate components can be produced by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation. It can furthermore be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate are sprayed together with other detergent ingredients in a drying device, wherein granulation can take place simultaneously with the drying.
  • the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner.
  • Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention.
  • the mixtures are then subjected to a compacting step, further ingredients being added to the agents only after the compacting step.
  • the ingredients are compacted in a press agglomeration process.
  • the press agglomeration process to which the solid premix (dried basic detergent) is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used.
  • the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roller pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes in the context of the present invention are extrusion, roller compacting, pelletizing - or tableting processes.
  • binders can be used as an aid to compaction.
  • a binder is used which is already completely in the form of a melt at temperatures up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C.
  • the binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.
  • the actual compression process preferably takes place at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
  • the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technical quite possible to set even higher temperatures; However, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages.
  • thermoly sensitive raw materials for example peroxygen bleaching agents such as perborate and / or percarbonate, but also enzymes, can be processed increasingly without serious loss of active substance.
  • peroxygen bleaching agents such as perborate and / or percarbonate, but also enzymes.
  • the possibility of precise temperature control of the binder in particular in the decisive step of compaction, i.e. between the mixing / homogenization of the premix and the shaping, permits an energetically very economical and extremely gentle process control for the temperature-sensitive components of the premix, since the premix only lasts for a short time exposed to higher temperatures.
  • the work tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of at most 150 ° C., preferably at most 100 ° C. and in particular to a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression range of the press agglomerators is preferably a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • Preferred binders which can be used alone or in a mixture with other binders, are polyethylene glycols, 1,2-polypropylene glycol and modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also employ C ⁇ -Cs glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
  • the polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used such Combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000.
  • polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
  • these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
  • suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred.
  • Polyvinylpyrrolidones are preferably not used as the sole binders but in combination with others, especially in combination with polyethylene glycols.
  • the compressed material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
  • the detergent according to the invention is produced by means of an extrusion, as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299.
  • a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers.
  • the premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives.
  • the hole diameter of the perforated nozzle plate and the strand cut length are based on the selected granule dimension Voted. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
  • the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
  • the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the detergents according to the invention can also be produced by means of roller compaction.
  • the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified.
  • the Schülpenband is subsequently broken into smaller pieces by a knock-off and comminution process and can be processed in this way to Granulkkömem, which can be refined by other known surface treatment methods, in particular brought into an approximately spherical shape.
  • the temperature of the pressing tools that is to say of the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
  • Particularly preferred manufacturing processes work in roller compacting with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the detergent according to the invention can also be produced by pelleting.
  • the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
  • the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1.
  • the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • Examples 1 to 12 comparative examples V1 to V4.
  • a washing machine Miele W 918
  • 3.5 kg of standard laundry and a terry towel (which was washed twice with a universal detergent for pretreatment) were washed in a full wash at 90 ° C.
  • 84 g of detergent of the composition shown in Table 1 were added to the dispenser immediately before the test.

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

Abstract

L'invention concerne des détergents, contenant (a) des agents tensio-actifs anioniques, non ioniques ou amphotères, (b) des composés tétraalkylammonium et (c) des zéolithes, à condition que le constituant (b) soit présent dans des quantités comprises entre 1 et 20 % en poids.
PCT/EP2000/009547 1999-10-08 2000-09-29 Detergents WO2001027231A1 (fr)

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DE19948671.9 1999-10-08
DE1999148671 DE19948671A1 (de) 1999-10-08 1999-10-08 Waschmittel

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WO2001027231A1 true WO2001027231A1 (fr) 2001-04-19

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GB2370843A (en) * 2001-01-08 2002-07-10 Reckitt Benckiser Nv Laundry cleaning agents and their manufacture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0000225A1 (fr) * 1977-06-29 1979-01-10 THE PROCTER & GAMBLE COMPANY Composition détergente solide pour une meilleure élimination des salissures grasses
GB2159534A (en) * 1984-06-01 1985-12-04 Colgate Palmolive Co Antistatic synthetic organic detergent composition
US4818422A (en) * 1987-09-17 1989-04-04 Colgate-Palmolive Co. Fabric softening detersive article
WO1998017755A1 (fr) * 1996-10-18 1998-04-30 The Procter & Gamble Company Compositions detergentes comprenant un melange de tensioactifs cationiques, anioniques et non ioniques
WO1998017753A1 (fr) * 1996-10-18 1998-04-30 The Procter & Gamble Company Composition detergente contenant un alkyle polysaccharide et des tensioactifs cationiques
WO1999035120A1 (fr) * 1998-01-09 1999-07-15 Witco Corporation Composes d'ammonium quaternaire, compositions a base de ces composes, et utilisations correspondantes

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Publication number Priority date Publication date Assignee Title
ZA776946B (en) * 1976-12-02 1979-06-27 Colgate Palmolive Co Free flowing high bulk density particulate detergent softener
EP0000224A1 (fr) * 1977-06-29 1979-01-10 THE PROCTER & GAMBLE COMPANY Composition détergente liquide pour une meilleure élimination des salissures grasses
US4818421A (en) * 1987-09-17 1989-04-04 Colgate-Palmolive Co. Fabric softening detergent composition and article comprising such composition
DE69113259T2 (de) * 1991-07-08 1996-05-15 Procter & Gamble Polyhydroxyfettsäureamidtenside und ein weichmachendes System auf Basis von Ton enthaltenden Waschmittelzusammensetzungen.
US5223179A (en) * 1992-03-26 1993-06-29 The Procter & Gamble Company Cleaning compositions with glycerol amides
DE69324084T2 (de) * 1992-07-31 1999-10-28 Procter & Gamble Verwendung von modifizierten Polyestern zum Entfernen von Fett aus Textilien
US5415807A (en) * 1993-07-08 1995-05-16 The Procter & Gamble Company Sulfonated poly-ethoxy/propoxy end-capped ester oligomers suitable as soil release agents in detergent compositions
GB2303858A (en) * 1995-08-02 1997-03-05 Procter & Gamble Detergent composition
GB2313603A (en) * 1996-05-31 1997-12-03 Procter & Gamble Detergent compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0000225A1 (fr) * 1977-06-29 1979-01-10 THE PROCTER & GAMBLE COMPANY Composition détergente solide pour une meilleure élimination des salissures grasses
GB2159534A (en) * 1984-06-01 1985-12-04 Colgate Palmolive Co Antistatic synthetic organic detergent composition
US4818422A (en) * 1987-09-17 1989-04-04 Colgate-Palmolive Co. Fabric softening detersive article
WO1998017755A1 (fr) * 1996-10-18 1998-04-30 The Procter & Gamble Company Compositions detergentes comprenant un melange de tensioactifs cationiques, anioniques et non ioniques
WO1998017753A1 (fr) * 1996-10-18 1998-04-30 The Procter & Gamble Company Composition detergente contenant un alkyle polysaccharide et des tensioactifs cationiques
WO1999035120A1 (fr) * 1998-01-09 1999-07-15 Witco Corporation Composes d'ammonium quaternaire, compositions a base de ces composes, et utilisations correspondantes

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