EP1212400B1 - Detergent en pastilles - Google Patents

Detergent en pastilles Download PDF

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Publication number
EP1212400B1
EP1212400B1 EP00960612A EP00960612A EP1212400B1 EP 1212400 B1 EP1212400 B1 EP 1212400B1 EP 00960612 A EP00960612 A EP 00960612A EP 00960612 A EP00960612 A EP 00960612A EP 1212400 B1 EP1212400 B1 EP 1212400B1
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EP
European Patent Office
Prior art keywords
acid
contain
proteins
weight
alcohol
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Expired - Lifetime
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EP00960612A
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German (de)
English (en)
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EP1212400A1 (fr
Inventor
Manfred Weuthen
Bernd Fabry
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • 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
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • 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
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/32—Protein hydrolysates; Fatty acid condensates thereof

Definitions

  • the invention is in the field of molded detergents and relates to tablets with surfactants, Builders and disintegrants which additionally contain proteins or protein derivatives as anti-caking agents.
  • Detergents are available on the market that not only clean the laundry, but also a special one Give soft handle.
  • Such preparations which are often referred to as soft detergents, usually contain cationic surfactants of the tetraalkylammonium compound type as finishing agents, mostly in combination with layered silicates.
  • the quaternary ammonium compounds mentioned are unsatisfactory in terms of their biodegradability, and it is also known that with laundry treated with them can cause irritation to very sensitive consumers. In combination Anionic surfactants also easily lead to undesirable salt formation. Out therefore there is a keen interest in substitutes that are free from these disadvantages.
  • the object of the present invention was to provide new shaped detergents, preferably in the form of tablets available with regard to their ecotoxicological Tolerance no longer objectionable and easily soluble under washing conditions, a sufficient one show chemical resistance and excellent, especially in laundry Give soft handle.
  • the detergent tablets of the invention meet the requirements mentioned in an excellent manner.
  • the non-enzymatic proteins and protein derivatives are ideal substitutes for cationic surfactants, as they have a comparable finish cause, but are also chemically stable under alkaline conditions and neither from ecological still give cause for complaint from a toxicological point of view.
  • Zeolites as builders are observed to have a particularly advantageous softening effect, which is due to the addition of layered silicates and / or the use of a surfactant system based on alkylbenzenesulfonates and alkyl sulfates can be further improved.
  • the detergents are preferably free of cationic surfactants.
  • the detergents can contain anionic, nonionic and / or amphoteric or zwitterionic surfactants as component (a); however, anionic surfactants or combinations of anionic and nonionic surfactants are preferably present.
  • anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin 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, mono (sulfide) sulfate, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sul
  • 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-Ph-SO 3 X (I) in which R stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • 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 dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts
  • 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 O-SO 3 Y (II) in which 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, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol as well as 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 C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C 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-containing olefins using the shop process.
  • 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 by 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-OX (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, petoleic acid, linoleic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic 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 are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (in particular vegetable products based on wheat), polyol, Zuckerester, sorbitan esters , Polysorbates and amine oxides.
  • the 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.
  • the preferred fatty alcohol polyglycol ethers follow the formula (IV) R 4 O (CH 2 CHR 5 O) n H (IV) in which 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 and 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 with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R 6 CO- (OCH 2 CHR 7 ) m OR 8 (V) in which 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 and m is a number from 1 to 20 stands.
  • Typical examples are the formal insert products of on average 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, arachidic acid, gadoleic acid, behenic acid and technical grade and erucas.
  • 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. Reaction 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 O- [G] p (VI) in which R 9 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature, reference is made here to the documents EP-A1 0 301 298 and WO 90/03977 .
  • 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 oligoglycosides are thus alkyl and / or alkenyl oligo glucosides .
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • 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 their technical mixtures, as described above, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • the surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 34-124 or J.Falbe (ed.), “Catalysts, Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217 .
  • the detergents can contain the surfactants in amounts of 1 to 50, preferably 5 to 25 and in particular 10 to 20% by weight, based on the detergents.
  • Non-enzymatic proteins and their derivatives are known substances that are used, for example, in skin care products [cf. Soap-Fat-Oil-Waxes, 108 , 117 (1982)].
  • the addition "non-enzymatic" was chosen to distinguish the substances from typical detergent enzymes, which are not used in the sense of the invention.
  • Typical examples of non-enzymatic proteins that can be used in the agents according to the invention are keratin, elastin, collagen, wheat proteins, milk proteins, protein proteins, silk proteins, almond proteins, soy proteins and other cereal proteins, and proteins from animal skins.
  • Protein hydrolysates are degradation products of these animal or vegetable proteins, which are cleaved by acidic, alkaline and / or enzymatic hydrolysis and then have an average molecular weight in the range from 600 to 4000, preferably 2000 to 3500.
