EP1214389A1 - Melanges de tensioactifs - Google Patents

Melanges de tensioactifs

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Publication number
EP1214389A1
EP1214389A1 EP00965986A EP00965986A EP1214389A1 EP 1214389 A1 EP1214389 A1 EP 1214389A1 EP 00965986 A EP00965986 A EP 00965986A EP 00965986 A EP00965986 A EP 00965986A EP 1214389 A1 EP1214389 A1 EP 1214389A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
weight
formula
saturated
unsaturated alcohols
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00965986A
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German (de)
English (en)
Other versions
EP1214389B1 (fr
Inventor
Manfred Weuthen
Karl Heinz Schmid
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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Publication of EP1214389A1 publication Critical patent/EP1214389A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—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 is in the field of surfactant mixtures for the production of solid, foam-controlled detergents and relates to surfactant mixtures with high levels of specially selected nonionic surfactants and no or only low levels of anionic surfactants. Further objects of the present invention relate to solid foam-controlled detergents containing such surfactant mixtures and the use of such surfactant mixtures for the production of solid, foam-controlled detergents.
  • Detergents for household and industrial laundry generally contain anionic surfactants, nonionic surfactants, builders and numerous organic and inorganic additives.
  • the anionic surfactants used to clean the laundry usually tend to develop foam during the washing cycle, which on the one hand has a negative effect on the washing result and on the other hand can lead to the washing machine overflowing. There is therefore a practical need to control the foam development during the washing process and in particular to minimize it.
  • defoamers or so-called anti-foaming agents are used, which on the one hand are intended to reduce the development of foam and on the other hand to reduce foam that has already formed.
  • 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 ordinary defoamers, for example based on paraffins.
  • Suitable paraffin wax mixtures as defoamers are described, for example, in European patent application EP 0309931 AI.
  • Defoaming or foam control has proven to be more problematic in the case of surfactant mixtures with high contents of nonionic surfactants and in particular above all when alkyloli oglucosides based on linear surfactants are used as nonionic surfactants Fatty alcohols or branched oxo alcohols can be used.
  • Such surfactant mixtures which are characterized by particularly advantageous dissolving properties and are therefore of particular interest to the consumer, have so far only been able to defoam reliably if silicones are used as defoamers, which are generally applied to carrier materials and, if appropriate, with other defoaming substances - be coatet.
  • defoamers containing silicone are known from European patent application EP 0496510 AI, a mixture of silicones and fatty alcohols, fatty acids or glycerol monoesters having special melting points being applied to the starch as the carrier material.
  • silicones tend to stick together due to their sticky, oily consistency, which can result in undesired silicone stains as residue on the washed laundry and secondly, the silicones are relatively expensive defoamers.
  • the object of the present invention was therefore to provide surfactant mixtures for the production of solid detergents with high contents of nonionic surfactants which, despite the alkyl oligoglycosides contained, are already controlled with small amounts of defoamers in their foam. Furthermore, good foam control should be possible with small amounts or without silicones as defoamers.
  • the surfactant mixtures or the solid detergents based thereon should meet the requirements for detergents with regard to primary detergency.
  • One object of the present invention therefore relates to surfactant mixtures for the production of solid detergents containing
  • nonionic surfactant mixture in amounts of more than 60% by weight, in each case based on the total surfactant mixture, the nonionic surfactant mixture containing
  • R 1 is a linear and / or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10
  • R is hydrogen, methyl and / or ethyl and R 2 is alkyl radicals which are derived from an alcohol mixture: 80 to 100% by weight of linear saturated and / or unsaturated alcohols 16 to 22 carbon atoms and 0 to 20% by weight of linear saturated and / or unsaturated alcohols with 6 to 14 carbon atoms and optionally
  • R is hydrogen, methyl and / or ethyl and R 4 is alkyl radicals which are derived from an alcohol mixture: 35 to 55% by weight of linear saturated and / or unsaturated alcohols 8 to 22 carbon atoms and 10 to 20 wt .-% saturated and / or unsaturated alcohols branched with methyl groups with 8 to 22 carbon atoms and 35 to 45 wt .-% with saturated and / or unsaturated alcohols branched with alkyl groups with at least 2 carbon atoms with 8 to 22 carbon atoms
  • Methyl and / or ethyl and R 5 represents alkyl radicals which are derived from an alcohol mixture of: 0 to 10% by weight of linear saturated and / or unsaturated alcohols having 6 to 10 carbon atoms and 40 to 90% by weight of linear saturated and / or unsaturated alcohols with 12 to 14 carbon atoms and 0 to 30 wt .-% linear saturated and / or unsaturated alcohols with 16 to 22 carbon atoms c4) fatty acid polyglycol esters of the formula (VI)
  • R CO linear or branched, saturated or unsaturated acyl radicals with 6 to 22 carbon atoms
  • R 7 for linear or branched alkyl radicals with 1 to 4 carbon atoms
  • R for hydrogen, methyl and / or ethyl stands.
