WO2001032818A1 - Enzyme-containing high-viscosity liquid detergents - Google Patents
Enzyme-containing high-viscosity liquid detergents Download PDFInfo
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- WO2001032818A1 WO2001032818A1 PCT/EP2000/010337 EP0010337W WO0132818A1 WO 2001032818 A1 WO2001032818 A1 WO 2001032818A1 EP 0010337 W EP0010337 W EP 0010337W WO 0132818 A1 WO0132818 A1 WO 0132818A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D3/2065—Polyhydric 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
Definitions
- the present invention relates to liquid detergents containing enzymes and surfactants which, due to the use of a thickener and an enzyme stabilization system, are stable in storage and viscosity under a wide variety of climatic conditions, are not subject to phase separation and have color stability even when exposed to light.
- liquid detergents are usually used through the use of thickeners such as agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose and other cellulose ethers such as hydroxyethyl and -propyl cellulose, powdered meal ether, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides. Polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas are converted into higher-viscosity products.
- the use of these thickeners to increase viscosity in a wide variety of liquids has long been state of the art.
- the use of polymers in liquid detergents is also well known.
- Liquid detergents with viscosities between 500 to 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European patent application EP 0 691 399. These compositions contain 10 to 45% by weight of surfactant (s), at least one builder and 0.01 to 5% by weight of a mercapto-terminated polymer with an average molecular weight of between 1500 and 50,000 gmol "1 .
- Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in European patent application EP 0 724 013. This effect is achieved through the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, whereby the concentrate has a viscosity of less than 2500 mPas and loses its micellar structure in favor of the formation of a lamellar phase when diluted with water.
- WO 96/01305 describes an aqueous cleaning and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes of 10 to 100 nm.
- the composition contains 20 to 70% by weight of water, 15 to 40% by weight of a surfactant system which contains at least one nonionic surfactant from the group of the alkoxylated alcohols and not more than 20 %
- a surfactant system which contains at least one nonionic surfactant from the group of the alkoxylated alcohols and not more than 20 %
- anionic, cationic, ampho- or zwitterionic surfactant contains 5 to 30% by weight of solvent and 5 to 20% by weight of water-insoluble oil.
- aqueous, higher-viscosity liquid detergents are known, containing surfactant (s) and other usual ingredients of detergents and cleaning agents, the agents as a thickening system, based in each case on the total agent, 0.1 to 5% by weight. -% of a polymeric thickener, 0.5 to 7 wt .-% of a boron compound and 1 to 8 wt .-% of a complexing agent.
- the agents known from this publication are stable in viscosity, do not tend to agglomerate or phase separation and have no reduction in color stability under the influence of light.
- the document contains no information on the possible stability of enzymes contained in such agents.
- enzyme-containing liquid detergents with the property profile mentioned can be prepared if a polymeric thickener, a special enzyme stabilizer system and a specific surfactant are incorporated into the detergents.
- the invention therefore relates to enzyme-containing, aqueous, highly viscous liquid detergents, containing surfactant and 0.1 to 5% by weight of polymeric thickener, and further conventional ingredients of detergents and cleaning agents, the agents being characterized in that they contain surfactant based on saccharide, contain at least one enzyme from the group comprising cellulase, amylase and protease and an enzyme stabilizer system from the components a) boron compound and / or sodium formate and b) polyhydric alcohol.
- the use of the polymeric thickener makes it possible to produce higher-viscosity liquid detergents which are free from the disadvantages mentioned. According to the invention, it is possible to produce concentrated, higher-viscosity liquid detergents which have surfactant contents above 35% by weight.
- An agent according to the invention contains at least one protease.
- Cellulase or amylase preferably at least two of these enzymes and particularly preferably all three enzymes being present.
- the agents according to the invention contain protease and amylase, protease and cellulase, amylase and cellulase or protease, amylase and cellulase. If desired, more than one representative from one of the enzyme classes mentioned can also be present.
- the proteases preferably used include the protease from Bacillus lentus, which is stable and active under alkaline conditions; it can be produced as described in international patent application WO 91/02792 in Bacillus lentus (DSM 5483).
- This Bacillus lentus alkaline protease (BLAP) can be obtained by fermentation of Bacillus licheniformis transformed with an expression plasmid which carries the gene for BLAP under the control of the Bacillus licheniformis ATCC 53926 promoter.
- composition as well as the spatial structure of BLAP is known (DW Godette et al., J. Mol. Biol. 228, 580-595, 1992).
- This protease is characterized by the sequence of 269 amino acids described in the cited literature, a calculated molecular weight of 26,823 daltons and a theoretical isoelectric point of 9.7.
- Variants of this Bacillus lentus DSM 5483 protease accessible by mutation are described in US Pat. No. 5,340,735. These include protease enzymes which, in particular when washing textiles made of proteinogenic fibers, for example textile fabrics made of natural silk or wool, result in particularly low substance damage or destruction of the fiber dressings without loss of cleaning performance.
- proteases which can be used according to the invention also include genetically modified ones Proteases of the abovementioned BLAP type, in which the amino acid leucine (L in the customary one-letter code) present at this point in the wild-type protease in position 211 (BLAP count) is replaced by aspartic acid (D) or glutamic acid (E) is (L21 1D or L21 1E).
- L amino acid leucine
- E glutamic acid
- Bacillus lentus protease such as at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or VI 991, may have been made. It is particularly preferred to use a variant in which at least one of the amino acid exchanges S3T, V4I, V193M, V199I or L21 1D has been carried out.
- protease nomenclature on the exchange of individual amino acids it should be noted that the numbering of the amino acid positions in BLAP differs from that which is frequently found for the subtilisin BPN '.
- positions 1 to 35 is identical in subtilisin BPN 'and BLAP; due to the lack of corresponding amino acids, positions 36 to 54 in BLAP correspond to positions 37 to 55 in BPN ', likewise positions 55 to 160 in BLAP correspond to positions 57 to 162 in BPN' and positions 161 to 269 correspond to those from 167 to 275 in BPN '.
- An agent according to the invention preferably contains Savinase® and / or an optionally genetically modified protase from Bacillus lentus.
- Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and for this purpose have been used for a long time in detergents for dishes, but also in detergents for use in textile washing.
- both amylases of the Termamyl® type and genetically modified amylases that is to say those having an amino acid sequence which has been modified in comparison to naturally occurring amylases with the aid of genetic engineering methods, can be used, as described, for example, in international patent applications WO 94/18314 or WO 95/21247 are known.
- the cellulase which can be used according to the invention belongs to the enzymes which can be obtained from bacteria or fungi and which preferably have a pH optimum of almost neutral to have a weakly alkaline pH range from 6 to 9.5.
- Such cellulases are known, for example, from German laid-open documents DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832.
- EP 269 077, EP 270 974, EP 273 125 and EP 339 550 known.
- Suitable commercial products are, for example, Celluzyme® and Carezyme® from Novo Nordisk or KAC® from Kao.
- the preferred cellulases also include those from Melanocarpus sp.
- Myriococcum sp. Available 20K cellulase, which is known from international patent application WO 97/14804. As described there, it has a molecular weight of about 20 kDa and has at least 80% of its maximum activity at 50 ° C. in the pH range from 4 to 9, with almost 50% of the maximum activity remaining at pH 10. As also described there, it can be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants.
- the agents according to the invention can, if desired, include further enzymes, in particular from the group consisting of lipases, cutinases, isopeptidases, xylanases, hemicellulases, pullulanases, neopullulanases, mannanases, mycodextranans, polygalacturanase, keratanases, chondroitinases, pectinases, laccatases and oxidases / or contain peroxidases.
- further enzymes in particular from the group consisting of lipases, cutinases, isopeptidases, xylanases, hemicellulases, pullulanases, neopullulanases, mannanases, mycodextranans, polygalacturanase, keratanases, chondroitinases, pectinases, laccatases and oxidases / or contain peroxidases.
- the saccharide-based surfactants include, on the one hand, alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides and can also take fractional numbers, is an analytically determinable number between 1 and 10; x is preferably 1.2 to 1.4.
- the saccharide-based surfactants also include polyhydroxy fatty acid amides of the formula I,
- RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
- R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
- [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula II
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 6 -alkyl or phenyl radicals being preferred
- [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical , [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of international patent application WO 95/07331 Reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst can be converted into the desired polyhydroxy fatty acid amides.
- the content of preferred liquid detergents in such surfactants based on saccharide is 0.5 to 25% by weight. preferably 1 to 10 wt .-% and in particular 1.5 to 5 wt .-%, each based on the total agent.
- Another essential component of the invention of the enzyme-containing, higher-viscosity liquid detergent is a polymeric thickener.
- These organic high-molecular substances which are also called swelling agents, soak up liquids, swell them up and finally convert into viscous real or colloidal solutions, come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers and their mixtures.