  • protein hydrolyzates in the absence of a hydrophobic residue, are not surfactants in the classical sense, they are widely used for the formulation of surface-active agents because of their dispersing properties. Overviews of the production and use of protein hydrolyzates are, for example, from G. Schuster and A. Domsch in Seifen ⁇ le Fette Wachsen , 108, 177 (1982) and Cosm.Toil. 99, 63 (1984), by HW Steisslinger in Parf. Kosm.
  • Protein fatty acid condensates are obtained by reacting the protein hydrolysates mentioned with fatty acids which generally contain 6 to 22 and preferably 12 to 18 carbon atoms in the acyl radical.
  • the condensates are usually used in the form of their alkali, alkaline earth, ammonium, alkylammonium or alkanolammonium salts.
  • Typical examples are the condensation products of wheat or soy protein hydrolyzates with 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, petroselachic acid, linoleic acid, linoleic acid , Behenic acid and erucic acid and their technical mixtures.
  • the agents according to the invention can contain the proteins or protein derivatives in amounts of 0.1 to 10, preferably 1 to 8 and in particular 3 to 5% by weight, based on the agents.
  • the detergents according to the invention may contain zeolites as builders (component c).
  • the fine crystalline, synthetic and bound water-containing zeolite frequently used as a detergent builder 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.
  • zeolite X and mixtures of A, X and / or P and Y are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production.
  • the zeolite can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, 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.
  • disintegrant component d
  • component d is to be understood as meaning substances which are added to the shaped bodies in order to accelerate their disintegration when they come into contact with water. Overviews can be found, for example, in J.Pharm.Sci. 61 (1972) or Römpp Chemilexikon, 9th edition, volume 6, p. 4440.
  • the disintegrants can be macroscopically distributed homogeneously in the molded body, but microscopically they form zones of increased concentration due to the manufacturing process.
  • the preferred disintegrants include polysaccharides such as natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinylpyrrolidone, collidone, alginic acid and their alkali salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems.
  • polysaccharides such as natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinylpyrrolidone, collidone, alginic acid and their alkali salt
  • disintegrants which may be present in the sense of the invention are, for example, the publications WO 98/40462 (Rettenmeyer), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 (Henkel) refer to. Reference is expressly made to the teaching of these writings.
  • the moldings can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.
  • compositions according to the invention are additional inorganic and organic builder substances, the inorganic builder substances being mainly crystalline Layered silicates and amorphous silicates with builder properties and - where permitted - also phosphates how tripolyphosphates are used.
  • the amount of co-builder is preferred Count amounts of zeolites.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, 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 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 Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method 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. However, smectites, in particular bentonites, are preferred here.
  • small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range from 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 .
  • Layered silicates are preferably used which 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 modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 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 / sealing or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • 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 run washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning 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 amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 .
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons.
  • Suitable are in particular the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphate.
  • Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent.
  • tripolyphosphates in small amounts up to a maximum of 10% by weight. based on the finished agents, in combination with other builder substances to a synergistic improvement of secondary washing power.
  • Useful organic builders are, for example, those that can be used in the form of their sodium salts
  • Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as 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.
  • an acidifying component typically also serve to set a lower and milder pH value of Detergents or cleaning agents.
  • 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, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights 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 and 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 at C 6 of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates , such as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 . Suitable amounts used in formulations containing zeolite and / or silicate are from 3 to 15% by weight.
  • 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 salts 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.
  • the 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, are salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, or, according to DE 4221381 C2, are 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 to be mentioned as further preferred builder 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 mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components that make the oil and fat washable made of textiles.
  • the preferred oil and fat-dissolving components include, for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and that from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives known from technology, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • 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 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 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 sodium silicate content of the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • the agents can include other known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, minor Contain quantities of neutral filling salts as well as colors and fragrances and the like.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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 perborate 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 are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-diacetyloxy, 2,5-ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent
  • hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 19616 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-salt 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 that from German patent application DE known cobalt 19620411 A1, iron-, copper- and ruthenium-ammine complexes, the manganese in the German patent application DE 4416438 A1 described, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0272030 A1 , the manganese ko known from European patent application EP 06