  • Another object of the present invention relates to solid foam-controlled detergents containing in amounts of 5 to 30 wt .-% containing a surfactant mixture
  • nonionic surfactant mixture in amounts of more than 60% by weight, in each case based on the total surfactant mixture, the nonionic surfactant mixture containing
  • R 1 is a linear and / or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10
  • R is hydrogen, methyl and / or ethyl and R 2 is alkyl radicals which are derived from an alcohol mixture: 80 to 100% by weight of linear saturated and / or unsaturated alcohols 16 to 22 Carbon atoms and 0 to 20 wt .-% linear saturated and / or unsaturated alcohols with 6 to 14 carbon atoms and optionally
  • y represents a number from 1 to 30
  • R represents hydrogen, methyl and / or ethyl
  • R 3 represents alkyl radicals which are derived from an alcohol mixture: 70 to 95% by weight of linear saturated and / or unsaturated alcohols 8 to 22 carbon atoms and 5 to 30% by weight saturated and / or unsaturated alcohols branched with methyl groups with 8 to 22 carbon atoms and 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
  • R is hydrogen, methyl and / or ethyl and R 4 is alkyl radicals which are derived from an alcohol mixture: 35 to 55% by weight of linear saturated and / or unsaturated alcohols 8 to 22 carbon atoms and 10 to 20 wt .-% saturated and / or unsaturated alcohols branched with methyl groups with 8 to 22 carbon atoms and 35 to 45 wt .-% with saturated and / or unsaturated alcohols branched with alkyl groups with at least 2 carbon atoms with 8 to 22 carbon atoms
  • R represents hydrogen, methyl and / or ethyl and R 5 represents alkyl radicals which are derived from an alcohol mixture: 0 to 10% by weight of linear saturated and / or unsaturated alcohols with 6 to 10 carbon atoms and 40 to 90% by weight of linear saturated and / or unsaturated alcohols with 12 to 14 carbon atoms and 0 to 30% by weight of linear saturated and / or unsaturated alcohols with 16 to 22 carbon atoms
  • R 6 CO for linear or branched, saturated or unsaturated acyl radicals with 6 to 22 carbon atoms
  • R 7 for linear or branched alkyl radicals with 1 to 4 carbon atoms
  • R for hydrogen, methyl and / or Ethyl stands.
  • the present application relates to the use of the surfactant mixture of the type described for the production of solid, foam-controlled detergents.
  • nonionic surfactants of the formula (II), which are simply 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.
  • additional nonionic surfactants such as short-chain alcohol alkoxylates or branched alcohol alkoxylates and / or fatty acid polyglycol esters.
  • the surfactant mixture according to the invention necessarily contains nonionic surfactants in amounts above 60% by weight to 100% by weight, preferably in amounts of 70 to 98.5% by weight, based on the total surfactant content.
  • the 100% by weight of surfactants missing can be, on the one hand, anionic surfactants which are present in amounts of 0 to 6% by weight, 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, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerin ether sulfates, fatty acid ethersulfates (fatty acid ethersulfates), fatty acid ethersulfates (fatty acid ethersulfates), ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and Dialkylsulfosuccina- mate, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, Fettklathio- nate, fatty acid taurides
  • anionic surfactants are added to the surfactant mixture.
  • impurities in anionic surfactants can be present in the surfactant mixture or in the solid detergent. brought in by the other constituents in minor amounts.
  • Cationic, zwitterionic or ampholytic surfactants can contain up to 100% by weight, based on the surfactant mixture, as further optional surfactants in the surfactant mixture.
  • Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and esterquats, in particular quaternized fatty acid trialkanolamine ester salts.
  • Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazoiiniumbetaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
  • nonionic surfactants of the formulas (I) and (II) are mandatory in the surfactant mixture according to the invention.
  • Other nonionic surfactants are preferably also present, preferably at least one nonionic surfactant of the formulas (III) to (VI) being present.