- Modified natural products come primarily from the group of modified starches and celluloses.
- carboxymethyl cellulose and other cellulose ethers are exemplary here.
- Hydroxyethyl and propyl cellulose and core meal ether called.
- a large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds. Vinyl polymers, polycarboxylic acids, polyethers. Polyimines, polyamides and polyurethanes.
- Such fully synthetic polymeric thickeners are preferably present in agents according to the invention in amounts from 0.2% by weight to 4% by weight, in particular from 0.4% by weight to 3% by weight and particularly preferably from 0.5% by weight. -% to 2 wt .-% contain.
- mixtures of optionally modified natural polymer and fully synthetic polymer are used as polymeric thickeners.
- Thickeners from the substance classes mentioned are commercially available and are sold, for example, under the trade names Acusol -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer. 30% strength in water, Rohm & Haas).
- Dapral ® -GT-282-S alkyl polyglycol ether, Akzo
- Deuteron polymer 11 dicarboxylic acid copolymer, Schönes GmbH
- Deuteron ® -XG anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH
- Deuteron ® -XN non-ionic polysaccharide, Schoener GmbH
- Dicrylan ® thickener-O ethylene oxide adduct, 50% in water isopropanol, Pfersse Chemie
- EMA ® -81 and EMA ® -91 ethylene-maleic anhydride copolymer, Monsanto).
- Thickener-QR-1001 polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox & -AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD -FX-1100 (hydrophobic urethane polymer. Servo Delden), Shellflo ® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell).
- Preferred aqueous liquid detergents contain 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of a polysaccharide as thickening agent.
- a preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons.
- Xanthan is formed from a chain with ß-1,4-bound glucose (cellulose) with side chains.
- Xanthan can be described by the following formula:
- Preferred aqueous liquid detergents each contain from 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of xanthan as the thickener.
- the first component of the enzyme stabilization system in the agents according to the invention is alkali metal formate and / or a boron compound, which are preferably used in amounts of 0.5 to 7% by weight, the alkali metal formates being selected from lithium formate, sodium formate, potassium formate and mixtures thereof can be.
- alkali metal formates being selected from lithium formate, sodium formate, potassium formate and mixtures thereof can be.
- boron compounds which can be used in the context of the present invention are boric acid, boron oxide, alkali borates such as ammonium, sodium and potassium ortho, meta and pyroborates, borax in its various hydration stages and polyborates such as alkali metal pentaborates.
- Organic boron compounds such as esters of boric acid can also be used.
- liquid detergents contain 0.5% by weight to 5% by weight, preferably 0.75% by weight to 3% by weight and in particular 1% by weight to 2% by weight of sodium formate, boric acid and / or sodium tetraborate.
- the liquid detergents according to the invention contain polyhydric alcohol, such as glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol and or hexylene glycol.
- glycerol and / or propylene glycol is particularly preferred, the latter preferably 1.2 -Propylenegylokol is, but also 1,3-Propypenglykol as well as mixtures of both can be used.
- This second component is preferably present in amounts of 0.5% by weight to 15% by weight in agents according to the invention.
- the liquid detergents according to the invention can contain further surfactant, it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, the proportion of the nonionic surfactants, including the saccharide-based surfactants essential to the invention, should be greater than the proportion of anionic surfactants.
- the total surfactant content of the liquid detergents according to the invention is preferably in the range from 15% by weight to 80% by weight, in particular from 20% by weight to 60% by weight.
- the additional nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- preferred Alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used.
- Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
- nonionic surfactants used with preference are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese Patent Application JP 58/217598 or which are preferably described in of the international patent application WO 90/13533.
- Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
- Anionic surfactants that can be used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C. 3 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 1 8 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates which are derived from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization be won.
- esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates).
- the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
- sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid. Caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of the -C 8 -C fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the -C 0 -C o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
- C 2 -C 6 alkyl sulfates and C 2 -Ci 5 alkyl sulfates and C 4 -C 5 alkyl sulfates are preferred.
- 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
- l - Alcohols such as 2-methyl-branched C _ ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ . ⁇ 8 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 - ⁇ fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Soaps are particularly suitable as further anionic surfactants.
- Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the content of preferred liquid detergents in anionic surfactants is 5 to 35% by weight, preferably 8 to 30% by weight and in particular 10 to 25% by weight, in each case based on the total composition.
- the viscosity of the agents according to the invention can be measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 500 to 5000 mPas.
- Preferred agents have viscosities of 1000 to 4000 mPas, values between 2000 and 3500 mPas being particularly preferred.
- the agents according to the invention may contain further ingredients which further improve the technical and / or aesthetic properties of the liquid detergent.
- preferred agents additionally contain one or more substances from the group of builders, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors. Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides. Antioxidants. Corrosion inhibitors. Antistatic agents. Ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.
- the builders that can be contained in the liquid detergents according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
- Suitable crystalline, layered sodium silicates have the general formula NaMSi O 2x + ⁇ ' y H 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 2 , 3 or 4 are.
- Such crystalline layered silicates are described, for example, in European patent application EP 0 164 514.
- 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 Si O 5 -yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.
- Amorphous sodium silicates with a modulus Na O: SiO 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 in dissolution, can also be used 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 are added
- Electron diffraction experiments provide washed-out or even sharp diffraction maxima. 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 44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the optionally used fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and or P are also suitable.
- zeolite X 80% by weight zeolite X
- VEGOBOND AX ® which has the formula nNa 2 O ⁇ (ln) K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiO 2 • (3.5 - 5.5) H 2 O
- 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 small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 8 -C 8 fatty alcohols with 2 to 5 ethylene oxide groups, C ⁇ -C ⁇ 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, for example using Coulter Counter) and preferably contain 18 to 22 wt .-%. in particular 20 to 22% by weight of bound water.
- 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.
- Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as those carboxylic acids which carry more than one acid function.
- these are citric acid.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
- the acids themselves can also be used.
- the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
- citric acid and succinic acid To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.
- Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
- the molar masses given for polymeric polycarboxylates are, for the purposes of the present specification, weight-average molar masses M w of the particular acid form, which can in principle be determined by means of gel permeation chromatography (GPC), a UV detector being used.
- GPC gel permeation chromatography
- the measurement is carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated.
- This information differs significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard, those measured against polystyrene sulfonic acids Molar masses are usually significantly higher.
- Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol.
- the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
- copolymeric polycarboxylates 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 polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid known from European patent EP 0 727 448 B1.
- biodegradable polymers composed of more than two different monomer units, for example those which, according to German patent application DE 43 00 772 AI, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to German patent DE 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
- Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
- Also to be mentioned as further preferred organic builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
- polyaspartic acids or their salts and derivatives are particularly preferred, of which it is disclosed in German patent application DE 195 40 086 A1 that they have a bleach-stabilizing effect in addition to cobuilder properties.
- Other suitable builder substances are 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 0 280 223.
- Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- 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 g / mol.
- 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 2000 to 30000 g / mol can be used.
- a preferred dextrin is described in European patent application EP 0 703 292 AI.
- 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 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110 , WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
- An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
- a product oxidized at C of the saccharide ring can be particularly advantageous.
- Ethylene diamine N, N'-disuccinate (EDDS) the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts.
- glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become.
- organic builders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 Contain carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such builders are described, for example, in international patent application WO 95/20029. Organic builder substances are preferably present in the agents according to the invention in amounts of 1% by weight to 8% by weight.
- a wide number of different salts can be used as electrolytes from the group of inorganic salts.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl in the agents according to the invention is preferred.
- the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
- Non-aqueous solvents that can be used in the agents according to the invention come, for example, from the group of monohydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
- the solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene ether glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybut
- pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation. In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and are not sensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity towards textile fibers. so as not to stain them.
- Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
- Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and on Polymers of phthalic acid and / or terephthalic acid or of 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.
- Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances absorb on the fiber and bring about a brightening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results.
- Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole , Benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
- the optical Brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished agent.
- 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 example glue, gelatin, salts of 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 (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition
- the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
- the agents according to the invention can contain antimicrobial agents.
- antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely with the agents according to the invention.
- the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates. Phosphites and phosphonates.
- Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
- External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
- silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties.
- Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
- Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C.
- the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
- UV absorbers which absorb onto the treated textiles and improve the light resistance of the fibers.
- Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
- Substituted benzotriazoles phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.
- Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- a preferred class of complexing agents are the phosphonates, which are used in preferred liquid detergents in amounts of 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular 0.03 to 0.5% by weight. -% are included.