  • 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.
  • Enzymes in particular include those from the class of hydrolases, such as proteases, esterases, Lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases carry in the Laundry for removing stains such as stains containing protein, fat or starch, and Graying at. Cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils help maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used.
  • Bacillus subtilis Especially are particularly suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active substances obtained.
  • Bacillus subtilis preferably Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active substances obtained.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, protease- and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest.
  • lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proved.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases are preferred as cellulases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof. 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 around them protect against premature decomposition.
  • the proportion of 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 0.5 to 1% by weight sodium formate can be used.
  • 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 (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • 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 carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferred. used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners .
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl 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) -diphenyis. Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are also present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even in small amounts, for example Contain 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).
  • 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 about 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. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. 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. Such are called “waxy” Understood compounds that have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably have above 50 ° C and in particular above 70 ° C.
  • the waxy defoamer substances are practically insoluble in water, i.e. at 20 ° C in 100 g of water solubility below 0.1% by weight.
  • Suitable waxy compounds are, for example Bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols as well as paraffin waxes or mixtures thereof. Alternatively, of course, you can also use them Purpose known silicone compounds are 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.
  • paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin.
  • this liquid fraction is as low as possible and preferably completely missing.
  • particularly preferred paraffin wax mixtures at 30 ° C a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still in the case of particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C.
  • the paraffin waxes can be petrolatum, act microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Suitable bisamides as defoamers are those derived from saturated fatty acids with 12 to 22, preferably 14 to 18, carbon atoms and from alkylenediamines with 2 to 7 carbon 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, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and their mixtures and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
  • 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, ethylene glycol and sorbitan, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl 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.
  • esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3 , and carnauba wax , which is a mixture of camamaic acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
  • beeswax which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3
  • carnauba wax which is a mixture of camamaic acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular 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 their mixtures, as made up natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. 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 constructed asymmetrically or symmetrically, ie contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-ioctyl 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 preparation, one starts from, for example, carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example in accordance with German published patent application 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 layered 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 a high rate of dissolution 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 names Aerosil® or Sipemat® 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 cellulose ethers in weight ratios from 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 zeolites are particularly suitable.
  • Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes which are known from the prior art are particularly preferred. However, compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins. As a rule, 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 e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones e.g.
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil.
  • 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 moldings are generally produced by tableting or press agglomeration.
  • the particulate press agglomerates obtained can either be used directly as detergents or previously treated and / or prepared by conventional methods.
  • the usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density.
  • a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , in which dusty or at least finely divided constituents (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as cores, and thus give rise to means , which have these so-called fines as an outer shell. In turn, this advantageously takes place by melting agglomeration.
  • the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
  • the base of these tablets can be circular or rectangular, for example.
  • Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
  • the tablets can also contain pressed and unpressed parts.
  • Shaped articles with a particularly advantageous dissolution rate are obtained if the granular constituents, before pressing, have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight.
  • a particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.
  • Detergent composition and soft handle Composition / performance V1 1 2 3 4 5 6 Dodecylbenzenesulfonate sodium salt 4.0 4.0 4.0 - - 4.0 C 12/18 coconut alcohol sulfate sodium salt 10.0 10.0 16.0 8.0 - - 8.0 C 12/18 coconut fatty acid sodium salt 2.0 2.0 - - - - - C 12/18 coconut fatty alcohol + 7EO 4.0 - - - - - C 12/14 cocoalkyl glucoside - - - 8.0 15.0 10.0 8.0 C 12/18 coconut amphoacetate sodium salt - - - - - 10.0 - Zeolite A 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Collagen coconut fatty acid condensate, sodium salt - 5.0 5.0 5.0 5.0 5.0 layered - - - - - - 5.0 polycarboxylate 5.0 5.0