  • nonionic surfactant mixture can contain other customary nonionic surfactants if required, 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 or glucoronic acid derivatives, fatty acid amide derivatives, fatty acid amides tein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters. Sugar esters, sorbitan esters, polysorbates and amine oxides.
  • other customary nonionic surfactants if required, 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)
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional or a narrow homolog distribution.
  • the further customary nonionic surfactants are preferably present 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 formula (I) and (II).
  • the nonionic surfactants of the formula (1) are alkyl and / or alkylene oligoglycosides. These are known nonionic surfactants. According to the relevant gene methods of preparative organic chemistry can be obtained. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in S ⁇ FW-Journal Issue 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 oligoglucosides.
  • 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.
  • the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and 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, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 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.
  • Brassidyl alcohol and their technical mixtures, as described above ben can be obtained.
  • 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 with 16 to 22 carbon atoms, preferably 16 to 18 carbon atoms. and contain from 0 to 30% by weight, preferably 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
  • Carbon atoms 0 to 10% by weight, preferably 3 to 8% by weight, of linear saturated alcohols with 14
  • Carbon atoms 20 to 50 wt .-%, preferably 25 to 35 wt .-% linear saturated alcohols with 16
  • Carbon atoms 50 to 80 wt .-%, preferably 60 to 70 wt .-% linear saturated alcohols with
  • Such alcohol mixtures can be obtained from tallow, palm kernel oil or by reducing aldehydes from Roelen's oxosynthesis.
  • the alcohol mixtures described have ethylene oxide, propylene oxide and / or butylene oxide. preferably ethylene oxide and / or propylene oxide added as block and / or random polymers. If ethylene oxide and propylene oxide are attached, the number of attached moles of propylene oxide is preferably in the range from 0.5 to 5 moles and the number of attached moles of ethylene oxide is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles ethylene oxide. A typical example of this are block copolymers with 1 mole of propylene oxide and 22 moles of ethylene oxide. Alcohol ethoxylates of the formula (II) which have 4 to 12, preferably 5 to 10, mol of ethylene oxide (x) added on average are particularly suitable.
  • 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) are alcohol alkoxylates which are derived from slightly branched alcohols. Such slightly branched alcohols represent an alcohol mixture
  • alcohol mixtures are particularly suitable in which the proportion of methyl-branched alcohols makes up at least 80% by weight, preferably at least 90% by weight, of the total branched alcohols present.
  • Such alcohol mixtures are by a special, known from the prior art oxosynthesis by reaction of carbon monoxide and hydrogen to ⁇ -olefins after SHOP accessible.
  • Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®.
  • Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45® or Neodol 91®, 1®, 23®, 25®, 45®.
  • Alcohol mixtures of the type described which are derived from alcohols having a total of 12 to 15 carbon atoms, the carbon atoms of the branches being counted in the total carbon number, are particularly suitable.
  • R 3 in formula (III) is in particular alkyl radicals of an alcohol mixture
  • the alcohol mixtures described have added ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, as block and / or random polymers. If ethylene oxide and propylene oxide are attached, the number of attached moles of propylene oxide is preferably in the range from 0.5 to 5 moles and the number of attached moles of ethylene oxide is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles ethylene oxide. A typical example of this 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, the number of moles of ethylene oxide attached being in the range from 1 to 20, preferably from 4 to 12 and particularly preferably from 5 to 10, the person skilled in the art being aware of this. that this is a statistical number.
  • the alcohol alkoxylates of the formula (IV) are alkoxylates of strongly branched alcohol mixtures such as those used in the classic oxo process. eat the Eni or Condea by adding carbon monoxide and hydrogen
  • Olefins are obtained which do not exclusively carry terminal double bonds.
  • alkyl groups with at least 2 carbon atoms branched saturated and / or unsaturated alcohols with 8 to 22 carbon atoms.
  • Particularly suitable are those alcohol mixtures on which the alkoxylates of the formula (IV) are based in which the proportion of branched alcohols - based on the alcohol mixture - in the range from 50 to 60% by weight and the proportion of linear alcohols in the range from 40 to 50 wt .-% is.
  • 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 added ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, as block and / or random polymers. If ethylene oxide and propylene oxide are attached, the number of attached moles of propylene oxide is preferably in the range from 0.5 to 5 moles and the number of attached moles of ethylene oxide is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles ethylene oxide. A typical example of this 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, the number of moles of ethylene oxide added in the range from 1 to 20, preferably from 4 to 12 and particularly preferably 5 to 10, it being clear to the person skilled in the art that this is a statistical number.