- organophosphonates such as, for example, 1-hydroxyethane-l, l-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-l, 2.4 tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
- organophosphonates such as, for example, 1-hydroxyethane-l, l-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-l, 2.4 tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
- Particularly preferred liquid detergents contain l-hydroxyethane-l, l-di
- the agents according to the invention can be prepared by simply mixing the constituents in stirred kettles, water, any non-aqueous solvents and surfactants which may be present being expediently introduced and the further constituents being added in portions. A separate heating during production is not necessary, if it is desired, the temperature of the mixture should not exceed 80 ° C. Examples
- liquid detergents E1 to E4 according to the invention were prepared by mixing the individual constituents.
- Keltrol ® T xanthan gum, polysaccharide (Kelco)
- Turpina 4 NL hydroxyethane-1,1-diphosphonic acid, tetra-Na salt
- Protease I BLAP® 260
- Protease II Savinase® 16.0 L
- Amylase Termamyl® L 300
- Cellulase Carezyme® 4500 L. (Novo Nordisk)
- the liquid detergents had viscosities in the range from 2400 mPas to 3200 mPas. To test their storage stability, they were stored for 16 weeks in different climatic conditions and their appearance was assessed visually. They showed good stability both in the summer climate (25 - 40 ° C) and in the autumn climate (10 - 30 ° C) or in the winter climate (0 - 10 ° C). The enzymatic activity did not decrease significantly.
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Abstract
The invention relates to enzyme-containing high viscosity liquid detergents. The aim of the invention is to improve the stability of aqueous, high-viscosity liquid detergents that contain a tenside and 0.1 % by weight to 5 % by weight of a polymer thickener and other conventional ingredients. To this end, the inventive detergents contain a tenside on the basis of saccharide, at least one enzyme from the group comprising cellulase, amylase and protease and an enzyme stabilizer system that consists of the components a) a boron compound and/or a sodium formiate and b) a polyvalent alcohol.
Description
Enzymhaltige höherviskose Flüssigwaschmittel Enzyme-containing, higher-viscosity liquid detergents
Die vorliegende Erfindung betrifft enzym- und tensidhaltige Flüssigwaschmittel, die durch den Einsatz eines Verdickungsmittels und eines Enzymstabilisierungssystems unter den verschiedensten klimatischen Bedingungen lager- und viskositätsstabil sind, keiner Phasentrennung unterliegen und auch bei Lichteinfluß Farbstabilität aufweisen.The present invention relates to liquid detergents containing enzymes and surfactants which, due to the use of a thickener and an enzyme stabilization system, are stable in storage and viscosity under a wide variety of climatic conditions, are not subject to phase separation and have color stability even when exposed to light.
Höherviskose Wasch- und Reinigungsmittel sowie Kosmetika werden in den letzten Jahren zunehmend angeboten, wobei solche Produkte mit gel-artiger Konsistenz vom Verbraucher stark akzeptiert werden. Auf dem Gebiet der Flüssigwaschmittel weisen höherviskose Gelprodukte den Vorteil auf, daß weniger nichtwäßrige Lösungsmittel eingesetzt werden können und das Produkt gezielt auf die Flecken aufgetragen werden kann, ohne dabei zu verlaufen. Üblicherweise werden dabei herkömmliche Flüssigwaschmittel durch den Einsatz von Verdickungsmitteln wie Agar-Agar, Carrageen, Traganth, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Gelatine, Casein, Carboxymethylcellulose und andere Celluloseether wie Hydroxyethyl- und -propylcellulose, Kernmehlether, Polyacryl- und Polymethacryl-Verbindungen, Vinylpolymere, Polycarbonsäuren, Polyether, Polyimine, Polyamide. Polykieselsäuren, Tonmineralien wie Montmorillonite, Zeolithe und Kieselsäuren in höherviskose Produkte überführt. Der Einsatz dieser Verdickungsmittel zur Viskositätserhöhung in den unterschiedlichstens Flüssigkeiten ist seit langem Stand der Technik. Auch der Einsatz von Polymeren in Flüssigwaschmitteln ist altbekannt.Higher viscosity detergents and cleaning agents as well as cosmetics have become increasingly popular in recent years, with such products with a gel-like consistency being widely accepted by consumers. In the field of liquid detergents, higher-viscosity gel products have the advantage that less non-aqueous solvents can be used and the product can be applied specifically to the stains without running. Conventional liquid detergents are usually used through the use of thickeners such as agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose and other cellulose ethers such as hydroxyethyl and -propyl cellulose, powdered meal ether, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides. Polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas are converted into higher-viscosity products. The use of these thickeners to increase viscosity in a wide variety of liquids has long been state of the art. The use of polymers in liquid detergents is also well known.
Die Einarbeitung der genannten Verdickungsmittel führt bei Flüssigwaschmitteln nicht zwangsläufig zu stabilen Gelen. Die Gelbildung gelingt üblicherweise nur durch eine Abstimmung von Art und Menge der einzelnen Inhaltsstoffe auf das eingesetzte Verdickungsmittel, wobei einige der Verdickungsmittel mit den Inhaltsstoffen eines Flüssigwaschmittels unverträglich sind. Solche Produkte zeigen nach einigen Wochen Lagerung eine Agglomeratbildung, die sich in einem Undurchsichtigwerden („Wolkenbildung") der Formulierung bemerkbar macht. Zusätzlich sinkt bei solchen Produkten die Viskosität während der Lagerung zum Teil drastisch. Da höherviskose Flüssigwaschmittel zur Unterstreichung der ästhetischen Merkmale in der Regel in
durchsichtigen Flaschen angeboten werden, ist es weiterhin erforderlich, daß die eingesetzten Verdickungsmittel gegen Licht stabil sind, da sonst ein radikalischer Zerfall der Polymeren eintritt, der sich in einer Zerstörung der Produktfarbe und unerwünschter „Wolkenbildung" äußert.The incorporation of the thickeners mentioned does not necessarily lead to stable gels in liquid detergents. Gel formation is usually only possible by coordinating the type and amount of the individual ingredients with the thickener used, some of the thickeners being incompatible with the ingredients of a liquid detergent. After a few weeks of storage, such products show an agglomerate formation, which becomes apparent when the formulation becomes opaque ("cloud formation"). In addition, the viscosity of such products drops drastically during storage. As a rule, higher-viscosity liquid detergents to underline the aesthetic characteristics in transparent bottles are offered, it is also necessary that the thickeners used are stable to light, since otherwise a radical decomposition of the polymers occurs, which is reflected in the destruction of the product color and undesirable "cloud formation".
Flüssigwaschmittel mit Viskositäten zwischen 500 bis 20000 mPas, vorzugsweise von 2000 bis 10000 mPas, in denen lamellare Tensidtröpfchen in einer wäßrigen Elektrolytphase dispergiert sind, werden in der europäischen Patentanmeldung EP 0 691 399 beschrieben. Diese Mittel enthalten 10 bis 45 Gew.-% Tensid(e), mindestens einen Gerüststoff sowie 0,01 bis 5 Gew.-% eines Mercapto-endverschlossenen Polymers mit mittlerem Molekulargewicht zwischen 1500 und 50000 gmol"1.Liquid detergents with viscosities between 500 to 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European patent application EP 0 691 399. These compositions contain 10 to 45% by weight of surfactant (s), at least one builder and 0.01 to 5% by weight of a mercapto-terminated polymer with an average molecular weight of between 1500 and 50,000 gmol "1 .
Der Einsatz von Borverbindungen in wäßrigen Flüssigwaschmitteln wird in der europäischen Patentanmeldung EP 0 381 262 beschrieben. Diese Flüssigwaschmittel enthalten Borverbindungen sowie ein Polyol als Enzymstabilisierungssystem für eine Mischung aus proteolytischen und lipolytischen Enzymen, wobei bevorzugte Stabilisierungssysteme aus einer Sorbitol/Borax-Mischung bestehen. Über Viskosität und Stabilität der Flüssigwaschmittel wird in dieser Schrift nichts ausgeführt.The use of boron compounds in aqueous liquid detergents is described in European patent application EP 0 381 262. These liquid detergents contain boron compounds and a polyol as an enzyme stabilization system for a mixture of proteolytic and lipolytic enzymes, preferred stabilization systems consisting of a sorbitol / borax mixture. Nothing is said in this document about the viscosity and stability of liquid detergents.
Flüssige, wäßrige Waschmittelkonzentrate, die ihre Viskosität bei Verdünnung mit Wasser beibehalten oder erhöhen, werden in der europäischen Patentanmeldung EP 0 724 013 beschrieben. Erreicht wird dieser Effekt durch den Einsatz von zwei Tensiden mit unterschiedlicher Beständigkeit gegen Elektrolyte und die Zugabe eines gelösten Elektrolyten, wobei das Konzentrat eine Viskosität von weniger als 2500 mPas hat und bei Verdünnung mit Wasser seine micellare Struktur zugunsten der Ausbildung einer lamellaren Phase verliert.Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in European patent application EP 0 724 013. This effect is achieved through the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, whereby the concentrate has a viscosity of less than 2500 mPas and loses its micellar structure in favor of the formation of a lamellar phase when diluted with water.
