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
  • C11D1/662—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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
• • 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
  • C11D1/721—End blocked ethers
• • 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
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

• the invention relates to detergents and cleaning agents which have a surfactant system based on alkyl and / or Contain alkenyl oligoglycosides and fatty alcohols, and its use for Increase washing performance at low temperatures.
• alkyl and / or alkenyl oligoglycosides are used in small amounts in the form of aqueous pastes or as granules with a fatty alcohol content below 1.5% for the formulation of washing and Detergents used.
• a fatty alcohol content below 1.5% for the formulation of washing and Detergents used.
• EP 0 301 298 A1 (Henkel) describes a process for the preparation of alkyl and / or alkenyl oligoglycosides, the excess fatty alcohol being distilled off to values below 0.5% by weight, preferably 3 to 5% by weight.
• the reaction product is processed into an easy-to-use 60% paste by adding water.
• products from these alkyl and / or alkenyl oligoglycoside mixtures are described which, on the one hand, are completely free of fatty alcohol, ie less than 0.5% by weight of fatty alcohol, but also 0.5 to 5, preferably 2.5 to 4,% by weight % Fatty alcohol contained.
• the present application describes washing and cleaning agents based on a surfactant system consisting of alkyl and / or alkenyl oligoglycoside and fatty alcohol, in which the fatty alcohol content was set in such a way that the washing performance is optimized low washing temperatures, preferably below 40 ° C.
• the fatty alcohol content (component b) is preferably 8 to 32% by weight, preferably 10 to 30 % By weight, in particular 11 to 25% by weight, based on the active substance alkyl and / or alkenyl oligoglycoside.
• the water content of the mixture of components a and b is optionally at most 2% by weight, preferably 0.1 to 1.5% by weight.
• Alkyl and / or alkenyl oligoglycosides which follow the formula (I) are preferably used to prepare the agents according to the invention, R 1 O- [G] p in which R 1 is a branched and unbranched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They are preferably produced by reacting glucose or dextrose monohydrate and fatty alcohol in the presence of catalysts.
• the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
• the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides.
• 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 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 18, carbon atoms.
• Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
• Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
• Another embodiment describes surfactant systems in detergents and cleaning agents, characterized in that fatty alcohol of the formula (II), R 1 OH are included, wherein R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, and the hydrocarbon radicals already described for R 1 are to be included. It is therefore preferred that the surfactant mixture according to the invention contains alkyl and / or alkenyl oligoglycoside and fatty alcohol with the same carbon chain cut. Depending on the process, the fatty alcohol can be introduced into the compositions via the alkyl and / or alkenyl oligoglycosides used, or in a separate form.
• Agents are furthermore preferred, characterized in that fatty alcohols of the formula (II) and / or fatty alcohols with alkyl and / or alkenyl radicals R 2 different from R 1 are present.
• the agents can therefore contain fatty alcohols, the C chain cut of which corresponds to that of the alkyl and / or alkenyl oligoglycosides.
• B have been introduced due to the process or separately.
• any fatty alcohols R 2 OH different from R 1 OH which, in turn, have been introduced via the alkyl and / or alkenyl oligoglycosides or can be added separately.
• Mixtures of different fatty alcohols (R 1 and R 2 ) are also possible in the surfactant system. It is also pointed out that the alkyl and / or alkenyl oligoglycosides can be freed from the fatty alcohol produced by distillation (depletion) and subsequently topped up with another fatty alcohol.
• R 2 stands for an aliphatic, linear or branched hydrocarbon radical with 4 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
• Typical examples are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolenyl alcohol, linolenyl alcohol, linoleyl alcohol, linoleyl alcohol Technical mixtures which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
• Technical fatty alcohols with 12 to 18 carbon
• the alkenyl radical R 2 can be derived from primary unsaturated alcohols.
• unsaturated alcohols are undecen-1-ol, laurolein alcohol, myristoline alcohol, palmitolein alcohol, petroselaidinal alcohol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol, palmoleyl alcohol, brassoleyl alcohol, brassol alcohol alcohol, brassidyl alcohol, brassoleyl alcohol, brassidyl alcohol, brassoleyl alcohol, brassidyl alcohol, brassol alcohol alcohol, brassidyl alcohol and brassidyl alcohol and saturated fatty alcohols which were obtained by the processes described in EP 0724 555 B1 .
