EP1214389B1 - Melanges de tensioactifs - Google Patents

Melanges de tensioactifs Download PDF

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Publication number
EP1214389B1
EP1214389B1 EP00965986A EP00965986A EP1214389B1 EP 1214389 B1 EP1214389 B1 EP 1214389B1 EP 00965986 A EP00965986 A EP 00965986A EP 00965986 A EP00965986 A EP 00965986A EP 1214389 B1 EP1214389 B1 EP 1214389B1
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Prior art keywords
weight
carbon atoms
formula
saturated
unsaturated alcohols
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German (de)
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EP1214389A1 (fr
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Manfred Weuthen
Karl Heinz Schmid
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the invention lies in the field of surfactant mixtures for the production of solid, foam-controlled detergents and concerns surfactant mixtures with high contents specially selected nonionic surfactants and no or only low contents anionic surfactants.
  • Other objects of the present invention relate to solid Foam-controlled detergents containing such surfactant mixtures and the use such surfactant mixtures for the production of solid, foam-controlled Detergents.
  • Detergents for household laundry and industrial laundry generally contain anionic surfactants and nonionic surfactants. Builders as well as numerous organic and inorganic additives.
  • the anionic surfactants used to clean the laundry usually tend to develop foam during the wash cycle, which on the one hand has a negative effect on the washing result and on the other hand can cause the washing machine to overflow. There is therefore a practical need to control the development of foam during the washing process and, in particular, to minimize it.
  • defoamers or so-called antifoam agents are used, which are intended to reduce the development of foam on the one hand and foam that has already formed on the other.
  • anionic surfactants such as alkylbenzenesulfonates (also known as ABS or LAS for short) or fatty alcohol sulfates (also known as FAS for short) can be defoamed relatively easily and reliably with conventional defoamers, for example based on paraffins. Suitable paraffin wax mixtures as defoamers are described, for example, in European patent application EP 0309931 A1 .
  • Defoaming or foam control proves to be more problematic in the case of surfactant mixtures with high levels of nonionic surfactants and especially above all Things if, as nonionic surfactants, alkyl oligoglucosides based on linear Fatty alcohols or branched oxo alcohols are used.
  • Such surfactant mixtures which are characterized by particularly advantageous dissolving properties and therefore for are of particular interest to consumers can only be reliably defoamed up to now if if silicones are used as defoamers, which are usually on carrier materials applied and, if necessary, coated with other substances with a defoaming effect will.
  • defoamers containing silicone are known from European patent application EP 0496510 A1 , a mixture of silicone and fatty alcohols, fatty acids or glycerol monoesters with special melting points being applied to starch as the carrier material. Silicones, however, tend to be sticky because of their stickiness. On the one hand, they have an oily consistency to stick together, which means that unwanted silicone stains can appear as residue on the washed laundry and, on the other hand, the silicones are relatively expensive defoamers.
  • surfactant mixtures with high nonionic contents Surfactants that contain alkyl oligoglycosides that are easier to defoam, whereby on silicones as defoamers at least partially, preferably completely, can be dispensed with.
  • the object of the present invention was therefore to create surfactant mixtures for the production of solid detergents with high levels of nonionic surfactants to make available, in spite of the contained alkyl oligoglycosides already with low levels of defoamers in their foam are controlled. Furthermore should If possible with small amounts or even without silicone as a defoamer a good one Foam control be possible. Of course, the surfactant mixtures or solid detergents based thereon meet the requirements for detergents Meet primary washing power.
  • the present application also relates to the use of the surfactant mixture from described type for the production of solid, foam-controlled detergents.
  • nonionic surfactants of the formula ( II ) which, in simplified terms, are alkoxylates of long-chain alcohols having 16 to 18 carbon atoms, very good foam control is achieved, in particular for the alkyl glycosides which are difficult to defoam. Particularly good results are achieved in terms of washing performance and foam control if additional nonionic surfactants are used, such as short-chain alcohol alkoxylates or branched alcohol alkoxylates and / or fatty acid polyglycol esters.
  • the surfactant mixture according to the invention mandatory nonionic surfactants in amounts of more than 60% by weight to 100% by weight, preferably in amounts of 70 to 98.5% by weight, based on the total surfactant content.
  • the surfactants missing by 100% by weight can on the one hand be anionic surfactants keep that in amounts of 0 to 6 wt .-%, preferably in amounts of 0 to 3 % By weight, in particular in amounts of 0 to 1.5% by weight, are present.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, fatty acid ether sulfates, fatty acid ether sulfates, fatty acid ether sulfates, fatty acid ether sulfates, mono-ether sulfates, fatty acid ether sulfates, monohydric acid sulfates, mono-ether sulfates, fatty acid ether sulfates, mono-methyl ether sulfates, fatty acid ether sulfates, mono-ether
  • no anionic surfactants are added to the surfactant mixture.
  • the surfactant mixture or in the solid detergent can become contaminated anionic surfactants, carried over by the other constituents in subordinate Quantities, to be included.
  • the surfactant mixture can contain cationic, zwitterionic or ampholytic surfactants up to 100% by weight, based on the surfactant mixture.
  • cationic surfactants are quaternary ammonium compounds, such as dimethyldistearylammonium chloride, and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
  • the surfactant mixture according to the invention necessarily contains the nonionic surfactants of the formulas ( I ) and ( II ). Further nonionic surfactants are preferably also contained, with at least one nonionic surfactant of the formulas ( III ) to ( VI ) preferably also being contained.
  • nonionic surfactant mixture can, if required, contain other customary nonionic surfactants, for example alkylphenol polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, partially oxidized alk (en) yl oligoglycosides (especially protein-alkyl glucuric acid derivatives, fatty acid derivatives, alkyl glucoramides, protein, or glucuronic acid derivatives) Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • other customary nonionic surfactants for example alkylphenol polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, partially oxidized
  • nonionic surfactants contain polyglycol ether chains, these can have a conventional or a narrow homolog distribution.
  • the other customary nonionic surfactants are preferably contained in minor amounts, generally up to a maximum of 40% by weight, preferably up to a maximum of 20% by weight and in particular in amounts of 0 to 10% by weight, based on the nonionic surfactant mixture.
  • the nonionic surfactant mixture consists exclusively of the nonionic surfactants of the formulas ( I ) and ( II ).
  • the nonionic surfactants of the formula ( I ) are alkyl and / or alkenyl oligoglycosides. These are known nonionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. As a representative of the extensive literature, reference is made to the overview article by Biermann et al. in Starch / Strength 45, 281 (1993), B. Salka in Cosm.Toil. 108, 89 (1993) and J. Kahre et al. in S ⁇ FW-Journal No. 8, 598 (1995) .
  • 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 oligoglycosides .
  • the index number p in the general formula ( I ) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • 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, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
  • Typical examples are butanol, caproic 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 oxo synthesis.
  • the alkyl or alkenyl radical R 1 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 technical mixtures thereof, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol or branched C 11/15 oxo alcohols with a DP of 1 to 3 are preferred.
  • the nonionic surfactants of the formula ( II ) are alkoxylates of mixtures of linear alcohols which contain 70 to 100% by weight, preferably 80 to 100% by weight, alcohols having 16 to 22 carbon atoms, preferably 16 to 18 Carbon atoms, and from 0 to 30% by weight, preferably from 0 to 20% by weight, of linear alcohols having 6 to 14 carbon atoms.
  • Particularly suitable alcohol mixtures on which the nonionic surfactants of the formula ( II ) are based consist of 0 to 5% by weight, in particular 0 to 2% by weight of linear saturated alcohols having 12 carbon atoms; 0 to 10% by weight, preferably 3 to 8% by weight of linear saturated alcohols with 14 carbon atoms, 20 to 50% by weight, preferably 25 to 35% by weight of linear saturated alcohols having 16 carbon atoms; 50 to 80% by weight, preferably 60 to 70% by weight of linear saturated alcohols having 18 carbon atoms and 0 to 5% by weight, preferably 0 to 2% by weight of linear saturated alcohols having 22 carbon atoms.
  • Such alcohol mixtures can be made from tallow, palm kernel oil or by reducing Aldehydes are obtained from Roelen's oxo synthesis.
  • the alcohol mixtures described have ethylene oxide.
  • Propylene oxide and / or butylene oxide preferably ethylene oxide and / or propylene oxide as block and / or random polymers attached. If ethylene oxide and propylene oxide are attached, the The number of moles of propylene oxide attached is preferably in the range from 0.5 to 5 moles and the number of moles of ethylene oxide attached is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles, of ethylene oxide. Case in point these are block copolymers with 1 mole of propylene oxide and 22 moles of ethylene oxide.
  • alcohol ethoxylates of the formula ( II ) which have added on average from 4 to 12, preferably from 5 to 10, mol of ethylene oxide (x).
  • the nonionic surfactant mixtures contain, in addition to the alkyl polyglycosides of the formula ( I ) and the alcohol alkoxylates of the formula ( II ), at least one of the nonionic surfactants of the formula ( III ), ( IV ), ( V ) and / or ( VI ).
  • the nonionic surfactants of the formula ( III ) (component c1) are alcohol alkoxylates which are derived from slightly branched alcohols.