  • the nonionic surfactants of the formula (V) are alkoxylates of an alcohol mixture of short-chain fatty alcohols containing from 0 to 10% by weight, preferably 0 to 5% by weight, of linear saturated and / or unsaturated alcohols 6 to 10 coblene atoms 40 to 90 wt .-%, preferably 55 to 85 wt .-% linear saturated and / or unsaturated alcohols with 12 to 14 carbon atoms and O to 30 wt .-%, preferably 10 to 25 wt .-% linear saturated and / or unsaturated alcohols with 16 to 22 carbon atoms.
  • Such alcohol mixtures can be obtained as cuts from coconut oil, for example, or by reducing aldehydes from Roelen's oxosynthesis.
  • the alcohol mixtures described have added ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, as block and / or random polymers. If ethylene oxide and propylene oxide are attached, the number of attached moles of propylene oxide is preferably in the range from 0.5 to 5 moles and the number of attached moles of ethylene oxide is preferably in the range from 0.5 to 25 moles, in particular in the range from 7 to 25 moles ethylene oxide. A typical example of this are block copolymers with 1 mole of propylene oxide and 22 moles of ethylene oxide.
  • the ethylene oxide adducts are particularly suitable, the number of moles of ethylene oxide attached being 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 for the same Number stands.
  • 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 onto linear or branched, saturated and / or unsaturated fatty acids, such as, for example, caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, technical and erotic acid, behenic acid and behenic acid eg in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids.
  • caproic acid
  • Non-ionic surfactants of the formula (VI) have proven to be particularly effective in which R 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.
  • R CO stands for an acyl radical with 16 to 18 carbon atoms
  • R 7 for a methyl group
  • R for hydrogen
  • s for numbers from 10 to 15.
  • the most suitable alkoxylated fatty acid esters are those that combine these four structural features.
  • the alkoxylated fatty acid alkyl esters can be prepared in a manner known per se, preferably by alkoxylation of the fatty acid alkyl esters in the presence of calcined hydrotalcite.
  • alkyl polyglycosides of the formula (I) (component a) in a weight ratio to the nonionic surfactants of the formula (II) (component b) from 20: 1 to 1:20, preferably from 10: 1 to 1: 5 and in particular from 10: 1 to 1: 2.
  • a further nonionic surfactant is present as component c) selected from components cl) to c4), it has proven to be advantageous if the weight ratio of the alkyl glycosides (component a) to the nonionic surfactants (component b + c) is in the range from 10: 1 to 1:20, preferably 5: 1 to 1:10 and in particular 2: 1 to 1: 5.
  • the ratio of the nonionic surfactants of the formula (II) (component b) to that of the formulas (III) to (VT) (component c) is largely uncritical and is advantageously in the range from 1:20 to 20: 1, preferably in the range from 1:10 to 1: 1 and in particular in the range from 1: 8 to 1: 1.5. laundry detergent
  • the surfactant mixtures according to the invention are present 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 already reduced in foam per se compared to detergents containing only alkyl polyglycoside, 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 the detergent - preferably in total amounts from 0.05 to 5% by weight, preferably from 0.1 to 3 and in particular from 0.5 to 2% by weight. According to one embodiment of the present invention, only wax-like defoamer compounds are contained as defoamers. Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C. are understood as “waxy”.
  • the wax-like defoamer substances which may be present according to the invention are practically insoluble in water, ie They have a solubility of less than 0.1% by weight in 100 g of water at 20 ° C.
  • suitable wax-like compounds being, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of a - and polyhydric alcohols as well as paraffin waxes or mixtures thereof
  • the silicone compounds known for this purpose can also be used.
  • Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420, and / or its solidification point , This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1, for example from 26% by weight to 49% by weight of microcrystalline paraffin, can be used.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.
  • the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Suitable bisamides as defoamers are those which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachinic and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bismyristoylethylene diamine, bispalmitoylethylene diamine, bisstearoylethylene diamine and mixtures thereof and the corresponding derivatives of hexamethylene diamine.
  • Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular they are esters of behenic acid, stearin acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of 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.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
  • suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) COO (CH 2 ) 2 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3 , and carnauba wax, which is a mixture of Carnau-based acid alkyl esters, often in combination with small amounts of free carnauba acid. other long-chain acids, high molecular weight alcohols and hydrocarbons.
  • Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, as are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
  • Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
  • Dialkyl ethers may also be present as defoamers.
  • the ethers can be constructed asymmetrically or symmetrically, ie two identical or different dene alkyl chains, preferably containing 8 to 18 carbon atoms.
  • Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.
  • Suitable defoamer compounds are fatty ketones of the formula (VII),
  • 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 the elimination of carbon dioxide and water, for example according to the German laid-open specification DE 2553900 OS.
  • Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachidic acid, galdic acid, behenic acid or erucic acid.
  • Hentriaconta-non-16 are preferred; (R 9 and R 10 stands for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R 9 and R 10 stands for an alkyl radical with 16 carbon atoms), stearone (pentatriacontanone-18; R 9 and R 10 stands for an alkyl radical with 17 carbon atoms), heptatriacontanone-19 (R 9 and R I0 stands for an alkyl radical with 18 carbon atoms), araquinone (nonatriacontanone-20; R 9 and R 10 stands for an alkyl radical with 19 carbon atoms)
  • R men hentetracontanone-21 (R and R 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 (VTII),
  • Such fatty acid polyethylene glyol esters are preferably obtained by addition of ethylene oxide onto fatty acids which is catalyzed in a homogeneous manner, in particular ethylene oxide is added to the fatty acids in the presence of alkanolamines as catalysts.
  • alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to it. to produce low ethoxylated compounds.
  • fatty acid polyethylene glycol esters of the formula (VIII) in which R n CO is a linear acyl radical having 12 to 18 carbon atoms and n is the number 1. Lauric acid ethoxylated with 1 mol of ethylene oxide is particularly suitable. Within the group of fatty acid polyethylene glycol esters, preference is given to those which have a melting point above 25 ° C., in particular above 40 ° C.
  • the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
  • the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
  • the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
  • the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
  • Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
  • Examples of organic carrier materials are film-forming polymers, for example polyvinyl alcohols.
  • Polyvinylpyrrolidones Poly (meth) acrylates, polycarboxylates. Cellulose derivatives and starch in question.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • native starch which is composed of amylose and amylopectin. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
  • a mixture of at least one wax-like defoamer, preferably a paraffin wax, and a defoaming silicone compound is used as the defoamer.
  • suitable silicones are conventional organopolysiloxanes which can have a content of finely divided silica, which in turn can also be silanated. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 AI. Polydiorganosiloxanes which are 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),
  • R 12 independently of one another can be 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.
  • compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins.
  • the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable.
  • the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C.
  • the silicones are preferably applied to carrier materials. Suitable carrier materials have already been described in connection with the paraffins.
  • the carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.
  • the content of silicone in the mixtures with the wax-like defoamers - based on the active substance content of the defoamers - is at most 50% by weight, preferably at most 30% by weight ,
  • zeolites crystalline layered silicates and amorphous silicates with builder properties and, where permissible, phosphates such as tripolyphosphates also being used as inorganic builder substances.
  • the builder substances are preferably contained in the detergents according to the invention in amounts of 10 to 60% by weight, based on the detergent.
  • the fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P and Y are also suitable.
  • a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX ® (commercial product from Condea Augusta SpA) is commercially available.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • 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 2 -C 8 fatty alcohols with 2 to 5 ethylene oxide groups, -C 2 -C 4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ 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 + ryH O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP 0164514 AI.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 ⁇ 5'yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • Other suitable layer silicates are known, for example, from patent applications DE 2334899 AI, EP 0026529 AI and DE 3526405 AI. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layer Silicates that belong to the group of water-swellable smectites are, for example, those of the general formulas
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na and Ca.
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful layer silicates are known for example from US 3,966,629, US 4,062,647, EP 0026529 AI and EP 0028432 AI.
  • Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / sealing or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm preferred are.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 AI.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • phosphates As builders, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 30% by weight, preferably not more than 25% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out according to customary, for example acid or enzyme, lysed procedures are carried out. 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 preparation are known, for example, from European patent applications EP 0232202 AI, EP 0427349 AI, EP 0472042 AI and EP 0542496 AI as well as 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 AI is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 AI and in Japanese patent application JP 93/339896. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • Granular polymers are usually subsequently mixed into one or more basic granules.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, are monomers as 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 the 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which are described in German patent applications DE 4303320 AI and DE 4417734 AI and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids are also salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the 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 content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • the detergents can contain other known additives commonly used in detergents, for example salts of polyphosphonic acids, optical brighteners, enzymes. Enzyme stabilizers, small amounts of neutral filler salts as well as colorants and fragrances, opacifiers or pearlescent agents.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates. Citrate perhydrates and H 2 O 2 providing peracidic salts or peracids such as perbenzoates. Peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the C atom number mentioned and / or optionally substituted benzoyl groups.