Die internationale Patentanmeldung WO 96/01305 beschreibt ein wäßriges Reinigungsund Flüssigwaschmittel, das bei Verdünnung mit mindestens der zweifachen Menge Wasser eine Mikroemulsion ausbildet, die Teilchengrößen von 10 bis 100 nm aufweist. Das Mittel enthält 20 bis 70 Gew.-% Wasser, 15 bis 40 Gew.-% eines Tensidsystems, das mindestens ein Niotensid aus der Gruppe der alkoxylierten Alkohole und nicht mehr als 20
Gew.-% Anion-, Kation-, Ampho- oder zwitterionisches Tensid enthält, 5 bis 30 Gew.-% Lösungsmittel und 5 bis 20 Gew.-% wasserunlösliches Öl.International patent application WO 96/01305 describes an aqueous cleaning and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes of 10 to 100 nm. The composition contains 20 to 70% by weight of water, 15 to 40% by weight of a surfactant system which contains at least one nonionic surfactant from the group of the alkoxylated alcohols and not more than 20 % By weight of anionic, cationic, ampho- or zwitterionic surfactant contains 5 to 30% by weight of solvent and 5 to 20% by weight of water-insoluble oil.
Aus der deutschen Patentanmeldung DE 197 52 165 sind wäßrige, höherviskose Flüssigwaschmittel bekannt, enthaltend Tensid(e) sowie weitere übliche Inhaltsstoffe von Wasch- und Reinigungsmitteln, wobei die Mittel als Verdickungssystem, jeweils bezogen auf das gesamte Mittel, 0,1 bis 5 Gew.-% eines polymeren Verdickungsmittels, 0,5 bis 7 Gew.-% einer Borverbindung sowie 1 bis 8 Gew.-% eines Komplexbildners enthalten. Die aus dieser Druckschrift bekannten Mittel sind viskositätsstabil, neigen nicht zur Agglomeratbüdung oder Phasentrennung und weisen keine Verringerung der Farbstabilität bei Lichteinfluß auf. Zur etwaigen Stabilität von in derartigen Mitteln enthaltenen Enzymen enthält das Dokument keine Aussage.From the German patent application DE 197 52 165 aqueous, higher-viscosity liquid detergents are known, containing surfactant (s) and other usual ingredients of detergents and cleaning agents, the agents as a thickening system, based in each case on the total agent, 0.1 to 5% by weight. -% of a polymeric thickener, 0.5 to 7 wt .-% of a boron compound and 1 to 8 wt .-% of a complexing agent. The agents known from this publication are stable in viscosity, do not tend to agglomerate or phase separation and have no reduction in color stability under the influence of light. The document contains no information on the possible stability of enzymes contained in such agents.
Keine der genannten Schriften befaßt sich mit dem Problem, höherviskose enzymhaltige Flüssigwaschmittel bereitzustellen, die eine stabile Viskosität garantieren, bei Lagerung möglichst keinen Verlust an enzymatischer Aktivität erleiden, nicht zu einer Agglomeratbüdung (sogenannte „Wolkenbildung") oder Phasentrennung fuhren und keine Verringerung der Farbstabilität bei Lichteinfluß aufweisen. Zur Lösung dieses Problems will die vorliegende Erfindung beitragen.None of the cited documents deals with the problem of providing higher-viscosity enzyme-containing liquid detergents which guarantee a stable viscosity, if possible suffer no loss of enzymatic activity when stored, do not lead to agglomerate formation (so-called “cloud formation”) or phase separation and do not reduce the color stability The present invention seeks to solve this problem.
Es wurde nun gefunden, daß sich enzymhaltige Flüssigwaschmittel mit dem genannten Eigenschaftsprofil herstellen lassen, wenn man ein polymeres Verdickungsmittel, ein besonderes Enzymstabilisatorsystem und ein bestimmtes Tensid in die Mittel inkorporiert.It has now been found that enzyme-containing liquid detergents with the property profile mentioned can be prepared if a polymeric thickener, a special enzyme stabilizer system and a specific surfactant are incorporated into the detergents.
Gegenstand der Erfindung sind daher enzymhaltige, wäßrige, höherviskose Flüssigwaschmittel, enthaltend Tensid und 0,1 bis 5 Gew.-% an polymerem Verdickungsmittel sowie weitere übliche Inhaltsstoffe von Wasch- und Reinigungsmitteln, wobei die Mittel dadurch gekennzeichnet sind, daß sie Tensid auf Saccharidbasis, mindestens ein Enzym aus der Gruppe umfassend Cellulase, Amylase und Protease sowie ein Enzymstabilisatorsystem aus den Bestandteilen a) Borverbindung und/oder Natriumformiat und b) mehrwertigem Alkohol enthalten.
Durch den Einsatz des polymeren Verdickungsmittels lassen sich höherviskose Flüssigwaschmittel herstellen, die frei von den genannten Nachteilen sind. Es ist erfmdungsgemäß möglich, konzentrierte höherviskose Flüssigwaschmittel herzustellen, die Tensidgehalte oberhalb 35 Gew.-% aufweisen.The invention therefore relates to enzyme-containing, aqueous, highly viscous liquid detergents, containing surfactant and 0.1 to 5% by weight of polymeric thickener, and further conventional ingredients of detergents and cleaning agents, the agents being characterized in that they contain surfactant based on saccharide, contain at least one enzyme from the group comprising cellulase, amylase and protease and an enzyme stabilizer system from the components a) boron compound and / or sodium formate and b) polyhydric alcohol. The use of the polymeric thickener makes it possible to produce higher-viscosity liquid detergents which are free from the disadvantages mentioned. According to the invention, it is possible to produce concentrated, higher-viscosity liquid detergents which have surfactant contents above 35% by weight.
Ein erfindungsgemäßes Mittel enthält mindestens eine Protease. Cellulase oder Amylase, wobei vorzugsweise mindestens zwei dieser Enzyme und besonders bevorzugt alle drei Enzyme vorhanden sind. In bevorzugten Ausführungsformen enthalten die erfindungsgemäßen Mittel Protease und Amylase, Protease und Cellulase, Amylase und Cellulase oder Protease, Amylase und Cellulase. Gewünschtenfalls können auch mehr als ein Vertreter aus einer der genannten Enzymklassen enthalten sein.An agent according to the invention contains at least one protease. Cellulase or amylase, preferably at least two of these enzymes and particularly preferably all three enzymes being present. In preferred embodiments, the agents according to the invention contain protease and amylase, protease and cellulase, amylase and cellulase or protease, amylase and cellulase. If desired, more than one representative from one of the enzyme classes mentioned can also be present.