• evaporators are considered that take this into account, but preferably thin-film evaporators, falling-film evaporators or short-path evaporators and - if necessary - any combination of these components.
• the depletion can then take place in a manner known per se, for example at temperatures in the range from 110 to 160 ° C. and reduced pressures from 0.1 to 10 mbar.
• detergents and cleaning agents are preferred, characterized in that the mixture of components a and b does not exceed 2% by weight, preferably 0.1 to 1.5% by weight, in particular 0.2 to 1.2% by weight Contains% water.
• Mixtures with viscosities in the range from 10 to 1000, preferably 50 to 600 [mPas, 110 ° C.] are further preferred.
• Mixtures which are bleached at temperatures of 60 to 150 ° C., preferably 80 to 110 ° C. are also preferred.
• Mixtures of a and b which combine all of these features are particularly preferably used.
• the viscosity is determined with a rotary viscometer (e.g. Rheomat 115, DIN 145). It is a measuring system with an internally rotating and an outer, fixed cylinder.
• the washing and cleaning agents contain alkoxylated alkanols, which are added as a mixture with components a and b, or else separately to the agents can.
• the alkoxylated alkanols introduced via the mixture can differ from the distinguish separately added.
• alkoxylated alkanols of the formula (III) as a rheology-modifying agent is preferred.
• Typical examples are fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (III) or fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (IV).
• fatty alcohol polyethylene glycol / polypropylene glycol ethers of the formula (III), which are optionally end-capped, are used as rheology-modifying agents, R 3 O (CH 2 CH 2 O) n [CH 2 (CH 3 ) CHO] m R 4 used, in which R 3 is an alkyl and / or alkylene radical having 8 to 22 C atoms, R 4 is H or an alkyl radical having 1 to 8 C atoms, n is a number from 1 to 40, preferably 1 to 30 , in particular 1 to 15, and m represents 0 or a number from 1 to 10.
• R 3 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
• n is a number from 1 to 10
• m represents 0
• R 4 represents hydrogen.
• These are addition products of 1 to 10 moles of ethylene oxide with monofunctional alcohols.
• the alcohols described above, such as fatty alcohols, oxo alcohols and Guerbet alcohols, are suitable as alcohols. Of such alcohol ethoxylates, those are also suitable which have a narrow homolog distribution.
• R 3 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
• n is a number from 2 to 7
• m is a number of 3 to 7
• R 4 represents hydrogen.
• the washing and cleaning agents contain further alcohols and / or alkylene oxides, preferably ethanol, n-butanol, n-propanol, isopropanol and mono-, Oligo- and poly-glycols based on ethylene, propylene, butylene, especially 1,2-propanediol and 1,3-propanediol, and their methyl, ethyl and butyl ethers.
• alcohols and / or alkylene oxides preferably ethanol, n-butanol, n-propanol, isopropanol and mono-, Oligo- and poly-glycols based on ethylene, propylene, butylene, especially 1,2-propanediol and 1,3-propanediol, and their methyl, ethyl and butyl ethers.
• detergents and cleaning agents characterized in that they contain further nonionic surfactants selected from the group formed by alkyl and / or alkenyl oligoglycosides (different from those according to the invention), further alkoxylated alkanols, hydroxy mixed ethers, fatty acid lower alkyl esters and amine oxides.
• nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkylglucamides, Protein hydrolysates (especially vegetable products based on wheat), polyol fatty acid esters, Sugar esters, sorbitan esters, polysorbates and amine oxides.
• nonionic surfactants Containing polyglycol ether chains these can be conventional, but preferably one have narrow homolog distribution.
• Alkyl and / or Alkenyl oligoglycosides (different from those according to the invention), further alkoxylated alkanols, Hydroxy mixed ether, fatty acid lower alkyl esters and amine oxides used.
• Hydroxy mixed ethers are known nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol components, which can be obtained, for example, by subjecting olefin epoxides to a ring opening reaction with fatty alcohol polyglycol ethers.
• HME Hydroxy mixed ethers
• Corresponding products and their use in the field of cleaning hard surfaces is, for example, the subject of the European patent EP-B1 0693049 and the international patent application WO 94/22800 (Olin) and the documents mentioned therein.