  • Such low-branched alcohols constitute an alcohol mixture 70 to 95% by weight linear saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 5 to 30% by weight saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and branched with methyl groups 0 to 10% by weight saturated and / or unsaturated alcohols branched with alkyl groups with at least 2 carbon atoms with 8 to 22 carbon atoms, preferably from 73 to 85 wt% linear saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 13 to 25% by weight saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and branched with methyl groups 2 to 7% by weight saturated and / or unsaturated alcohols with 8 to 22 carbon atoms which are branched with alkyl groups with at least 2 carbon atoms
  • alcohol mixtures in which the proportion of methyl-branched alcohols at least 80% by weight, preferably at least 90% by weight of the total branched alcohols present. Such alcohol mixtures are due to a special oxo synthesis known from the prior art by converting carbon monoxide and hydrogen to ⁇ -olefins according to the SHOP accessible. Such alcohol mixtures are commercially available under the trade name Dobanol® or Neodol® available. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45® or Neodol 91®, 1®, 23®, 25®, 45®.
  • R 3 in formula ( III ) stands in particular for alkyl radicals of an alcohol mixture 73 to 85 wt% linear saturated and / or unsaturated alcohols with 12 to 15 carbon atoms and 13 to 25% by weight saturated and / or unsaturated alcohols with 12 to 15 carbon atoms and branched with methyl groups 2 to 7% by weight saturated and / or unsaturated alcohols with 10 to 15 carbon atoms which are branched with alkyl groups with at least 2 carbon atoms.
  • the alcohol mixtures described have ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide as block and / or random polymers attached. If ethylene oxide and propylene oxide are attached, the The number of moles of propylene oxide attached is preferably in the range from 0.5 to 5 moles and the number of moles of ethylene oxide attached is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles, of ethylene oxide. Case in point these are block copolymers with 1 mole of propylene oxide and 22 moles of ethylene oxide.
  • Ethylene oxide adducts of such alcohol mixtures are particularly suitable, with the number of added moles of ethylene oxide in the range from 1 to 20, preferably from 4 to 12 and particularly preferably from 5 to 10, it being understood by those skilled in the art that it is this is a statistical number.
  • the alcohol alkoxylates of the formula ( IV ) are alkoxylates on highly branched alcohol mixtures as obtained by the classic oxo process of Eni or Condea by adding carbon monoxide and hydrogen to olefins which do not exclusively have terminal double bonds .
  • These highly branched alcohol mixtures are a mixture of alcohols 35 to 55% by weight linear saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 10 to 20% by weight saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and branched with methyl groups 35 to 45 wt% saturated and / or unsaturated alcohols with 8 to 22 carbon atoms which are branched with alkyl groups with at least 2 carbon atoms.
  • Particularly suitable alcohol mixtures are those on which the alkoxylates of the formula ( IV ) are based, in which the proportion of branched alcohols - based on alcohol mixture - in total in the range from 50 to 60% by weight and the proportion of linear alcohols in the range from 40 to 50% by weight.
  • Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are the types Lial 91®, Lial 111®, Lial 123®, Lial 125®, Lial 145®.
  • the alcohol mixtures described have ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide as block and / or random polymers attached. If ethylene oxide and propylene oxide are attached, the The number of moles of propylene oxide attached is preferably in the range from 0.5 to 5 moles and the number of moles of ethylene oxide attached is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles, of ethylene oxide. Case in point these are block copolymers with 1 mole of propylene oxide and 22 moles of ethylene oxide.
  • ethylene oxide adducts of such alcohol mixtures are particularly suitable, where the number of added moles of ethylene oxide in the range from 1 to 20, preferably from 4 to 12 and particularly preferably from 5 to 10, it being understood by those skilled in the art that it is this is a statistical number.
  • the nonionic surfactants of the formula ( V ) are alkoxylates of an alcohol mixture of short-chain fatty alcohols 0 to 10% by weight, preferably 0 to 5% by weight of linear saturated and / or unsaturated alcohols having 6 to 10 carbon atoms 40 to 90% by weight, preferably 55 to 85% by weight of linear saturated and / or unsaturated alcohols having 12 to 14 carbon atoms and 0 to 30% by weight, preferably 10 to 25% by weight of linear saturated and / or unsaturated alcohols having 16 to 22 carbon atoms.
  • Such alcohol mixtures are available as cuts, for example from coconut oil or through Reduction of aldehydes accessible from Roelen's oxo synthesis.
  • the alcohol mixtures described have ethylene oxide.
  • Propylene oxide and / or butylene oxide preferably ethylene oxide and / or propylene oxide as block and / or random polymers attached. If ethylene oxide and propylene oxide are attached, the The number of moles of propylene oxide attached is preferably in the range from 0.5 to 5 moles and the number of moles of ethylene oxide attached is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles, of ethylene oxide. Case in point these are block copolymers with 1 mole of propylene oxide and 22 moles of ethylene oxide.
  • the ethylene oxide adducts are particularly suitable, where the number of moles added Ethylene oxide in the range from 1 to 20, preferably from 4 to 12, in particular from 5 to 10, it being clear to the person skilled in the art that this is a statistical number.
  • nonionic surfactants of the formulas ( II ) and ( III ) to ( V ) have the same (statistical) degree of ethoxylation. ie x and y or z or q stand for the same number.
  • the nonionic surfactants of the formula (VI) are preferably addition products of an average of 1 to 30 mol of ethylene and / or propylene oxide with linear or branched, saturated and / or unsaturated fatty acids, such as caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palm oleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, as well as the technical mixtures of erucic acid, as well as in the case of the technical erucic acid, as well as the technical mixtures thereof Fats and oils, arise in the reduction of aldehydes from the Roelen oxo synthesis or
  • Nonionic surfactants of the formula ( VI ) in which R 6 CO stands for an acyl radical with 16 to 18 carbon atoms, R 7 for a methyl group, R for hydrogen and s for numbers from 10 to 15 have proven to be particularly effective defoamers.
  • the most suitable alkoxylated fatty acid esters are those which combine these four structural features.
  • the alkoxylated fatty acid alkyl esters can be prepared in a manner known per se, preferably by alkoxylating the fatty acid alkyl esters in the presence of calcined hydrotalcite.
  • the alkyl polyglycosides of the formula ( I ) (component a) in a weight ratio to the nonionic surfactants of the formula ( II ) (component b) of 20: 1 to 1:20, preferably 10: 1 to 1: 5 and in particular from 10: 1 to 1: 2 to be used.
  • a further nonionic surfactant is included as component c) selected from components c1) to c4), it has proven to be advantageous if the weight ratio of the alkyl glycosides (component a) to the nonionic surfactants (components b + c) is in the range from 10: 1 to 1:20, preferably 5: 1 to 1:10 and in particular 2: to 1: 5.
  • the ratio of the nonionic surfactants of the formula ( II ) (component b) to those of the formulas ( III ) to ( VI ) (component c) is largely uncritical and is advantageously in the range from 1:20 to 20: 1, preferably in the range of 1: 10 to 1: 1 and in particular in the range from 1: 8 to 1: 1.5.
  • the surfactant mixtures according to the invention are contained in the solid detergents in amounts of 5 to 30% by weight, preferably in amounts of 10 to 25 and in particular in amounts of 15 to 25% by weight, based on the detergent.
  • the surfactant mixtures according to the invention are inherently reduced in the foam compared to detergents containing only alkyl polyglycosides, but in order to ensure good foam control, the addition of further defoamers is recommended.
  • the detergents according to the invention contain the defoamers - calculated as the active substance content and based on detergent - preferably in total amounts of 0.05 to 5% by weight, preferably 0.1 to 3 and in particular 0.5 to 2% by weight.
  • waxy defoamer compounds are present as defoamers.
  • "Waxy” is understood to mean those compounds which have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably above 50 ° C and in particular above 70 ° C.
  • the waxy defoamer substances optionally present according to the invention 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. In principle, all waxy defoamer substances known from the prior art can be included.
  • Suitable wax-like compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of monohydric and polyhydric alcohols and 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 freezing point . This is the temperature at which the paraffin changes from the liquid to the solid state through slow cooling. Paraffins which are completely liquid at room temperature, that is to say those with a solidification point below 25 ° C., cannot be used in accordance with the invention.
  • the paraffin wax mixtures known from EP 0309931 A1 can be used, for example, consisting of, for example, 26% by weight to 49% by weight microcrystalline paraffin wax with a solidification point of 62 ° C.
  • paraffins or paraffin mixtures which solidify in the range from 30.degree. C. to 90.degree. C. are preferably used. It should be noted that paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the case of the paraffin waxes which can be used according to the invention, this liquid content is as low as possible and is preferably completely absent.
  • particularly preferred paraffin wax mixtures have a liquid content of less than 10% by weight at 30 ° C., in particular from 2% by weight to 5% by weight, and at 40 ° C. a liquid content of less than 30% by weight, preferably 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid content 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, in particularly preferred paraffin wax mixtures, below 85 ° C, in particular 75 ° C to 82 ° C.
  • the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Bisamides suitable as defoamers are those which are derived from saturated fatty acids having 12 to 22, preferably 14 to 18, carbon atoms and from alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachidic and behenic acids 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 tolylenediamine.
  • Preferred diamines are ethylene diamine and hexamethylene diamine.
  • Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters as defoamers are derived from carboxylic acids having 12 to 28 carbon atoms. In particular, they 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 and also ethylene glycol, glycerol, 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 polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate. Sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate. Sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- 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.
  • Glycerin monostearate glycerin monooleate, glycerin monopalmitate, glycerin monobehenate and glycerin distearate are examples of these.
  • suitable natural 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 carnaubic acid alkyl esters, often in combination with small amounts of free carnaubic acid, other long-chain acids, high molecular weight alcohols and hydrocarbons.
  • Suitable carboxylic acids as further defoamer compounds are in particular behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, such as are obtainable from natural fats or optionally hydrogenated 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 further defoamer compounds are the hydrogenated products of the fatty acids described.
  • Dialkyl ethers can also be included 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-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.
  • ketones of the formula ( VII ), R 9 -CO-R 10 (VII) in which R 9 and R 10 represent, independently of one another, linear or branched hydrocarbon radicals having 11 to 25 carbon atoms and 0 or 1 double bond.
  • ketones are known substances that can be obtained by the relevant methods of preparative organic chemistry. For their preparation one starts, for example, from carboxylic acid magnesium salts, which are pyrolyzed at temperatures above 300 ° C. with elimination of carbon dioxide and water, for example in accordance with the German patent application DE 2553900 OS.
  • Suitable fatty ketones are those obtained by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, arachidic acid, gadoleic acid. Behenic acid or erucic acid.
  • Hentriacontanone-16 is preferred; (R 9 and R 10 stand for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R 9 and R 10 stand for an alkyl radical with 16 carbon atoms), stearon (pentatriacontanone-18; R 9 and R 10 stand for an alkyl radical with 17 Carbon atoms), heptatriacontanone-19 (R 9 and R 10 stand for an alkyl radical with 18 carbon atoms), arachinone (nonatriacontanone-20; R 9 and R 10 stand for an alkyl radical with 19 carbon atoms), hentetracontanone-21 (R 7 and R 8 stands for an alkyl radical with 20 carbon atoms) and / or behenone (triatetracontanone-22; R 9 and R 10 stands for an alkyl radical with 21 carbon atoms).
  • Suitable defoamers are fatty acid polyethylene glycol esters of the formula ( VIII ), R 11 COO (CH 2 CH 2 O) n H (VIII) in which R 11 CO stands for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms and n stands for numbers from 0.5 to 1.5.
  • Fatty acid polyethylene glycol esters of this type are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide onto fatty acids; in particular, the addition of ethylene oxide onto the fatty acids takes place in the presence of alkanolamines as catalysts.
  • alkanolamines especially triethanolamine
  • Fatty acid polyethylene glycol esters of the formula ( VIII ) in which R 11 CO is a linear acyl radical having 12 to 18 carbon atoms and n is the number 1 are preferred for the purposes of the present invention.
  • Lauric acid ethoxylated with 1 mol of ethylene oxide is particularly suitable.
  • the paraffin waxes described are particularly preferably used alone as waxy defoamers or in a mixture with one of the other waxy defoamers, the proportion of paraffin waxes in the mixture preferably being over 50% by weight, based on the waxy defoamer mixture.
  • the paraffin waxes can be applied to carriers.
  • All known inorganic and / or organic carrier materials are suitable as carrier material. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminosilicates, water-soluble sheet silicates, alkali metal silicates, alkali metal sulfates, for example sodium sulfate, and alkali metal 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 resistance and yet 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 phyllosilicates include, for example, amorphous or crystalline water glass.
  • silicates can be used which are commercially available under the name Aerosil® or Sipernat®.
  • film-forming polymers for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch come into consideration as organic carrier materials.
  • Cellulose ethers which can be used are, in particular, alkali metal carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called mixed cellulose ethers, such as methyl hydroxyethyl cellulose and methylhydroxypropyl 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 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 composed of amylose and amylopectin is also suitable as a carrier. Native starch is the term used for starch that can be obtained as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Native starch is a commercially available product and therefore easily accessible.
  • carrier materials one or more of the above-mentioned compounds can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble phyllosilicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • Alkali silicates especially sodium silicate, alkali sulfates, especially sodium sulfate and zeolites.
  • the defoamer used is a mixture of at least one waxy defoamer, preferably a paraffin wax, and a defoaming silicone compound.
  • suitable silicones are customary organopolysiloxanes which can contain finely divided silica, which in turn can also be silanized. Organopolysiloxanes of this type are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes known from the prior art are particularly preferred.
  • Suitable polydiorganosiloxanes can have an almost linear chain and are characterized according to the following formula ( IX ), where R 12 can independently represent an alkyl or an aryl radical and m can stand for numbers in the range from 40 to 1,500.
  • R 12 can independently represent an alkyl or an aryl radical and m can stand for numbers in the range from 40 to 1,500.
  • suitable substituents R 12 are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
  • 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 the defoamer.
  • silicone defoamers it is preferred to use the smallest possible amounts of silicone defoamers get along, preferably the content of silicone in the mixtures with the waxy defoamers - based on the active substance content of the defoamers - a maximum of 50% by weight, preferably a maximum of 30% by weight.
  • Further preferred ingredients of the solid detergents are inorganic and organic Builder substances, the inorganic builder substances mainly being zeolites, crystalline sheet silicates and amorphous silicates with builder properties and - where permitted - Phosphates such as tripolyphosphates are also used.
  • the builders are preferably in the detergents according to the invention in amounts of 10 to 60 % By weight, based on detergent.
  • the finely crystalline, synthetic zeolite containing bound water which is frequently used as 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.
  • 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 in the event that the zeolite is used as a suspension, it 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.
  • 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 of 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline sheet silicates are described, for example, in the European patent application EP 0164514 A1 .
  • Preferred crystalline sheet silicates of the formula given are those in which M stands for sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, ⁇ -sodium disilicate, for example, being able to be obtained by the process described in international patent application WO 91/08171.
  • Further suitable sheet silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their use is not restricted to a specific 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 sheet silicates according to the above formulas.
  • the sheet silicates can contain hydrogen, alkali, alkaline earth metal 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 state of swelling and the type of processing.
  • Usable sheet silicates are known, for example, from US Pat. No. 3,966,629, US Pat. No. 4,062,647, EP 0026529 A1 and EP 0028432 A1 .
  • Layered silicates are preferably used which, due to an alkali treatment, are largely free of calcium ions and strongly coloring iron ions.
  • the preferred builder substances also include amorphous sodium silicates with a Na 2 O: SiO 2 module of 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 with conventional amorphous sodium silicates can be brought about in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not give sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation which have a width of several degree units of the diffraction angle.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolving compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 .
  • Compressed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.
  • the sodium salts of orthophosphates, pyrophosphates and especially tripolyphosphates are particularly suitable. Their content is generally not more than 30% by weight, preferably not more than 25% by weight, based in each case on the finished product. In some cases it has been found 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 detergency.
  • Organic builder substances that can be used 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), provided that 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 in detergents or cleaning agents.
  • Citric acid, succinic acid and glutaric acid are particularly important here.
  • Adipic acid, gluconic acid and any mixtures of these may be mentioned.
  • 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 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 able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their production are, for example, from the European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as the 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.
  • cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • Glycerol disuccinates and glycerol trisuccinates as described, for example, in US patents US Pat. No. 4,524,009, US Pat. No. 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896 , are also particularly preferred.
  • Suitable amounts used in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which can optionally 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 co-builders are described, for example, in the 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 each measured against polystyrene sulfonic acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and 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 particularly suitable.
  • Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000 (each measured against polystyrene sulfonic acid).
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% by weight aqueous solutions being preferred.
  • Granular polymers are usually added to one or more basic granules afterwards.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or according to DE 4221381 C2 as monomers salts of acrylic acid and containing 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 preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids, their salts or their precursors are 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 polyol carboxylic 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 allow oil and fat to be washed out from textiles have a positive effect.
  • Components include, for example, nonionic cellulose ethers such as methyl cellulose and Methylhydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 Wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as the polymers known from the prior art of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers from 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.
  • water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which do not have outstanding builder properties, or mixtures of these; in particular, alkali metal carbonate and / or amorphous alkali metal silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are used.
  • alkali metal carbonate and / or amorphous alkali metal silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content in the detergents according to the invention is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
  • the sodium silicate content of the agents (without particular builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • the agents can contain other known ones in detergents commonly used additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts as well as dyes and fragrances, opacifiers or pearlescent agents.
  • Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
  • Other bleaching agents that can be used are, for example, sodium percarbonate and peroxypyrophosphates. Citrate perhydrates and peracid salts or peracids such as perbenzoates which provide H 2 O 2.
  • the content of bleaching agents in the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, with perborate monohydrate or percarbonate advantageously being used.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable.
  • Polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU),
  • N- are preferred Acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetine, ethylene diacetate 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767
  • hydrophilically substituted acyl acetals known from German patent application DE 19616769 A1 and the acyllactams described in German patent application DE 19616 770 and international patent application WO 95/14075 are also used with preference.
  • the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Such bleach activators are contained in the usual quantity range, preferably in quantities 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 contained as so-called bleach 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 the German patent application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands known from the German patent application DE 19620411 A1 cobalt, iron, copper and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0272030 A1, from the European patent application EP 0693550 A1 known manganese complex
  • 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 from 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, based in each case on the total agent.
  • Particularly suitable enzymes are 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 contribute to the removal of stains, such as protein, fat or starch-containing stains, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain the color and increase the softness of the textile. Oxidoreductases can also be used to bleach or to inhibit color transfer. Bacterial strains or fungi such as Bacillus subtilis and Bacillus licheniformis are particularly suitable.
  • Enzymatic agents obtained from Streptomyces griseus and Humicola insolens Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used. These are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease. Lipase or lipolytic enzymes and cellulase, but in particular protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytically acting enzymes are the known cutinases.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include, in particular, ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • the cellulases used are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures of these. Since the different cellulase types differ in their CMCase and Avicelase activities, the desired activities can be set by means of targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carrier substances and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, be about 0.1 to 5% by weight, preferably 0.1 to about 2 wt%.
  • the agents can contain other enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight of 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, is particularly advantageous. Boron oxide. Borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyoboric acid (tetraboric acid H 2 B 4 O 7 ).
  • the task of graying inhibitors is to keep the dirt detached from the fiber suspended in the liquor and thus to prevent the dirt from being pulled up again.
  • 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 acid sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use soluble starch preparations and other starch products than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (Na salt) and methyl cellulose are preferred.
  • 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 agent, are used.
  • the agents can contain derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof as optical brighteners.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type can be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the abovementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, also small amounts, for example 10 - 6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
  • Suitable soil repellants are those 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 distinguished 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 of about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Furthermore, those polymers are preferred which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 1000 to about 3000 and a polymer molecular weight of from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhone-Poulenc).
  • odoriferous compounds for example 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, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexyl propionate, allylcyclohexyl propionate, stalyl cyclohexyl propionate, and allyl cyclohexyl propionate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 carbon atoms.
  • Phenylethyl alcohol and terpineol the hydrocarbons mainly include terpenes such as limonene and pinene.
  • terpenes such as limonene and pinene.
  • mixtures of different fragrances which together produce an appealing fragrance note.
  • perfume oils can also contain natural odorant mixtures, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, pat-chouly, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper 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, it but it can also be advantageous to apply the fragrances to a carrier which ensures the adhesion of the perfume on the laundry and by a slower fragrance release ensure the long-lasting fragrance of the textiles.
  • carrier materials have proven
  • cyclodextrins proven, with the cyclodextrin-perfume complexes in addition can still be coated with other auxiliaries.
  • the detergents according to the invention can also contain inorganic salts as fillers or adjusting agents, such as, for example, sodium sulfate, which is preferably contained in amounts of 0 to 40, in particular 1 to 30% by weight, based on the detergent.
  • inorganic salts such as, for example, sodium sulfate, which is preferably contained in amounts of 0 to 40, in particular 1 to 30% by weight, based on the detergent.
  • the detergents according to the invention can be in the form of powders, extrudates, granules or tablets are produced or used. To produce such agents are the corresponding methods known from the prior art. Preferred the means are produced by the fact that various particulate components, the detergent ingredients contain, are mixed with one another.
  • the particulate components can be easily spray-dried Mixing or complex granulation processes, e.g. fluidized bed granulation, getting produced. It is particularly preferred that at least one surfactant-containing Component is produced by fluidized bed granulation. Further it can in particular be preferred when aqueous preparations of the alkali metal silicate and the alkali metal carbonate sprayed together with other detergent ingredients in a drying device granulation can take place at the same time as 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 in a known manner to a stream of drying gas in finely divided form.
  • the applicant describes an embodiment of spray drying with superheated steam in a number of published documents. The working principle disclosed there is hereby also expressly made the subject of the present disclosure of the invention.
  • the mixtures are then subjected to a compaction step, further ingredients being added to the compositions only after the compaction 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 implemented in various devices. 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 compression or compression, hole compression (pelletizing) and tabletting, so that compression agglomeration processes preferred in the context of the present invention are extrusion, roller compaction.
  • compression agglomeration processes preferred in the context of the present invention are extrusion, roller compaction.
  • pelletizing or tableting operations All the processes have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed against one another, reducing their porosity, and adhere to one another. In all processes (with some restrictions in the case of tableting), the tools can be heated to higher temperatures or cooled to dissipate the heat generated by shear forces.
  • binders can be used as an aid for compaction will.
  • a binder is used that at temperatures up to a maximum of 130.degree. C., preferably up to a maximum of 100.degree and in particular is already completely in the form of a melt up to 90 ° C.
  • the binder must that is, depending on the process and process conditions, are selected or the process conditions, in particular the process temperature must - if a specific one Binder is desired - to be matched to the binder.
  • the actual compression process is preferably carried out at processing temperatures which at least in the compression step is at least the temperature of the softening point, if not 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 present as a melt.