Zu den bevorzugt eingesetzten Proteasen gehört neben den aus verschiedenen Bacillus Spezies erhältlichen oder gentechnisch modifizierten Proteasen wie Alcalase®, Esperase®, Savinase®, Durazym® oder Everlase® die Protease aus Bacillus lentus, die unter alkalischen Bedingungen stabil und aktiv ist; sie kann wie in der internationalen Patentanmeldung WO 91/02792 beschrieben in Bacillus lentus (DSM 5483) produziert werden. Diese Bacillus lentus alkalische Protease (BLAP) kann durch Fermentation von Bacillus licheniformis erhalten werden, der mit einem Expressionsplasmid transformiert wurde, welches das Gen für BLAP unter der Kontrolle des Promotors aus Bacillus licheniformis ATCC 53926 trägt. Die Zusammensetzung wie auch die räumliche Struktur von BLAP ist bekannt (D.W. Godette et al., J. Mol. Biol. 228, 580-595,1992). Diese Protease ist durch die in der zitierten Literatur beschriebene Sequenz aus 269 Aminosäuren, ein rechnerisches Molekulargewicht von 26 823 Dalton und einen theoretischen isoelektrischen Punkt von 9,7 charakterisiert. Durch Mutation zugängliche Varianten dieser Bacillus lentus DSM 5483 Protease sind in der US-amerikanischen Patentschrift US 5 340 735 beschrieben. Unter diesen sind Proteaseenzyme, die bei insbesondere mehrfacher Waschbehandlung von Textilien aus proteinogenen Fasern, beispielsweise textilen Flächengebilden aus Naturseide oder Wolle, ohne Verlust an Reinigungsleistung zu besonders geringen Substanzschädigungen beziehungsweise Zerstörungen der Faserverbände führen. Zu den erfindungsgemäß brauchbaren Proteasen zählen neben der natürlich vorkommenden Protease aus Bacillus lentus auch gentechnisch veränderte
Proteasen des obengenannten BLAP-Typs, bei denen in Position 211 (BLAP-Zählung) die an dieser Stelle in der Wildtyp-Protease vorhandene Aminosäure Leucin (L im gebräuchlichen Ein-Buchstaben-Code) gegen Asparaginsäure (D) beziehungsweise Glutaminsäure (E) ausgetauscht ist (L21 1D beziehungsweise L21 1E). Diese können wie in der internationalen Patentanmeldung WO 95/23221 beschrieben hergestellt werden. Stattdessen oder zusätzlich können weitere Veränderungen gegenüber der ursprünglichen Bacillus lentus-Protease, wie beispielsweise mindestens einer der Aminosäureaustausche S3T, V4I, R99G, R99A, R99S, A188P, V193M und/oder VI 991, vorgenommen worden sein. Besonders bevorzugt ist der Einsatz einer Variante, bei welcher mindestens einer der Aminosäureaustausche S3T, V4I , V193M, V199I oder L21 1D vorgenommen wurde. Bei der vorstehend beschriebenen Proteasenomenklatur über den Austausch einzelner Aminosäuren ist zu beachten, daß die Numerierung der Aminosäurepositionen in BLAP sich von der häufig anzutreffenden des Subtilisin BPN' unterscheidet. Die Numerierung der Positionen 1 bis 35 ist in Subtilisin BPN' und BLAP identisch; aufgrund fehlender korrespondierender Aminosäuren entsprechen die Positionen 36 bis 54 in BLAP den Positionen 37 bis 55 in BPN', ebenso die Positionen 55 bis 160 in BLAP den Positionen 57 bis 162 in BPN' und die Positionen 161 bis 269 denen von 167 bis 275 in BPN'. Vorzugsweise enthält ein erfindungsgemäßes Mittel Savinase® und/oder eine gegebenenfalls gentechnisch veränderte Protase aus Bacillus lentus.In addition to the proteases obtainable or genetically modified from various Bacillus species, such as Alcalase®, Esperase®, Savinase®, Durazym® or Everlase®, the proteases preferably used include the protease from Bacillus lentus, which is stable and active under alkaline conditions; it can be produced as described in international patent application WO 91/02792 in Bacillus lentus (DSM 5483). This Bacillus lentus alkaline protease (BLAP) can be obtained by fermentation of Bacillus licheniformis transformed with an expression plasmid which carries the gene for BLAP under the control of the Bacillus licheniformis ATCC 53926 promoter. The composition as well as the spatial structure of BLAP is known (DW Godette et al., J. Mol. Biol. 228, 580-595, 1992). This protease is characterized by the sequence of 269 amino acids described in the cited literature, a calculated molecular weight of 26,823 daltons and a theoretical isoelectric point of 9.7. Variants of this Bacillus lentus DSM 5483 protease accessible by mutation are described in US Pat. No. 5,340,735. These include protease enzymes which, in particular when washing textiles made of proteinogenic fibers, for example textile fabrics made of natural silk or wool, result in particularly low substance damage or destruction of the fiber dressings without loss of cleaning performance. In addition to the naturally occurring protease from Bacillus lentus, the proteases which can be used according to the invention also include genetically modified ones Proteases of the abovementioned BLAP type, in which the amino acid leucine (L in the customary one-letter code) present at this point in the wild-type protease in position 211 (BLAP count) is replaced by aspartic acid (D) or glutamic acid (E) is (L21 1D or L21 1E). These can be produced as described in international patent application WO 95/23221. Instead or in addition, further changes to the original Bacillus lentus protease, such as at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or VI 991, may have been made. It is particularly preferred to use a variant in which at least one of the amino acid exchanges S3T, V4I, V193M, V199I or L21 1D has been carried out. In the above-described protease nomenclature on the exchange of individual amino acids, it should be noted that the numbering of the amino acid positions in BLAP differs from that which is frequently found for the subtilisin BPN '. The numbering of positions 1 to 35 is identical in subtilisin BPN 'and BLAP; due to the lack of corresponding amino acids, positions 36 to 54 in BLAP correspond to positions 37 to 55 in BPN ', likewise positions 55 to 160 in BLAP correspond to positions 57 to 162 in BPN' and positions 161 to 269 correspond to those from 167 to 275 in BPN '. An agent according to the invention preferably contains Savinase® and / or an optionally genetically modified protase from Bacillus lentus.
Amylasen haben die Aufgabe, die Entfernung stärkehaltiger Anschmutzungen durch die katalytische Hydrolyse des Stärke-Polysaccharids zu erleichtern und werden zu diesem Zweck seit längerer Zeit in Reinigungsmitteln für Geschirr, aber auch in Waschmitteln zum Einsatz in der Textilwäsche eingesetzt. In erfindungsgemäßen Mitteln können sowohl Amylasen vom Typ des Termamyl® wie auch gentechnisch veränderte Amylasen, das heißt solche mit im Vergleich zu natürlich vorkommenden Amylasen mit Hilfe gentechnologischer Methoden veränderter Aminosäuresequenz, zum Einsatz kommen, wie sie zum Beispiel aus den internationalen Patentanmeldungen WO 94/18314 oder WO 95/21247 bekannt sind.Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and for this purpose have been used for a long time in detergents for dishes, but also in detergents for use in textile washing. In the agents according to the invention, both amylases of the Termamyl® type and genetically modified amylases, that is to say those having an amino acid sequence which has been modified in comparison to naturally occurring amylases with the aid of genetic engineering methods, can be used, as described, for example, in international patent applications WO 94/18314 or WO 95/21247 are known.
Die erfindungsgemäß verwendbare Cellulase gehört zu den aus Bakterien oder Pilzen gewinnbaren Enzymen, welche ein pH-Optimum vorzugsweise im fast neutralen bis
schwach alkalischen pH-Bereich von 6 bis 9,5 aufweisen. Derartige Cellulasen sind beispielsweise aus den deutschen Offenlegungsschriften DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 oder den europäischen Patentanmeldungen EP 265 832. EP 269 077, EP 270 974, EP 273 125 sowie EP 339 550 bekannt. Geeignete Handelsprodukte sind beispielsweise Celluzyme® und Carezyme ® der Novo Nordisk oder KAC® von Kao. Zu den bevorzugt eingesetzten Cellulasen gehört neben Carezyme® auch die aus Melanocarpus sp. oder Myriococcum sp. erhältliche 20K-Cellulase, die aus der internationalen Patentanmeldung WO 97/14804 bekannt ist. Sie besitzt wie dort beschrieben ein Molekulargewicht von etwa 20 kDa und weist bei 50 °C im pH-Bereich von 4 bis 9 mindestens 80 % ihrer maximalen Aktivität auf, wobei noch fast 50 % der maximalen Aktivität bei pH 10 erhalten bleiben. Sie kann, wie ebenfalls dort beschrieben, aus Melanocarpus albomyces isoliert und in gentechnisch hergestellten Trichoderma reseei-Transformanten produziert werden.The cellulase which can be used according to the invention belongs to the enzymes which can be obtained from bacteria or fungi and which preferably have a pH optimum of almost neutral to have a weakly alkaline pH range from 6 to 9.5. Such cellulases are known, for example, from German laid-open documents DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832. EP 269 077, EP 270 974, EP 273 125 and EP 339 550 known. Suitable commercial products are, for example, Celluzyme® and Carezyme® from Novo Nordisk or KAC® from Kao. In addition to Carezyme®, the preferred cellulases also include those from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase, which is known from international patent application WO 97/14804. As described there, it has a molecular weight of about 20 kDa and has at least 80% of its maximum activity at 50 ° C. in the pH range from 4 to 9, with almost 50% of the maximum activity remaining at pH 10. As also described there, it can be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants.
Zusätzlich zu den genannten Enzymen können die erfindungsgemäßen Mittel gewünschtenfalls weitere Enzyme, insbesondere aus der Gruppe der Lipasen, Cutinasen, Isopeptidasen, Xylanasen, Hemicellulasen, Pullulanasen, Neopullulanasen, Mannanasen, Mycodextranansen, Polygalacturanase, Keratanasen, Chondroitinasen, Pectinasen, Phosphatasen, Oxidasen, Laccasen und/oder Peroxidasen enthalten.In addition to the enzymes mentioned, the agents according to the invention can, if desired, include further enzymes, in particular from the group consisting of lipases, cutinases, isopeptidases, xylanases, hemicellulases, pullulanases, neopullulanases, mannanases, mycodextranans, polygalacturanase, keratanases, chondroitinases, pectinases, laccatases and oxidases / or contain peroxidases.
Zu den Tensiden auf Saccharidbasis gehören zum einen Alkylglykoside der allgemeinen Formel RO(G)x, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt und auch gebrochene Zahlenwerte annehmen kann, ist eine analytisch ermittelbare Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.