• R 7 represents a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms
• R 2 represents hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms
• R 3 represents hydrogen or methyl
• R 10 represents a linear or branched, alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms
• e represents numbers from 1 to 50, preferably 2 to 25 and in particular 5 to 15, with the proviso that the sum of the carbon atoms in the radicals R 7 and R 8 is at least 4 and preferably 12 to 18.
• the HME ring opening products can be either internal olefins (R 8 not equal to hydrogen) or terminal olefins (R 8 equal to hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties.
• the polar part of the molecule can be a polyethylene glycol (PE) or a polypropylene glycol chain (PP); Mixed chains of PE and PP units, whether in statistical or block distribution, are also suitable.
• Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decenepoxid, 4,5-Decenepoxid, 1,2-Dodecenepoxid, 2,3-Dodecenepoxid, 3,4-Dode-Cenepoxid, 4,5-Dodecenepoxid, 5,6-Dodecenepoxid, 1,2-Tetradecenepoxid, 2,3 -Tetradecenepoxid, 3,4-Tetradecenepoxid, 4,5-Tetradecenepoxid, 5,6-Tetradecenepoxid, 6,7-Tetradecenepoxid, 1,2-Hexa-decenepoxid,
• Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) R 11 CO (OCH 2 CHR 12 ) s OR 13 in which R 11 CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R 12 for hydrogen or methyl, R 13 for linear or branched alkyl radicals with 1 to 4 carbon atoms and s for numbers from 1 to 20 stands.
• Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and technical grade mixtures and erucas.
• the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
• the preparation of the amine oxides of the formula (VII) is based on tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide.
• R 16 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms
• R 14 and R 15 independently of one another are R 16 or, if appropriate hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.
• Amine oxides of the formula (VII) are preferably used in which R 16 and R 14 are C 12/14 and C 12/18 cocoalkyl radicals and R 15 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (VII) in which R 16 is a C 12/14 or C 12/18 cocoalkyl radical and R 14 and R 15 are methyl or hydroxyethyl.
• alkylamido amine oxides of the formula (VIII), the alkylamido radical R 23 CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from C 12/14 or C 12/18 - fatty acids with amines.
• R 24 represents a linear or branched alkylene group having 2 to 6, preferably 2 to 4 carbon atoms and R 14 and R 15 have the meaning given in formula (VII) .
• detergents and cleaning agents characterized in that they contain anionic surfactants selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, soaps, monoglyceride (ether) sulfates and alkane sulfonates.
• anionic surfactants selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, soaps, monoglyceride (ether) sulfates and alkane sulfonates.
• anionic surfactants are soaps, alkylbenzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerin ether sulfates, mono ether sulfate sulfate, hydroxymischogether sulfate, fatty acid ether sulfate sulfates, Mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarc
• anionic surfactants are alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, monoglyceride (ether) sulfates and secondary alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates.
• Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (IX) R 40 O-SO 3 X in which R 40 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
• alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
• the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
• Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
• ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
• SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
• ether sulfates are suitable which follow the formula (X) R 17 O- (CH 2 CH 2 O) a SO 3 X in which R 17 represents a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
• Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, aryl alcohol alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, o
• the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
• Alkylbenzenesulfonates preferably follow the formula (XI) , R 18 -Ph-SO 3 X in which R 18 represents a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph a phenyl radical and X an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
• R 18 represents a branched but preferably linear alkyl radical having 10 to 18 carbon atoms
• Ph a phenyl radical
• X an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
• Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used
• Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
• the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
• the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)].
• Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67 , 8 (1990) .
• the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (XI), in which R 19 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, c, d and e in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal.
• Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide.
• Monoglyceride sulfates of the formula (XII) are preferably used, in which R 19 CO represents a linear acyl radical having 8 to 18 carbon atoms.
• Alkane sulfonates are taken to mean compounds of the formula (XIII) .
• R 20 and R 21 represent alkyl radicals, where R 20 and R 21 together should not have more than 50 carbon atoms.
• soaps are to be understood as meaning fatty acid salts of the formula (XIV) R 41 CO-OX in which R 41 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X represents alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
• Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, petol acid Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
• coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.
• detergents and cleaning agents are described, characterized in that they contain cationic, amphoteric or zitterionic surfactants selected from the group formed by esterquats , alkyl betaines, amidoamine betaines and imidazolinium betaines.
• cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats .
• quaternized fatty acid triethanolamine ester salts of the formula (XV) in which R 44 CO is an acyl radical having 6 to 22 carbon atoms, R 45 and R 46 independently of one another are hydrogen or R 14 CO, R 15 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate.