  • the process temperature in the compression step not more than 20 ° C above the melting temperature or the is the upper limit of the melting range of the binder. It is indeed technically quite possible to set even higher temperatures; but it has been shown that one Temperature difference to the melting temperature or to the softening temperature of the binder of 20 ° C is generally sufficient and even higher temperatures cause no additional benefits.
  • Such a temperature control has the further advantage that also thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious losses of active substances can be.
  • peroxy bleaching agents such as perborate and / or percarbonate
  • enzymes increasingly processed without serious losses of active substances can be.
  • the possibility of precise temperature control of the binder in particular in the decisive step of compression, i.e. between mixing / homogenization of the premix and the shaping allows an energetic very cheap and extremely for the temperature-sensitive components of the premix Gentle process management, since the premix only for a short time the higher temperatures is exposed.
  • the work tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roll (s) of the pellet press) have a maximum temperature 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process temperature is at 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 action in the compression range is preferably Press agglomerators 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 glycols 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 use C 3 -C 5 glycols and glycerol and mixtures thereof as starter molecules. Furthermore, 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, where polyethylene glycols with relative molecular weights below 3,500 and above 5,000 can be used, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000 Such combinations advantageously contain more than 50% by weight, based on the total amount of polyethylene glycols, polyethylene glycols with a relative molecular weight between 3,500 and 5,000.
  • polyethylene glycols which are in liquid form at room temperature and a pressure of 1 bar can also be used as binders; This is mainly about polyethylene glycol with a relative molecular weight of 200, 400 and 600.
  • these polyethylene glycols which are liquid per se, should only be used in a mixture with at least one other binder, this mixture again having to meet the requirements according to the invention, that is to say has to have a melting point or softening point of at least above 45.degree.
  • binders are low molecular weight polyvinylpyrrolidones and derivatives of these with relative molecular weights of up to a maximum of 30,000. Preferred are relative molecular weight ranges between 3,000 and 30,000, for example around 10,000. especially used in combination with polyethylene glycols.
  • the compacted material preferably has it directly after leaving the production apparatus Temperatures not above 90 ° C, with temperatures between 35 and 85 ° C are particularly preferred. It has been found that exit temperatures - before especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, particularly advantageous are.
  • the detergent according to the invention is produced by means of an extrusion , as described, for example, in the European patent EP 0486592 B1 or the international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 .
  • a solid premix is compressed into a strand under pressure and the strand is cut to the predeterminable granulate dimension by means of a cutting device after exiting the hole shape.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure or under the input 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-screw extruder or 2-screw extruder with concurrent or counter-rotating screw guidance, the housing and extruder granulating 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 nozzle 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 reduced to approximately spherical to cylindrical granules by means of a rotating cut-off knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way it is possible to produce granules with an essentially uniformly predeterminable particle size, it being possible for the absolute particle sizes to be adapted to the intended use.
  • particle diameters of up to a maximum of 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 cut-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; in the process, any edges present on the raw extrudate are rounded so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • dry powder for example zeolite powder such as zeolite NaA powder
  • This shaping can be done in standard rounding devices. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the above-mentioned documents of the prior art, is then possible, but not absolutely necessary. It may just be preferable not to carry out any more drying after the compaction step.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bepex be-extruder.
  • the temperature control in the transition area of the screw, the predistributor and the nozzle plate is preferably designed in such a way 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 action 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 rollers with a defined shape and is rolled out between the two rollers under pressure to form a sheet-like compact, the so-called scab.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured scabs are obtained, while the use of structured rollers can produce correspondingly structured scabs in which, for example, certain shapes of the later detergent particles can be specified.
  • the sliver band is subsequently broken into smaller pieces by a chopping and shredding process and can in this way be processed into granules that can be refined by other known surface treatment processes, in particular brought into an approximately spherical shape.
  • the temperature of the pressing tools that is to say the rollers
  • the temperature of the pressing tools is preferably a maximum of 150.degree. C., preferably a maximum of 100.degree. C. and in particular a maximum of 75.degree.
  • Particularly preferred production processes for roller compaction work at 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.
  • the duration of the temperature action in the compression area of the smooth rollers or rollers provided with depressions of a defined shape is a maximum of 2 minutes and in particular is in a range between 30 seconds and 1 minute.
  • the detergent according to the invention can also be produced by means of pelleting.
  • the premix is applied to a perforated surface and pressed through the holes by means of a pressure-giving body with plasticization.
  • the premix is compacted under pressure, plasticized, pressed in the form of fine strands through a perforated surface by means of a rotating roller and finally crushed into granules with a chopping device.
  • printing roller and perforated die are conceivable here.
  • flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed by means of one or more pressure rollers.
  • the pressure rollers can also be conically shaped in the case of the plate devices; in the ring-shaped devices, the dies and pressure roller (s) can rotate in the same direction or in opposite directions.
  • An apparatus suitable for carrying out the method is described, for example, in the German patent application DE 3816842 A1 .
  • the ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material fed to the die space through the press channels into a material outlet.
  • the ring die and the press roller can be driven in the same direction, so that a reduced shear load and thus a lower temperature increase in the premix can be achieved.
  • the temperature of the pressing tools that is to say the pressure rollers or press rollers, is preferably a maximum of 150.degree. C., preferably a maximum of 100.degree. C. and in particular a maximum of 75.degree.
  • Particularly preferred production processes for roller compaction work at 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.
  • Another press agglomeration process that can be used to produce the detergents according to the invention is tableting. Due to the size of the molded bodies produced, it can be useful during tableting to add conventional disintegration aids, for example cellulose and its derivatives, in particular in coarsened form, or cross-linked PVP, in addition to the binder described above, which facilitate the disintegration of the compacts in the washing liquor.
  • the particulate press agglomerates obtained can either be used directly as detergents or post-treated and / or processed beforehand by customary methods.
  • the usual after-treatments include, for example, powdering with finely divided ingredients of detergents 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 , whereby powdery or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products produced according to the invention, which serve as the core, and thus agents are formed which have these so-called fines as an outer shell.
  • This is advantageously done in turn by melt 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 be different in color, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
  • Detergent tablets generally contain a disintegrant which is intended to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor.
  • a disintegrant which is intended to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor.
  • German patent applications DE 19709991 A1 and DE 19710254 A1 in which preferred cellulose-based disintegrant granules are described.
  • the solid detergents according to the invention are distinguished by a reliably controlled foam behavior, even in the case of detergents with high proportions of nonionic surfactants, which are particularly difficult to defoam.
  • the solid detergents can also be controlled in their foam without the addition of silicones, usually only by adding waxy defoamers, which are considerably cheaper, especially since they only have to be used in relatively small quantities. Without being tied to a theory, the presence of the linear nonionic surfactants of the formula ( II ) appears to be essential for this effect.
  • Table 1 shows that the examples according to the invention with C 16/18 coconut alcohol + 7EO and alkyl glucoside both in the presence of linear alcohol ethoxylates such as C 12/14 coconut alcohol 7EO (Ex. 1, 2, 4 for V1) and with highly branched alcohol ethoxylates (Ex. 3, 5 to V2) in phosphate-containing as well as zeolite-containing detergents (Ex. 6, 8 to V3 or Ex. 7, 9 to V4) with lower amounts of defoamer the same or better foam grades or always better with the same amounts of defoamer Achieve foam notes.
  • linear alcohol ethoxylates such as C 12/14 coconut alcohol 7EO (Ex. 1, 2, 4 for V1)
  • highly branched alcohol ethoxylates Example. 3, 5 to V2
  • zeolite-containing detergents Example. 6, 8 to V3 or Ex. 7, 9 to V4