Zu den Tensiden auf Saccharidbasis gehören zum anderen Polyhydroxyfettsäureamide der Formel I,The saccharide-based surfactants include, on the one hand, alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides and can also take fractional numbers, is an analytically determinable number between 1 and 10; x is preferably 1.2 to 1.4. The saccharide-based surfactants also include polyhydroxy fatty acid amides of the formula I,
R1 R 1
R-CO-N-[Z]R-CO-N- [Z]
in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel II,in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula II
R0O-R2 R0O-R 2
R-CO-N-[Z] IIR-CO-N- [Z] II
in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R1 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C -Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch
Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 6 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical , [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of international patent application WO 95/07331 Reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst can be converted into the desired polyhydroxy fatty acid amides.
Der Gehalt bevorzugter Flüssigwaschmittel an derartigen Tensiden auf Saccharid-Basis beträgt 0.5 bis 25 Gew.-%. vorzugsweise 1 bis 10 Gew.-% und insbesondere 1.5 bis 5 Gew.- %, jeweils bezogen auf das gesamte Mittel.The content of preferred liquid detergents in such surfactants based on saccharide is 0.5 to 25% by weight. preferably 1 to 10 wt .-% and in particular 1.5 to 5 wt .-%, each based on the total agent.
Eine weitere erfindungswesentliche Komponente des enzymhaltigen höherviskosen Flüssigwaschmittels ist ein polymeres Verdickungsmittel. Diese auch Quell(ungs)mittel genannten, organischen hochmolekularen Stoffe, die Flüssigkeiten aufsaugen, dabei aufquellen und schließlich in zähflüssige echte oder kolloide Lösungen übergehen, stammen aus den Gruppen der natürlichen Polymere, der abgewandelten natürlichen Polymere und der vollsynthetischen Polymere und deren Mischungen.Another essential component of the invention of the enzyme-containing, higher-viscosity liquid detergent is a polymeric thickener. These organic high-molecular substances, which are also called swelling agents, soak up liquids, swell them up and finally convert into viscous real or colloidal solutions, come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers and their mixtures.
Aus der Natur stammende Polymere, die als Verdickungsmittel erfindungsgemäß Verwendung finden können, sind "beispielsweise Agar-Agar, Carrageen, Tragant, Gummi arabicum. Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Gelatine und Casein.From nature-derived polymers which can be used as thickening agents according to the invention using, "for example, agar-agar, carrageen, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.
Abgewandelte Naturstoffe stammen vor allem aus der Gruppe der modifizierten Stärken und Cellulosen. beispielhaft seien hier Carboxymethylcellulose und andere Celluloseether. Hydroxyethyl- und -propylcellulose sowie Kernmehlether genannt.Modified natural products come primarily from the group of modified starches and celluloses. carboxymethyl cellulose and other cellulose ethers are exemplary here. Hydroxyethyl and propyl cellulose and core meal ether called.
Eine große Gruppe von Verdickungsmitteln, die breite Verwendung in den unterschiedlichsten Anwendungsgebieten finden, sind die vollsynthetischen Polymere wie Polyacryl- und Polymethacryl-Verbindungen. Vinylpolymere, Polycarbonsäuren, Polyether. Polyimine, Polyamide und Polyurethane. Derartige vollsynthetische polymere Verdickungsmittel sind in erfindungsgemäßen Mitteln vorzugsweise in Mengen von 0,2 Gew.-% bis 4 Gew.-%, insbesondere von 0,4 Gew.-% bis 3 Gew.-% und besonders bevorzugt von 0,5 Gew.-% bis 2 Gew.-% enthalten. In einer bevorzugten Ausgestaltung der Erfindung kommen als polymere Verdickungsmittel Mischungen aus gegebenenfalls abgewandeltem natürlichem Polymer und vollsynthetischem Polymer zum Einsatz.
Verdickungsmittel aus den genannten Substanzklassen sind kommerziell erhältlich und werden beispielsweise unter den Handelsnamen Acusol -820 (Methacrylsäure- (stearylalkohol-20-EO)-ester-Acrylsäure-Copolymer. 30%ig in Wasser, Rohm & Haas). Dapral®-GT-282-S (Alkylpolyglykolether, Akzo), Deuteron-Polymer- 11 (Dicarbonsäu- re-Copolymer, Schöner GmbH), Deuteron®-XG (anionisches Heteropolysaccharid auf Basis von ß-D-Glucose, D-Manose, D-Glucuronsäure, Schöner GmbH), Deuteron®-XN (nicht- ionogenes Polysaccharid, Schöner GmbH), Dicrylan®-Verdicker-O (Ethylenoxid-Addukt, 50%ig in Wasser Isopropanol, Pfersse Chemie), EMA®-81 und EMA®-91 (Ethylen-Maleinsäureanhydrid-Copolymer, Monsanto). Verdicker-QR-1001 (Polyurethan Emulsion, 19-21%ig in Wasser/Diglykolether, Rohm & Haas), Mirox&-AM (anionische Acrylsäure-Acrylsäureester-Copolymer-Dispersion, 25%ig in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobes Urethanpolymer. Servo Delden), Shellflo®-S (hochmolekulares Polysaccharid, mit Formaldehyd stabilisiert, Shell) sowie Shellflo®-XA (Xanthan-Biopolymer, mit Formaldehyd stabilisiert, Shell) erhältlich.A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds. Vinyl polymers, polycarboxylic acids, polyethers. Polyimines, polyamides and polyurethanes. Such fully synthetic polymeric thickeners are preferably present in agents according to the invention in amounts from 0.2% by weight to 4% by weight, in particular from 0.4% by weight to 3% by weight and particularly preferably from 0.5% by weight. -% to 2 wt .-% contain. In a preferred embodiment of the invention, mixtures of optionally modified natural polymer and fully synthetic polymer are used as polymeric thickeners. Thickeners from the substance classes mentioned are commercially available and are sold, for example, under the trade names Acusol -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer. 30% strength in water, Rohm & Haas). Dapral ® -GT-282-S (alkyl polyglycol ether, Akzo), Deuteron polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH), Deuteron ® -XN (non-ionic polysaccharide, Schoener GmbH), Dicrylan ® thickener-O (ethylene oxide adduct, 50% in water isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (ethylene-maleic anhydride copolymer, Monsanto). Thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox & -AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD -FX-1100 (hydrophobic urethane polymer. Servo Delden), Shellflo ® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell).
Bevorzugte wäßrige Flüssigwaschmittel enthalten als Verdickungsmittel 0,2 bis 4 Gew.-%, vorzugsweise 0,3 bis 3 Gew.-% und insbesondere 0,4 bis 1,5 Gew.-%, eines Polysaccharids. Ein bevorzugt einzusetzendes polymeres Verdickungsmittel ist Xanthan, ein mikrobielles anionisches Heteropolysaccharid, das von Xanthomonas campestris und einigen anderen Species unter aeroben Bedingungen produziert wird und eine Molmasse von 2 bis 15 Millionen Dalton aufweist. Xanthan wird aus einer Kette mit ß-1,4- gebundener Glucose (Cellulose) mit Seitenketten gebildet. Die Struktur der Untergruppen besteht aus Glucose, Mannose, Glucuronsäure, Acetat und Pyruvat, wobei die Anzahl der Pyruvat-Einheiten die Viskosität des Xanthan bestimmt. Xanthan läßt sich durch folgende Formel beschreiben:
Preferred aqueous liquid detergents contain 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of a polysaccharide as thickening agent. A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain with ß-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:
Grundeinheit von XanthanBasic unit of xanthan
Bevorzugte wäßrige Flüssigwaschmittel enthalten als Verdickungsmittel jeweils bezogen auf das gesamte Mittel 0,2 bis 4 Gew.-%, vorzugsweise 0,3 bis 3 Gew.-% und insbesondere 0,4 bis 1 ,5 Gew.-%, Xanthan.Preferred aqueous liquid detergents each contain from 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of xanthan as the thickener.
Als erste Komponente des Enzymstabilisierungssystems in den erfindungsgemäßen Mitteln kommt Alkaliformiat und/oder eine Borverbindung, die vorzugsweise in Mengen von 0,5 bis 7 Gew.-% eingesetzt werden, in Frage, wobei die Alkaliformiate aus Lithiumforrniat, Natriumformiat, Kaliumformiat und deren Mischungen ausgewählt werden können. Beispiele für Borverbindungen, die im Rahmen der vorliegenden Erfindung einsetzbar sind, sind Borsäure, Boroxid, Alkaliborate wie Ammonium-, Natrium- und Kalium-ortho-, -meta- und -pyroborate, Borax in seinen verschiedenen Hydratationsstufen und Polyborate wie beispielsweise Alkalimetallpentaborate. Auch organische Borverbindungen wie Ester der Borsäure sind einsetzbar. Bevorzugte Flüssigwaschmittel enthalten 0,5 Gew.-% bis 5 Gew.-%, vorzugsweise 0,75 Gew.-% bis 3 Gew.-% und insbesondere 1 Gew.-% bis 2 Gew.-% Natriumformiat, Borsäure und/oder Natriumtetraborat.