• R 44 CO is an acyl radical having 6 to 22 carbon atoms
• R 45 and R 46 independently of one another are hydrogen or R 14 CO
• R 15 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, al
• ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
• Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as high elaidic acid C 16/18 fatty acid cuts are preferably used.
• the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
• an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
• the preferred ester quats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 - tallow or. Palm fatty acid (iodine number 0 to 40).
• quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven particularly advantageous, in which R 44 CO for an acyl radical with 16 to 18 carbon atoms, R 45 for R 45 CO, R 46 for hydrogen, R 17 for a methyl group, m1 , m2 and m3 stands for 0 and Y for methyl sulfate.
• quaternized ester salts of fatty acids with diethanolalkylamines of the formula (XVI) are also suitable as esterquats, in which R 48 CO for an acyl radical with 6 to 22 carbon atoms, R 49 for hydrogen or R 48 CO, R 50 and R 51 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate.
• ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (XVII) should be mentioned as a further group of suitable ester quats, in the R 52 CO for an acyl radical with 6 to 22 carbon atoms, R 53 for hydrogen or R 52 CO, R 54 , R 55 and R 56 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12 and X again represents halide, alkyl sulfate or alkyl phosphate.
• suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XVIII) based on diethylenetriamine, in which R 57 CO represents an acyl radical with 6 to 22 carbon atoms, R 58 for hydrogen or R 57 CO, R 59 and R 60 independently of one another for alkyl radicals with 1 to 4 carbon atoms and Y again for halide, alkyl sulfate or alkyl phosphate.
• Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.
• alkyl betaines examples include alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
• alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII) in which R 31 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 32 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 33 for alkyl radicals with 1 to 4 carbon atoms, q1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium.
• Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl-amine, oleyl dimethyl amine, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.
• Carboxyalkylation products of amidoamines which follow the formula (XX) are also suitable, in which R 34 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 35 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 36 for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers from 1 to 6, q3 for numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium.
• Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino propylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
• Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
• polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
• AEEA aminoethylethanolamine
• the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
• Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
• the detergents can be anionic, nonionic and / or amphoteric or zwitterionic Surfactants in amounts of 0.5 to 50, preferably 5 to 25 and in particular 10 to 20 wt .-% - based on the detergent - included.
• the detergents and cleaning agents contain 0.5 to 25% by weight, preferably 1 to 15% by weight, in particular 2 to 10% by weight, of alkyl and / or alkenyl oligoglycosides, based on the active substance of the formulation.
• Another object of the invention is the use of the mixture of components a and b in washing and cleaning agents to increase the washing performance at low temperatures, preferably at 30 to 40 ° C.
• the detergents and cleaning agents can be in various dosage forms. The use of components a and b in detergents and cleaning agents which are in the form of tablets, powders, liquids or gels is preferred.
• the washing and cleaning agents can be prepared by spray drying and the addition of a liquid or solid fatty alcohol-containing alkyl and / or alkenyl oligoglycoside in the preparation, but also by spray mixing processes and direct addition of the liquid or solid mixture.
• the fatty alcohol can be introduced separately into the detergent and cleaning agent. Furthermore, all known processes for the production of detergents and cleaning agents are possible.
• the detergents and cleaning agents according to the invention can also contain additional inorganic and organic builder substances, for example in amounts of 10 to 50 and preferably 15 to 35 % By weight, based on the composition, mainly as inorganic builder substances Zeolite crystalline layered silicates, amorphous silicates and - where permissible - also phosphates, e.g. Tripolyphosphate are used.
• the amount of co-builder is based on the preferred amounts to be counted against zeolite and phosphates.
• 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 may contain minor 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 from 0 to 20 and preferred values for x are 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1 .
• Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171 .
• Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
• small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
• the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
• the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
• Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1 .
• 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 be caused in various ways, for example by surface treatment, compounding, compacting / compression 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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 .
• Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• the sodium salts of orthophosphates, pyrophosphates and in particular are particularly suitable the tripolyphosphate.
• Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent.
• tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic Improve secondary washing ability.
• Examples of useful organic scaffolding substances that can be used as co-builders are polycarboxylic acids which 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), if such use is not objectionable for ecological reasons, as well as mixtures from 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 too in itself can be used.