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Claims (20)

  1. Mélanges tensioactifs pour la fabrication de produits de lavage solides, contenant
    A) des agents tensioactifs anioniques en quantités de 0 à 6 % en poids et
    B) un mélange tensioactif non ionique en quantités supérieures à 60 % en poids, par rapport à l'ensemble du mélange tensioactif, le mélange tensioactif non ionique contenant
    a) au moins un alkyl- et/ou alcényl-oligoglycoside de formule (I), R1O-[G]p dans laquelle R1 représente un radical alkyle et/ou alcényle linéaire et/ou ramifié comportant de 4 à 22 atomes de carbone, G représente un radical saccharique comportant 5 ou 6 atomes de carbone et p représente des nombres allant de 1 à 10, et
    b) au moins un agent tensioactif non ionique de formule (II) R2O(CH2CHRO)xH dans laquelle x représente un nombre allant de 1 à 30, R représente l'hydrogène, un méthyle et/ou un éthyle et R2 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de : 80 à 100 % en poids d'alcools linéaires saturés et/ ou insaturés comportant de 16 à 22 atomes de carbone et de 0 à 20 % en poids d'alcools linéaires saturés et/ou insaturés comportant de 6 à 14 atomes de carbone, ainsi que le cas échéant
    c) au moins un autre agent tensioactif non ionique choisi dans le groupe formé par
    c1) les éthoxylates d'alcool de formule (III) R3O(CH2CHRO)yH dans laquelle y représente un nombre allant de 1 à 30, R représente l'hydrogène, un méthyle et/ou un éthyle, et R3 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de : 70 à 95 % en poids d'alcools linéaires saturés et/ou insaturés comportant de 8 à 22 atomes de carbone, de 5 à 30 % en poids d'alcools saturés et/ou insaturés ramifiés avec des groupes méthyle et comportant de 8 à 22 atomes de carbone, et de 0 à 10 % en poids d'alcools saturés et/ou insaturés ramifiés avec des groupes alkyle ayant au moins 2 atomes de carbone et comportant de 8 à 22 atomes de carbone,
    c2) les éthoxylates d'alcool de formule (IV) R4O(CH2CHRO)zH dans laquelle z représente un nombre allant de 1 à 30, R représente un hydrogène, un méthyle et/ou un éthyle et R4 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de : 35 à 55 % en poids d'alcools linéaires saturés et/ou insaturés comportant de 8 à 22 atomes de carbone, de 10 à 20 % en poids d'alcools saturés et/ou insaturés ramifiés avec des groupes alkyle ayant des groupes méthyle et comportant de 8 à 22 atomes de carbone, et de 35 à 45 % en poids d'alcools saturés et/ou insaturés ramifiés avec au moins 2 atomes de carbone et comportant de 8 à 22 atomes de carbone,
    c3) les éthoxylates d'alcool de formule (V) R5O(CH2CHRO)qH dans laquelle q représente un nombre allant de 1 à 30, R représente l'hydrogène, un méthyle et/ou un éthyle et R5 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de 0 à 10 % en poids d'alcools linéaires saturés et/ou insaturés comportant de 6 à 10 atomes de carbone, de 40 à 90 % en poids d'alcools linéaires saturés et/ou insaturés comportant de 12 à 14 atomes de carbone, et de 0 à 30 % en poids d'alcools linéaires saturés et/ou insaturés comportant de 16 à 22 atomes de carbone,
    c4) les polyglycolesters d'acides gras de formule (VI) R6COO(CH2CHRO)sR7 dans laquelle s représente un nombre allant de 1 à 30, R6CO représente des radicaux acyle linéaires ou ramifiés, saturés ou insaturés, comportant de 6 à 22 atomes de carbone, R7 représente des radicaux alkyle linéaire ou ramifiés comportant de 1 à 4 atomes de carbone et R représente l'hydrogène, un méthyle et/ou un éthyle.
  2. Mélanges tensioactifs selon la revendication 1,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (II) dans laquelle R2 représente un radical alkyle qui dérive d'un mélange d'alcools constitué de
    0 à 2 % en poids d'alcools saturés linéaires comportant 12 atomes de carbone,
    3 à 8 % en poids d'alcools saturés linéaires comportant 14 atomes de carbone,
    25 à 35 % en poids d'alcools saturés linéaires comportant 16 atomes de carbone,
    60 à 70 % en poids d'alcools saturés linéaires comportant 18 atomes de carbone et
    0 à 2 % en poids d'alcools saturés linéaires comportant 22 atomes de carbone.
  3. Mélanges tensioactifs selon l'une des revendications 1 ou 2,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (II), dans laquelle R représente l'hydrogène et x représente un nombre allant de 4 à 12, de préférence de 5 à 10.
  4. Mélanges tensioactifs selon l'une des revendications 1 à 3,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (III) dans laquelle R3 représente un radical alkyle qui dérive d'un mélange d'alcools constitué de
    73 à 85 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 8 à 22 atomes de carbone,
    13 à 25 % en poids d'alcools saturés et/ou insaturés, ramifiés avec des groupes méthyle et comportant de 8 à 22 atomes de carbone et
    2 à 7 % en poids d'alcools saturés et/ou insaturés, ramifiés avec des groupes alkyle ayant au moins 2 atomes de carbone et comportant de 8 à 22 atomes de carbone.
  5. Mélanges tensioactifs selon l'une des revendications 1 à 4,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (III), dans laquelle R3 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de
    73 à 85 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 12
    à 15 atomes de carbone,
    13 à 25 % en poids d'alcools saturés et/ou insaturés, ramifiés avec des groupes méthyle et comportant de 12 à 15 atomes de carbone et
    2 à 7 % en poids d'alcools saturés et/ou insaturés, ramifiés avec des groupes alkyle ayant au moins 2 atomes de carbone et comportant de 10 à 15 atomes de carbone.
  6. Mélanges tensioactifs selon l'une des revendications 1 à 5,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs de formule (III) dans laquelle R représente l'hydrogène et y représente un nombre situé dans un intervalle allant de 4 à 12, de préférence de 5 à 10.
  7. Mélanges tensioactifs selon l'une des revendications 1 à 6,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (IV) dans laquelle R4 représente un radical alkyle qui dérive d'un mélange d'alcools constitué de 50 à 60 % en poids d'alcools ramifiés et de 40 à 50 % en poids d'alcools linéaires - par rapport au mélange d'alcools.
  8. Mélanges tensioactifs selon l'une des revendications 1 à 7,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (IV) dans laquelle R représente l'hydrogène et z représente un nombre situé dans un intervalle allant de 4 à 12, de préférence dans un intervalle allant de 5 à 10.
  9. Mélanges tensioactifs selon l'une des revendications 1 à 8,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (V) dans laquelle R5 représente un radical alkyle qui dérive d'un mélange d'alcools constitué de