Als zweite Komponente des Enzymstabilisierungssystems enthalten die erfindungsgemäßen Flüssigwaschmittel mehrwertigen Alkohol, wie Glykol, Propan- oder Butandiol, Glycerin, Diglykol, Propyl- oder Butyldiglykol und oder Hexylenglycol, Besonders bevorzugt ist der Einsatz von Glycerin und/oder Propylenglykol, wobei letzteres vorzugsweise 1,2-Propylengylokol ist, aber auch 1.3-Propypenglykol sowie Mischungen aus beiden zum Einsatz kommen können. Diese zweite Komponente ist vorzugsweise in Mengen von 0,5 Gew.-% bis 15 Gew.-% in erfindungsgemäßen Mitteln enthalten.The first component of the enzyme stabilization system in the agents according to the invention is alkali metal formate and / or a boron compound, which are preferably used in amounts of 0.5 to 7% by weight, the alkali metal formates being selected from lithium formate, sodium formate, potassium formate and mixtures thereof can be. Examples of boron compounds which can be used in the context of the present invention are boric acid, boron oxide, alkali borates such as ammonium, sodium and potassium ortho, meta and pyroborates, borax in its various hydration stages and polyborates such as alkali metal pentaborates. Organic boron compounds such as esters of boric acid can also be used. Preferred liquid detergents contain 0.5% by weight to 5% by weight, preferably 0.75% by weight to 3% by weight and in particular 1% by weight to 2% by weight of sodium formate, boric acid and / or sodium tetraborate. As a second component of the enzyme stabilization system, the liquid detergents according to the invention contain polyhydric alcohol, such as glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol and or hexylene glycol. The use of glycerol and / or propylene glycol is particularly preferred, the latter preferably 1.2 -Propylenegylokol is, but also 1,3-Propypenglykol as well as mixtures of both can be used. This second component is preferably present in amounts of 0.5% by weight to 15% by weight in agents according to the invention.
Neben dem erfindungswesentlichen Tensid auf Saccharidbasis können die erfindungsgemäßen Flüssigwaschmittel weiteres Tensid enthalten, wobei anionische, nichtionische, kationische und/oder amphotere Tenside eingesetzt werden können. Bevorzugt sind aus anwendungstechnischer Sicht Mischungen aus anionischen und nichtionischen Tensiden, wobei der Anteil der nichtionischen Tenside - inklusive der erfindungswesentlichen Tenside auf Saccharidbasis - größer sein sollte als der Anteil an anionischen Tensiden. Der Gesamttensidgehalt der erfindungsgemäßen Flüssigwaschmittel liegt vorzugsweise im Bereich von 15 Gew.-% bis 80 Gew.-%, insbesondere von 20 Gew.- % bis 60 Gew.-%.In addition to the saccharide-based surfactant essential to the invention, the liquid detergents according to the invention can contain further surfactant, it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, the proportion of the nonionic surfactants, including the saccharide-based surfactants essential to the invention, should be greater than the proportion of anionic surfactants. The total surfactant content of the liquid detergents according to the invention is preferably in the range from 15% by weight to 80% by weight, in particular from 20% by weight to 60% by weight.
Als zusätzliche nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C- Atomen, z.B. aus Kokos-, Palm-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise Cι .] -Alkohole mit 3 EO, 4 EO oder 7 EO, C9.n -Alkohol mit 7 EO, Cι3.ι5- Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18- Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14- Alkohol mit 3 EO und Cι _ι8-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte
Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Taigfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch nichtionische Tenside, die EO- und PO- Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar. Hierbei können Blockcopolymere mit EO-PO-Blockeinheiten bzw. PO-EO-Blockeinheiten eingesetzt werden, aber auch EO-PO-EO-Copolymere bzw. PO-EO-PO-Copolymere. Selbstverständlich sind auch gemischt alkoxylierte Niotenside einsetzbar, in denen EO- und PO-Einheiten nicht blockweise sondern statistisch verteilt sind. Solche Produkte sind durch gleichzeitige Einwirkung von Ethylen- und Propylenoxid auf Fettalkohole erhältlich.The additional nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example. ] Alcohols with 3 EO, 4 EO or 7 EO, C 9 .n alcohol with 7 EO, Cι 3 .ι 5 - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-1 4 alcohol containing 3 EO and Cι _ι 8 alcohol containing 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. preferred Alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden.Another class of nonionic surfactants used with preference are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese Patent Application JP 58/217598 or which are preferably described in of the international patent application WO 90/13533.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N- dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäure- alkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
Als anionische Tenside können beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt werden. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C .ι3- Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansul- fonaten sowie Disulfonaten, wie man sie beispielsweise aus C1 .ι8-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasformigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus Cι2_ι8-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation
gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate). z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren geeignet.Anionic surfactants that can be used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C. 3 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 1 8 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are derived from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization be won. Likewise, the esters of α-sulfo fatty acids (ester sulfonates). For example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure. Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid. Caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der Cι -Cι8-Fettalkohole, beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der Cι0-C o- Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die Cι2- Cι6-Alkylsulfate und Cι2-Ci5-Alkylsulfate sowie Cι4-Cι5-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem namen DAN® erhalten werden können, sind geeignete Aniontenside.As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the -C 8 -C fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the -C 0 -C o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C 2 -C 6 alkyl sulfates and C 2 -Ci 5 alkyl sulfates and C 4 -C 5 alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7. l- -Alkohole, wie 2-Methyl-verzweigte C _π -Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder Cι .ι8-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobemsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureεster bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8-ι -Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.The sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with 1 to 6 mol of ethylene oxide. l - Alcohols, such as 2-methyl-branched C _π alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι .ι 8 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 -ι fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern-, Olivenöl- oder Taigfettsäuren, abgeleitete Seifengemische.Soaps are particularly suitable as further anionic surfactants. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kaliumoder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Der Gehalt bevorzugter Flüssigwaschmittel an anionischen Tensiden beträgt 5 bis 35 Gew.-%, vorzugsweise 8 bis 30 Gew.-% und insbesondere 10 bis 25 Gew.-%, jeweils bezogen auf das gesamte Mittel.The content of preferred liquid detergents in anionic surfactants is 5 to 35% by weight, preferably 8 to 30% by weight and in particular 10 to 25% by weight, in each case based on the total composition.
Die Viskosität der erfindungsgemäßen Mittel kann mit üblichen Standardmethoden (beispielsweise Brookfield-Viskosimeter LVT-II bei 20 U/min und 20°C, Spindel 3) gemessen werden und liegt vorzugsweise im Bereich von 500 bis 5000 mPas. Bevorzugte Mittel haben Viskositäten von 1000 bis 4000 mPas, wobei Werte zwischen 2000 und 3500 mPas besonders bevorzugt sind.
Zusätzlich zu den bisher genannten Bestandteilen können die erfindungsgemäßen Mittel weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften des Flüssigwaschmittels weiter verbessern. Im Rahmen der vorliegenden Erfindung enthalten bevorzugte Mittel zusätzlich einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Elektrolyte, nichtwäßrigen Lösungsmittel, pH-Stellmittel, Duftstoffe, Parfümträger, Fluoreszenzmittel, Farbstoffe, Hydrotope, Schauminhibitoren. Silikonöle, Antiredepositionsmittel, optischen Aufheller, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide. Antioxidantien. Korrosionsinhibitoren. Antistatika. Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel sowie UV- Absorber.The viscosity of the agents according to the invention can be measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 500 to 5000 mPas. Preferred agents have viscosities of 1000 to 4000 mPas, values between 2000 and 3500 mPas being particularly preferred. In addition to the constituents mentioned so far, the agents according to the invention may contain further ingredients which further improve the technical and / or aesthetic properties of the liquid detergent. In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors. Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides. Antioxidants. Corrosion inhibitors. Antistatic agents. Ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.