  • hydrophilically substituted acylacetals known from German patent application DE 19616769 AI and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 4443177 AI can also be used. Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight. based on total mean.
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 AI and their N-analog compounds known from German patent application DE 19620267 AI, which are known from German Patent application DE 19536082 AI known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 - And copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 19620411 AI.
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 19613103 AI and international patent application WO 95/27775.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. up to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • hydrolases such as proteases. Esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains in the laundry. and graying. Cellulases and other glycosyl hydrolases can be used for color
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, is particularly advantageous. Borax and other alkali metal borates such as the salts of ortho- boric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ).
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. 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 also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition. used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned brighteners can also be used. Uniform white granules are obtained when the agents, in addition to the usual brighteners, are used in the usual amounts, for example between 0.1 and 0.5% by weight.
  • Soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers are characterized by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20.
  • Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropylate propylate allyl propylate propionate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms.
  • Phenylethyl alcohol and terpineol the hydrocarbons mainly include terpenes such as limonene and pinene.
  • terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the detergents according to the invention can also contain inorganic salts as fillers or fillers, for example sodium sulfate, which is preferably present in amounts of 0 to 40, in particular 1 to 30,% by weight, based on the composition.
  • inorganic salts for example sodium sulfate, which is preferably present in amounts of 0 to 40, in particular 1 to 30,% by weight, based on the composition.
  • the detergents according to the invention can be produced or used in the form of powders, extrudates, granules or tablets.
  • the corresponding methods known from the prior art are suitable for producing such agents.
  • the agents are preferably produced by mixing different particulate components which contain detergent ingredients.
  • the particulate components can be produced by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation. It can furthermore be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate are sprayed together with other detergent ingredients in a drying device, wherein granulation can take place simultaneously with the drying.
  • the drying device into which the aqueous preparation is sprayed can be any drying apparatus. In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner.
  • the mixtures are then subjected to a compacting step, further ingredients being added to the agents only after the compacting step.
  • the ingredients are compacted in a press agglomeration process.
  • the press agglomeration process to which the solid premix (dried basic detergent) is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used.
  • the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting. hole pressing (pelleting) and tabletting, so that preferred press agglomeration processes in the context of the present invention are extrusion, roll compaction, pelletizing or tableting processes.
  • binders can be used as an aid to compaction.
  • a binder is used which is already completely present as a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C. The binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.
  • the actual compression process preferably takes place at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
  • the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; However, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages.
  • thermoly sensitive raw materials for example peroxy bleaching agents such as perborate and / or percarbonate. but also enzymes, which can increasingly be processed without serious loss of active substance.
  • peroxy bleaching agents such as perborate and / or percarbonate.
  • enzymes which can increasingly be processed without serious loss of active substance.
  • the work tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression range of the press agglomerators is preferably a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also 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 5 -C 5 -glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
  • the polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used such combinations advantageously have more than 50% by weight, based on the total amount of the polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000.
  • polyethylene glycols can also be used as binders Room temperature and a pressure of 1 bar in liquid state; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
  • these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
  • suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred.
  • Polyvinylpyrrolidones are preferably not used as the sole binders but in combination with others. used in particular in combination with polyethylene glycols.
  • the compressed material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
  • the detergent according to the invention is produced by means of an extrusion, as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 and WO 98/12299.
  • a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and or polymers.
  • the premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, its housing and its extruder pelletizing head can be heated to the predetermined extrusion temperature.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
  • the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
  • the duration of the temperature Influence of temperature in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the detergents according to the invention can also be produced by means of roller compaction.
  • the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified.
  • the sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further known surface treatment processes, in particular in an approximately spherical shape.
  • the temperature of the pressing tools that is to say of the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the detergent according to the invention can also be produced by pelleting.
  • the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
  • the premix is compressed under pressure, plasticized. pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally crushed into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method is described, for example, in German published patent application DE 3816842 AI.