• the acids typically have also the property of an acidifying component and thus also serve to adjust one lower and milder pH of detergents or cleaning agents.
• an acidifying component typically be Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of to call this.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used.
• a preferred dextrin is described in British patent application GB 9419091 A1 ,
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
• An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable .
• a product oxidized 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 described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 . Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are from 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be in lactone form and which have at least 4 carbon atoms and at least one hydroxyl group and a maximum contain two acid groups.
• Such cobuilders are described, for example, in international patent application WO 95/20029 .
• Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid).
• Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
• Granular polymers are usually subsequently mixed into one or more basic granules.
• biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
• Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids their 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 that make the oil and fat washable made of textiles.
• the preferred oil and fat dissolving components include for example with nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Technically known polymers of phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
• bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying 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. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-diacetyloxy, 2,5-ethylene glycol 2,5-dihydrofuran and the enol esters known from German
• hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 19616770 and international patent application WO 95/14075 are also preferably used.
• the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
• the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts.
• the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, described in German patent application DE 19605688 A1 and copper complexes with nitrogen-containing tripod ligands that from German patent application DE known cobalt 19620411 A1, iron-, copper- and ruthenium-ammine complexes, the manganese, copper described in the German patent application DE 4416438 A1 and cobalt complexes , the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganese
• Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
• 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 carry in the Laundry for removing stains, such as stains containing protein, fat or starch, and Graying at. Cellulases and
• proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus be used.
• Enzyme mixtures for example of protease and amylase or Protease and lipase or lipolytic enzymes or protease and cellulase or from Cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic 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.
• lipolytically active Enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven suitable.
• Suitable amylases include in particular ⁇ -amylases, iso-amylases, Pullulanases and pectinases.
• Cellobiohydrolases are preferably used as cellulases, Endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures of used this. Because the different cellulase types are characterized by their CMCase and Avicelase activities can differentiate, the desired by specific mixtures of the cellulases Activities can be discontinued.
• the enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition.
• the percentage of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
• the agents can contain further enzyme stabilizers.
• enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
• calcium salts magnesium salts also serve as stabilizers.
• boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
• Graying inhibitors have the task of removing the dirt detached from the fibers in the liquor to keep suspended and thus prevent the dirt from re-opening.
• water soluble Colloids mostly of an organic nature are suitable, for example the water-soluble salts polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids 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.
• Farther soluble starch preparations and starch products other than those mentioned above can be used, e.g. degraded starch, aldehyde starches, etc.
• Polyvinylpyrrolidone can also be used.
• cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example in quantities from 0.1 to 5% by weight, based on the composition.
• the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.
• Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
• a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
• Suitable soil-repellants are substances which preferably Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10.
• the molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, i.e. the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approx. 15 up to 100.
• the polymers have an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure.
• Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the Milease® products T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
• Wax-like compounds can be used as defoamers. Such are called “waxy” Compounds understood that have a melting point at atmospheric pressure above 25 ° C. (Room temperature), preferably above 50 ° C and in particular above 70 ° C.
• the wax-like defoamer substances are practically insoluble in water, i.e. at 20 ° C they show a solubility of less than 0.1% by weight in 100 g of water.
• Suitable waxy Compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of one and polyhydric alcohols and paraffin waxes or mixtures thereof.
• the silicone compounds known for this purpose can also be used.
• Suitable paraffin waxes are generally 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.
• the soft waxes which have a melting point in the range from 35 to 50 ° C., preferably include the group of petrolates and their hydrogenation products.
• solid hydrocarbons with melting points between 63 and 79 ° C which are separated from the highly viscous, paraffin-containing lubricating oil distillates during the dewaxing.
• These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffins.
• the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C.
• paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
• Particularly preferred paraffin wax mixtures at 30 ° C have a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, 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 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 particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
• the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
• Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms.
• suitable Fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof as they are from natural fats or hardened oils, such as tallow or hydrogenated palm oil are.
• Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
• Diamines are ethylenediamine and hexamethylenediamine.
• Bisamides are particularly preferred Bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
• Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
• these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
• the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
• suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
• Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
• Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol monostearate, ethylene glycol and sorbitan, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl and diesters.
• Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred.
• Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
• 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
• carnauba wax which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
• Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stearic acid, Oleic acid, palmitic acid, myristic acid and lauric acid and their mixtures, as made up natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are.
• Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
• the corresponding fatty alcohols of the same C chain length can be used.
• Dialkyl ethers may also be present as defoamers.
• the ethers can be asymmetric or be constructed symmetrically, i.e. two identical or different alkyl chains, preferably contain from 8 to 18 carbon atoms.
• Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point above Have 25 ° C, especially above 40 ° C.
• Suitable defoamer compounds are fatty ketones, which 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, arachic acid, gadoleic acid, behenic acid or erucic acid.
• Suitable defoamers are fatty acid polyethylene glycol esters, which are preferably basic homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained. Especially done the addition of ethylene oxide to the fatty acids in the presence of alkanolamines as catalysts.
• alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation of fatty acids, especially when it comes to low ethoxylated compounds manufacture.
• 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 layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
• the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
• the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
• the aluminosilicates referred to as carrier material include in particular the zeolites, for example zeolite NaA and NaX.
• the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
• suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
• Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
• Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
• the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
• native starch which is composed of amylose and amylopectin. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
• Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
• alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
• Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have an almost linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
• silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which can also be silanated.
• Silicic acid-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
• the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C.
• silicones in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
• the silicones are preferably used in the form of their aqueous emulsions. As a rule, the silicone is added to the water initially introduced with stirring. If desired, thickeners such as are known from the prior art can be added to increase the viscosity of the aqueous silicone emulsions.
• nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyoxy cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC) are particularly preferred.
• Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
• aqueous silicone solutions are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat.
• the starch is advantageously present in amounts of 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned.
• the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added.
• the silicones are expediently incorporated with the aid of effective stirring and mixing devices.
• the solid preparations can further contain disintegrants or disintegrants.
• Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
• Swelling disintegration aids are, for example, synthetic polymers such as optionally crosslinked polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
• PVP polyvinylpyrrolidone
• Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention. Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
• Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
• celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
• the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant.
• Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
• Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
• microcrystalline celluloses which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
• the disintegrants can be macroscopically homogeneously distributed in the shaped body, but microscopically they form zones of increased concentration due to the manufacturing process.
• Disintegrants which can be present within the meaning of the invention, such as, for example, collidone, alginic acid and its alkali metal salts, amorphous or also partially crystalline sheet silicates (bentonites), polyacrylates, polyethylene glycols are, for example, the publications WO 98/40462 (Rettenmaier), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 (Henkel) can be found. Reference is expressly made to the teaching of these writings.
• the moldings can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.
• fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
• Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, Benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and Benzyl salicylate.
• the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g.
• the hydrocarbons mainly include terpenes such as Lime and pinene.
• terpenes such as Lime and pinene.
• perfume oils can also be natural Fragrance mixtures contain, as are available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil.
• muscatel sage oil
• Chamomile oil clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, Olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.
• the fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the perfume adheres to the laundry intensify and ensure a long-lasting fragrance of the textiles through a slower fragrance release.
• Cyclodextrins for example, have proven successful as such carrier materials, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
• 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;
• alkali carbonate and / or amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
• the content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
• the 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.
• Sodium sulfate for example, may also be present as a filler or filler in amounts of 0 to 10, in particular 1 to 5,% by weight, based on the agent.
• test fabrics from the Krefeld laundry research (WFK) in Krefeld with various types of soiling are used (Table 1). 2 test fabrics each are attached to a terry towel
• test fabrics and 3.5 kg of clean accompanying laundry are washed with a Miele W 918 in a color wash program at 30 and 60 ° C, and with a dosage of 75 g / powder per wash cycle.
• water water hardness 16 ° d
• the washing result of the detergents according to the invention was determined using a triple determination in different machines of the same type.
• test specimens are detached from the carrier cloth and ironed.
• the reflectance of the tissue is measured with a Minolta Cromameter in Y xy mode. In this way, two measurement values were first generated per cycle and tissue (flap 1 + 2). The resulting mean value corresponds to the result of a simple determination. Three of these simple determinations were averaged for the final result (see Table 3).
• Table 2 below compares the formulations of two comparative tests (V1 and V2) of a formulation (B) according to the invention. All data are to be understood as% by weight and are calculated as active substance.
• the comparison of the washing results shows that the use of the surfactant systems according to the invention (B) results in improved washing performance.
• a significant improvement in washing performance can be seen e.g. for soiling with lipstick at washing temperatures of 30 °.

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