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Claims (10)

  1. Pastilles détergentes contenant
    (a) des tensioactifs anioniques, non ioniques et/ou amphotères,
    (b) des protéines non enzymatiques et/ou des dérivés de celles-ci,
    (c) des zéolithes et
    (d) des agents désintégrants.
  2. Pastilles détergentes selon la revendication 1,
    caractérisées en ce qu'
    elles contiennent des tensioactifs anioniques choisis dans le groupe constitué des sulfonates d'alkylbenzène, alkylsulfates, savons, sulfonates d'alcanes, sulfonates d'oléfines, sulfonates d'ester méthylique, polyglycol éthers d'alcool gras, esters alkyliques inférieurs d'acides gras alcoxylés et oligoglycosides d'alkyle et/ou d'alcényle.
  3. Pastilles détergentes selon les revendications 1 et/ou 2,
    caractérisées en ce qu'
    elles contiennent les tensioactifs en des quantités allant de 1 à 50 % en poids, rapportées au détergent.
  4. Pastilles détergentes selon au moins une des revendications 1 à 4,
    caractérisées en ce qu'
    elles contiennent des protéines choisies dans le groupe constitué de la kératine, l'élastine, le collagène, les protéines de froment, les protéines de lait, les protéines du blanc d'oeuf, les protéines de soie, les protéines d'amande et les protéines de soja.
  5. Pastilles détergentes selon la revendication 4,
    caractérisées en ce qu'
    elles contiennent lesdites protéines sous la forme d'hydrolysats de celles-ci ou de produits de condensation des hydrolysats avec des acides gras.
  6. Pastilles détergentes selon au moins une des revendications 1 à 5,
    caractérisées en ce qu'
    elles contiennent les protéines ou les dérivés de celles-ci en des quantités allant de 0,1 à 10 % en poids, rapportées au détergent.
  7. Pastilles détergentes selon au moins une des revendications 1 à 6,
    caractérisées en ce qu'
    elles contiennent des zéolithes A, des zéolithes P, des zéolithes X ou des mélanges de celles-ci.
  8. Pastilles détergentes selon au moins une des revendications 1 à 7,
    caractérisées en ce qu'
    elles contiennent les zéolithes en des quantités allant de 10 à 60 % en poids, rapportées au détergent.
  9. Pastilles détergentes selon au moins une des revendications 1 à 8,
    caractérisées en ce qu'
    elles contiennent des agents désintégrants choisis dans le groupe constitué des polysaccharides, de la polyvinylpyrrolidone, de la collidone, de l'acide alginique et des sels alcalins de celui-ci, des silicates lamellaires amorphes ou partiellement cristallins, des polyuréthanes et des polyéthylèneglycols.
  10. Pastilles détergentes selon au moins une des revendications 1 à 9,
    caractérisées en ce qu'
    elles contiennent les agents désintégrants en des quantités allant de 0,1 à 25 % en poids, rapportées au produit détergent.
EP00960612A 1999-09-15 2000-09-06 Detergent en pastilles Expired - Lifetime EP1212400B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19944222A DE19944222A1 (de) 1999-09-15 1999-09-15 Waschmitteltabletten
DE19944222 1999-09-15
PCT/EP2000/008688 WO2001019952A1 (fr) 1999-09-15 2000-09-06 Detergent en pastilles

Publications (2)

Publication Number Publication Date
EP1212400A1 EP1212400A1 (fr) 2002-06-12
EP1212400B1 true EP1212400B1 (fr) 2004-08-18

Family

ID=7922126

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00960612A Expired - Lifetime EP1212400B1 (fr) 1999-09-15 2000-09-06 Detergent en pastilles

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EP (1) EP1212400B1 (fr)
AT (1) ATE274048T1 (fr)
DE (2) DE19944222A1 (fr)
ES (1) ES2226912T3 (fr)
WO (1) WO2001019952A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240010946A1 (en) * 2020-09-09 2024-01-11 Conopco, Inc., D/B/A Unilever Laundry composition
WO2024160934A1 (fr) * 2023-02-02 2024-08-08 Amsilk Gmbh Composition d'aide au rinçage comprenant un polypeptide structural
EP4410938A1 (fr) * 2023-02-02 2024-08-07 AMSilk GmbH Composition pour lave-vaisselle automatique comprenant un polypeptide structurel
WO2024160933A1 (fr) * 2023-02-02 2024-08-08 Amsilk Gmbh Composition de détergent à lessive comprenant un polypeptide structural

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2147443A5 (en) * 1971-07-28 1973-03-09 Dynachim Sarl Neutral detergents without phosphates - for all fibre types
DE3228479A1 (de) * 1982-07-30 1984-02-09 Dénes 7312 Kirchheim Pötschke Waschmittel fuer textilien
DE3827895A1 (de) * 1988-08-17 1990-02-22 Henkel Kgaa Verfahren zur herstellung phosphatreduzierter waschmitteltabletten
GB9114184D0 (en) * 1991-07-01 1991-08-21 Unilever Plc Detergent composition
DE4129993C2 (de) * 1991-09-10 1999-10-14 Kreussler Chem Fab Waschmittel
GB9501112D0 (en) * 1995-01-20 1995-03-08 Procter & Gamble Detergent compositions comprising stabilised polyamino acid compounds
DE19801085A1 (de) * 1998-01-14 1999-07-15 Henkel Kgaa Homogene Tensidgranulate für die Herstellung von stückigen Wasch- und Reinigungsmitteln
DE19802409B4 (de) * 1998-01-23 2006-09-21 Ceos Corrected Electron Optical Systems Gmbh Anordnung zur Korrektur des Öffnungsfehlers dritter Ordnung einer Linse, insbesondere der Objektivlinse eines Elektronenmikroskops
DE19803410A1 (de) * 1998-01-28 1999-07-29 Henkel Kgaa Mehrphasige Waschmitteltabletten

Also Published As

Publication number Publication date
ATE274048T1 (de) 2004-09-15
DE50007504D1 (de) 2004-09-23
WO2001019952A1 (fr) 2001-03-22
ES2226912T3 (es) 2005-04-01
DE19944222A1 (de) 2001-03-29
EP1212400A1 (fr) 2002-06-12

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