  • the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • Another pressing agglomeration process that can be used to produce the detergents according to the invention is tableting. Because of the size of the molded articles produced, it may be useful for tableting to add conventional disintegration aids, for example cellulose and its derivatives, in particular in coarser form, or crosslinked PVP in addition to the binder described above, which facilitate the disintegration of the compacts in the wash liquor.
  • the particulate press agglomerates obtained can either be used directly as detergents or aftertreated and / or prepared beforehand by customary methods.
  • the usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density is increased.
  • a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 AI and DE 19547457 AI, where dusty or at least fine-particle ingredients (the so-called fine particles) are adhered to the particulate end products of the process, which serve as the core, and thus agents arise, which have these so-called fines as an outer shell.
  • the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
  • the base of these tablets can be circular or rectangular, for example.
  • Multi-layer tablets in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
  • 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 AI and DE 19710254 AI 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 the detergents which are particularly difficult to defoam and have high proportions of nonionic surfactants.
  • the solid detergents can also be checked in their foam without the addition of silicones, usually only by adding wax-like defoamers, which are considerably cheaper, especially since they only have to be used in relatively small amounts.
  • the presence of the linear nonionic surfactants of the formula (II) appears to be essential for this effect. Examples
  • the powder detergents were examined for their foaming behavior.
  • a Miele washing machine (Miele W 918)
  • 3.5 kg of standard laundry was washed at a temperature of 90 ° C in a full wash cycle.
  • 75 g of the test formulations in Table 1 were placed in the dispenser immediately before washing. The foam generated during the washing process was observed and measured every 10 minutes, the maximum foam height was rated with marks. The following grades were awarded:
  • Lial® 125 is a C 11-1 alcohol mixture consisting of 43.5% by weight saturated linear alcohols, 15.5% by weight methyl-branched alcohols and 41% by weight alcohols branched with alkyl groups with at least 2 C atoms ,
  • Lial® 125 is a C ⁇ - ⁇ 5 alcohol mixture of 43.5% by weight saturated linear alcohols, 15.5% by weight methyl-branched alcohols and 41% by weight alcohols branched with alkyl groups with at least 2 C atoms ,
  • Table 1 shows that the inventive examples with C ⁇ 6 / ⁇ 8 coconut oil fatty alcohol + 7EO and alkyl glucoside linear both in the presence of alcohol such as hol + 7EO (Ex. 1, 2, 4 to VI) as well as strongly branched alcohol ethoxylates (Ex. 3, 5 to V2) in phosphate-containing as well as in zeolite-containing detergents (Ex. 6, 8 to V3 or Ex. 7, 9 to V4) achieve the same or better foam notes with lower defoamer quantities or always better foam notes with the same defoamer quantities.
  • alcohol such as hol + 7EO (Ex. 1, 2, 4 to VI)
  • strongly branched alcohol ethoxylates Example. 3, 5 to V2
  • phosphate-containing as well as in zeolite-containing detergents
  • Example 6, 8 to V3 or Ex. 7, 9 to V4 achieve the same or better foam notes with lower defoamer quantities or always better foam notes with the same defoamer quantities.

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

Abstract

L'invention concerne des mélanges de tensioactifs pour la fabrication de détergents solides à mousse contrôlée, en particulier des mélanges de tensioactifs présentant de fortes teneurs en tensioactifs non-anioniques sélectionnés, et des teneurs nulles ou très faibles en tensioactifs anioniques. L'invention concerne également des détergents solides à mousse contrôlée contenant de tels mélanges de tensioactifs, ainsi que l'utilisation de tels mélanges de tensioactifs pour la fabrication de détergents solides à mousse contrôlée.
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

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

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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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US20090023820A1 (en) * 2006-02-22 2009-01-22 Basf Se Surfactant mixture containing short-chain and also long-chain components
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
US8567702B2 (en) 2011-02-09 2013-10-29 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
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
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
WO2023025766A1 (fr) * 2021-08-25 2023-03-02 Unilever Ip Holdings B.V. Composition détergente
EP4392513A1 (fr) * 2021-08-25 2024-07-03 Unilever IP Holdings B.V. Composition détergente

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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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DE19945353A1 (de) 2001-03-29
US6812201B1 (en) 2004-11-02
EP1214389B1 (fr) 2005-12-14
DE50011864D1 (de) 2006-01-19
WO2001021743A1 (fr) 2001-03-29
ES2254231T3 (es) 2006-06-16

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