    0 à 5 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 6 à 10 atomes de carbone,
    55 à 85 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 12 à 14 atomes de carbone et
    10 à 25 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 16 à 22 atomes de carbone.
  10. Mélanges tensioactifs selon l'une des revendications 1 à 9,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (V) dans laquelle R représente l'hydrogène et q représente un nombre situé dans un intervalle allant de 4 à 12, de préférence de 5 à 10.
  11. Mélanges tensioactifs selon l'une des revendications 1 à 10,
    caractérisés en ce qu'
    ils contiennent des agents tensioactifs non ioniques de formule (VI) dans laquelle R6CO représente un radical acyle comportant de 16 à 18 atomes de carbone, R7 représente un groupe méthyle, R représente l'hydrogène et s représente des nombres allant de 10 à 15.
  12. Mélanges tensioactifs selon l'une des revendications 1 à 11,
    caractérisés en ce qu'
    ils contiennent les alkylpolyglycosides de formule (I) et les agents tensioactifs non ioniques de formule (II) dans un rapport pondéral de 20 : 1 à 1 : 20, de préférence de 10 : 1 à 1 : 5 et en particulier de 10 : 1 à 1 : 2.
  13. Mélanges tensioactifs selon l'une des revendications 1 à 12,
    caractérisés en ce qu'
    ils contiennent les alkylpolyglycosides de formule (I) par rapport aux agents tensioactifs non ioniques de formule (II) + (III) et/ou (IV) et/ou (V) et/ou (VI) dans un rapport pondéral de 10 : 1 à 1 : 20, de préférence de 5 : 1 à 1 : 10 et en particulier de 2 : 1 à 1 : 5.
  14. Mélanges tensioactifs selon l'une des revendications 1 à 13,
    caractérisés en ce qu'
    ils contiennent les agents tensioactifs non ioniques de formule (II) par rapport aux agents tensioactifs non ioniques de formule (III) et/ou (IV) et/ou (V) et/ou (VI) dans un rapport pondéral de 1 : 20 à 20 : 1, de préférence de 1 : 10 à 1 : 1 et en particulier de 1 : 8 à 1 : 1,5.
  15. Produits de lavage solides à caractère moussant contrôlé contenant en quantités de 5 à 30 % en poids - par rapport au produit de lavage - un mélange tensioactif contenant
    A) des agents tensioactifs anioniques en quantités de 0 à 6 % en poids et
    B) un mélange tensioactif non ionique en quantités supérieures à 60 % en poids - le pourcentage pondéral se rapportant à l'ensemble du mélange tensioactif - le mélange tensioactif non ionique contenant
    a) au moins un alkyl- et/ ou alcényloligoglycoside de formule (I) R1O-[G]p dans laquelle R1 représente un radical alkyle et/ou alcényle linéaire et/ou ramifié comportant de 4 à 22 atomes de carbone, G représente un radical saccharique comportant 5 ou 6 atomes de carbone et p représente des nombres allant de 1 à 10, et
    b) au moins un agent tensioactif non ionique de formule (II) R2O(CH2CHO)xH dans laquelle x représente un nombre allant de 1 à 30, R représente l'hydrogène, un méthyle et/ou un éthyle et R2 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de : 80 à 100 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 16 à 22 atomes de carbone et de 0 à 20 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 6 à 14 atomes de carbone, ainsi que, le cas échéant
    c) au moins un autre agent tensioactif non ionique choisi dans le groupe formé par
    c1) les éthoxylates d'alcool de formule (III) R3O(CH2CHO)yH dans laquelle y représente un nombre allant de 1 à 30, R représente l'hydrogène, un méthyle et/ou un éthyle, et R3 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de : 70 à 95 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 8 à 22 atomes de carbone et de 5 à 30 % en poids d'alcools saturés et/ou insaturés ramifiés avec des groupes méthyle et comportant de 8 à 22 atomes de carbone et de 0 à 10 % en poids d'alcools saturés et/ou insaturés, ramifiés avec au moins 2 atomes de carbone et comportant de 8 à 22 atomes de carbone,
    c2) les éthoxylates d'alcool de formule (IV) R4O(CH2CHRO)zH dans laquelle z représente un nombre allant de 1 à 30, R représente l'hydrogène, un méthyle et/ou un éthyle et R4 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de : 35 à 55 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 8 à 22 atomes de carbone et de 10 à 20 % en poids d'alcools saturés et/ou insaturés, ramifiés avec des groupes méthyle et comportant de 8 à 22 atomes de carbone, et de 35 à 45 % en poids d'alcools saturés et/ou insaturés, ramifiés avec des groupes alkyle ayant au moins 2 atomes de carbone et comportant de 8 à 22 atomes de carbone,
    c3) les éthoxylates d'alcool de formule (V) R5O(CH2CHRO)qH dans laquelle q représente un nombre allant de 1 à 30, R représente l'hydrogène, un méthyle et/ou un éthyle et R5 représente des radicaux alkyle qui dérivent d'un mélange d'alcools constitué de : 0 à 10 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 6 à 10 atomes de carbone, de 40 à 90 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 12 à 14 atomes de carbone et de 0 à 30 % en poids d'alcools saturés et/ou insaturés linéaires comportant de 16 à 22 atomes de carbone,
    c4) les polyglycolesters d'acides gras de formule (VI) R6COO(CH2CHRO)sR7 dans laquelle s représente un nombre allant de 1 à 20, R6CO représente des radicaux acyle saturés ou insaturés, linéaires ou ramifiés, comportant de 6 à 22 atomes de carbone, R7 représente des radicaux alkyle linéaires ou ramifiés comportant de 1 à 4 atomes de carbone et R représente l'hydrogène, un méthyle et/ou un éthyle.
  16. Produits de lavage solides selon la revendication 15,
    caractérisés en ce qu'
    ils contiennent en outre des antimousses en quantités de 0,05 à 5 % en poids - calculées sous la forme de la teneur en matière active et par rapport au produit de lavage.
  17. Produits de lavage solides selon l'une des revendications 15 ou 16,
    caractérisés en ce qu'
    ils contiennent comme antimousses au moins un composé cireux.
  18. Produits de lavage solides selon l'une des revendications 15 à 17,
    caractérisés en ce qu'
    ils contiennent comme antimousses au moins un composé cireux et un composé de silicone à propriété antimousses.
  19. Produits de lavage solides selon l'une des revendications 15 à 18,
    caractérisés en ce qu'
    ils se présentent sous forme de poudres, de produits d'extrusion, de granulés ou de pastilles.
  20. Utilisation de mélanges tensioactifs selon la revendication 1, pour la fabrication de produits de lavage solides à caractère moussant contrôlé.
EP00965986A 1999-09-22 2000-09-13 Melanges de tensioactifs Expired - Lifetime EP1214389B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19945353 1999-09-22
DE19945353A DE19945353A1 (de) 1999-09-22 1999-09-22 Tensidmischungen
PCT/EP2000/008922 WO2001021743A1 (fr) 1999-09-22 2000-09-13 Melanges de tensioactifs

Publications (2)

Publication Number Publication Date
EP1214389A1 EP1214389A1 (fr) 2002-06-19
EP1214389B1 true EP1214389B1 (fr) 2005-12-14

Family

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Application Number Title Priority Date Filing Date
EP00965986A Expired - Lifetime EP1214389B1 (fr) 1999-09-22 2000-09-13 Melanges de tensioactifs

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US (1) US6812201B1 (fr)
EP (1) EP1214389B1 (fr)
DE (2) DE19945353A1 (fr)
ES (1) ES2254231T3 (fr)
WO (1) WO2001021743A1 (fr)

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CN108611200A (zh) * 2018-06-15 2018-10-02 河北晨晨环境科技股份有限公司 环保洁厕剂及其制备方法

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CN101389398B (zh) * 2006-02-22 2012-03-21 巴斯夫欧洲公司 含有短链和长链组分的表面活性剂混合物
WO2011003904A1 (fr) * 2009-07-10 2011-01-13 Basf Se Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue
US9138749B2 (en) 2011-02-09 2015-09-22 Wisconsin Film & Bag, Inc. Post consumer scrap film recycling process
US8820666B2 (en) 2011-02-09 2014-09-02 Wisconsin Film & Bag, Inc. Post consumer scrap film recycling process
US8567702B2 (en) 2011-02-09 2013-10-29 Wisconsin Film & Bag, Inc. Post consumer scrap film recycling process
FR3075662B1 (fr) * 2017-12-21 2022-06-24 Ifp Energies Now Procede de pretraitement pour ameliorer le remplissage d'une enceinte avec des particules solides
EP4392512A1 (fr) * 2021-08-25 2024-07-03 Unilever IP Holdings B.V. Composition détergente
WO2023025761A1 (fr) * 2021-08-25 2023-03-02 Unilever Ip Holdings B.V. Composition de détergent

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DE3732947A1 (de) * 1987-09-30 1989-04-13 Henkel Kgaa Zur verwendung in wasch- und reinigungsmitteln geeignetes schaumregulierungsmittel
DE4029035A1 (de) * 1990-09-13 1992-03-19 Huels Chemische Werke Ag Waschmittel
DE4233699A1 (de) * 1992-10-07 1994-04-14 Henkel Kgaa Klarspüler für das maschinelle Geschirrspülen
DE19509752A1 (de) * 1995-03-17 1996-09-19 Henkel Kgaa Verfahren zur Herstellung eines pulverförmigen Waschmittels
DE19548843A1 (de) * 1995-12-27 1997-07-03 Henkel Ecolab Gmbh & Co Ohg Verfahren zum Waschen von Wäsche

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108611200A (zh) * 2018-06-15 2018-10-02 河北晨晨环境科技股份有限公司 环保洁厕剂及其制备方法

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EP1214389A1 (fr) 2002-06-19
DE50011864D1 (de) 2006-01-19
US6812201B1 (en) 2004-11-02
ES2254231T3 (es) 2006-06-16
WO2001021743A1 (fr) 2001-03-29
DE19945353A1 (de) 2001-03-29

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