Als Gerüststoffe, die in den erfindungsgemäßen Flüssigwaschmitteln enthalten sein können, sind insbesondere Silikate, Aluminiumsilikate (insbesondere Zeolithe), Carbonate, Salze organischer Di- und Polycarbonsäuren sowie Mischungen dieser Stoffe zu nennen.The builders that can be contained in the liquid detergents according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
Geeignete kristalline, schichtförmige Natriumsilikate besitzen die allgemeine Formel NaMSi O2x+ι ' y H2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate Na Si O5-yH2O bevorzugt, wobei ß-Natrium- disilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO 91/08171 beschrieben ist.Suitable crystalline, layered sodium silicates have the general formula NaMSi O 2x + ι ' y H 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 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na Si O 5 -yH 2 O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na O : SiO von 1 :2 bis 1 :3,3, vorzugsweise von 1 :2 bis 1 :2,8 und insbesondere von 1 :2 bis 1 :2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/ Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung
wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, daß die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel beiAmorphous sodium silicates with a modulus Na O: SiO 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 in dissolution, can also be used 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. Within the scope of this invention the term "amorphous" is also understood to mean "X-ray amorphous". This means that the 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. However, it can very well lead to particularly good builder properties if the silicate particles are added
Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige sogenannte röntgenamorphe Silikate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, werden beispielsweise in der deutschen Patentanmeldung DE 44 00 024 beschrieben. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate.Electron diffraction experiments provide washed-out or even sharp diffraction maxima. 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 44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
Der gegebenenfalls eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith A und/oder P. Als Zeolith P wird Zeolith MAP® (Handelsprodukt der Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X und oder P. Kommerziell erhältlich und im Rahmen der vorliegenden Erfindung bevorzugt einsetzbar ist beispielsweise auch ein Co- Kristallisat aus Zeolith X und Zeolith A (ca. 80 Gew.-% Zeolith X), das von der Firma CONDEA Augusta S.p.A. unter dem Markennamen VEGOBOND AX® vertrieben wird und durch die Formel nNa2O ■ (l-n)K2O ■ Al2O3 ■ (2 - 2,5)SiO2 • (3,5 - 5,5) H2O beschrieben werden kann. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten Cι -Cι8-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen, Cι -Cι -Fettalkoholen mit 4 bis 5 Ethylenoxidgruppen oder ethoxylierten Isotridecanolen. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 μm (Volumenverteilung; Meßmethode zum Beispiel mittels Coulter
Counter) auf und enthalten vorzugsweise 18 bis 22 Gew.-%. insbesondere 20 bis 22 Gew.- % an gebundenem Wasser.The optionally used fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X) , which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and which has the formula nNa 2 O ■ (ln) K 2 O ■ Al 2 O 3 ■ (2 - 2.5) SiO 2 • (3.5 - 5.5) H 2 O can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 8 -C 8 fatty alcohols with 2 to 5 ethylene oxide groups, Cι -Cι fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method, for example using Coulter Counter) and preferably contain 18 to 22 wt .-%. in particular 20 to 22% by weight of bound water.
Selbstverständlich ist auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden sollte. Geeignet sind insbesondere die Natriumsalze der Orthophosphate, der Pyrophosphate und insbesondere der Tripolyphosphate.Of course, it is also possible to use the generally known 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.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polvcarbonsäuren, wobei unter Polvcarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure. Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure. Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH- Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure. Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen. Als Builder sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol. Bei den für polymere Polycarboxylate angegebenen Molmassen handelt es sich im Sinne der vorliegenden Schrift um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt werden können, wobei ein UV-Detektor eingesetzt wird. Die Messung erfolgt dabei gegen einen externen Polyacrylsäure-Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden wobei die gegen Polystyrolsulfonsäuren gemessenen
Molmassen in der Regel deutlich höher sind. Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein. Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol. Zur Verbessung der Wasserlöslichkeit können die Polymere auch Allylsulfonsäuren, wie beispielsweise aus der europäischen Patentschrift EP 0 727 448 Bl bekannte Allyloxybenzolsulfonsäure und Methallylsulfonsäure, als Monomer enthalten. Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die gemäß der deutschen Patentanmeldung DE 43 00 772 AI als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinyl- alkohol-Derivate oder gemäß der deutschen Patentschrift DE 42 21 381 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE- A-43 03 320 und DE-A-44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen. Ebenso sind als weitere bevorzugte organische Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate, von denen in der deutschen Patentanmeldung DE 195 40 086 AI offenbart wird, daß sie neben Cobuilder- Eigenschaften auch eine bleichstabilisierende Wirkung aufweisen. Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP 0 280 223 beschrieben, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus
Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten. Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500000 g/mol. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Poly- saccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 bis 30000 g/mol. Ein bevorzugtes Dextrin ist in der europäischen Patentanmeldung EP 0 703 292 AI beschrieben. Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Derartige oxidierte Dextrine und Verfahren ihrer Herstellung sind beispielsweise aus den europäischen Patentanmeldungen EP 0 232 202, EP 0 427 349, EP 0 472 042 und EP 0 542 496 sowie den internationalen Patentanmeldungen WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 und WO 95/20608 bekannt. Ebenfalls geeignet ist ein oxidiertes Oligosaccharid gemäß der deutschen Patentanmeldung DE-A-196 00 018. Ein an C des Saccharidrings oxidiertes Produkt kann besonders vorteilhaft sein. Auch Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat, sind weitere geeignete Buildermaterialien. Dabei wird Ethylendiamin-N,N'-disuccinat (EDDS), dessen Synthese beispielsweise in US 3 158 615 beschrieben wird, bevorzugt in Form seiner Natrium- oder Magnesiumsalze verwendet. Weiterhin bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate, wie sie beispielsweise in den US-amerikanischen Patentschriften US 4 524 009, US 4 639 325, in der europäischen Patentanmeldung EP-A-0 150 930 und der japanischen Patentanmeldung JP 93/339896 beschrieben werden. Weitere brauchbare organische Builder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4
Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten. Derartige Builder werden beispielsweise in der internationalen Patentanmeldung WO 95/20029 beschrieben. Organische Buildersubstanzen sind in erfindungsgemäßen Mitteln vorzugsweise in Mengen von 1 Gew.-% bis 8 Gew.-% enthalten.Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as those carboxylic acids which carry more than one acid function. For example, these are citric acid. Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid. Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. In particular, citric acid and succinic acid. To name glutaric acid, adipic acid, gluconic acid and any mixtures of these. Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. The molar masses given for polymeric polycarboxylates are, for the purposes of the present specification, weight-average molar masses M w of the particular acid form, which can in principle be determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement is carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard, those measured against polystyrene sulfonic acids Molar masses are usually significantly higher. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. To improve the solubility in water, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid known from European patent EP 0 727 448 B1. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to German patent application DE 43 00 772 AI, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to German patent DE 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred organic builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE 195 40 086 A1 that they have a bleach-stabilizing effect in addition to cobuilder properties. Other suitable builder substances are 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 0 280 223. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Other 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 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. 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 2000 to 30000 g / mol can be used. A preferred dextrin is described in European patent application EP 0 703 292 AI. 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 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110 , WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C of the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable builder materials. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this connection are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become. Further useful organic builders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 Contain carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such builders are described, for example, in international patent application WO 95/20029. Organic builder substances are preferably present in the agents according to the invention in amounts of 1% by weight to 8% by weight.
Als Elektrolyte aus der Gruppe der anorganischen Salze kann eine breite Anzahl der verschiedensten Salze eingesetzt werden. Bevorzugte Kationen sind die Alkali- und Erdalkalimetalle, bevorzugte Anionen sind die Halogenide und Sulfate. Aus herstellungstechnischer Sicht ist der Einsatz von NaCl oder MgCl in den erfindungsgemäßen Mitteln bevorzugt. Der Anteil an Elektrolyten in den erfindungsgemäßen Mitteln beträgt üblicherweise 0.5 bis 5 Gew.-%.A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
Nichtwäßrige Lösungsmittel, die in den erfindungsgemäßen Mitteln eingesetzt werden können, stammen beispielsweise aus der Gruppe der einwertigen Alkohole, der Alkanolamine oder Glycolether, sofern sie im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n- oder i-Propanol, den Butanolen, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykol-methylether, Diethylenglykolethylether, Propylenglykolmethyl-, -ethyl- oder -propyl-ether, Dipropylen- glykolmonomethyl-, oder -ethylether, Di-isopropylenglykolmonomethyl-, oder -ethylether, Methoxy-, Ethoxy- oder Butoxytriglykol, 1 -Butoxyethoxy-2-propanol, 3-Methyl-3- methoxybutanol, Propylen-glykol-t-butylether sowie Mischungen dieser Lösungsmittel. Nichtwäßrige Lösungsmittel können in den erfindungsgemäßen Flüssigwaschmitteln in Mengen zwischen 0,5 und 10 Gew.-%, bevorzugt aber unter 5 Gew.-% und insbesondere unterhalb von 3 Gew.-% eingesetzt werden.Non-aqueous solvents that can be used in the agents according to the invention come, for example, from the group of monohydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene ether glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures thereof Solvent. Non-aqueous solvents can be used in the liquid detergents according to the invention in amounts between 0.5 and 10% by weight, but preferably below 5% by weight and in particular below 3% by weight.
Um den pH- Wert der erfindungsgemäßen Mittel in den gewünschten Bereich zu bringen, kann der Einsatz von pH-Stellmitteln angezeigt sein. Einsetzbar sind hier sämtliche bekannten Säuren bzw. Laugen, sofern sich ihr Einsatz nicht aus anwendungstechnischen oder ökologischen Gründen bzw. aus Gründen des Verbraucherschutzes verbietet. Üblicherweise überschreitet die Menge dieser Stellmittel 2 Gew.-% der Gesamtformulierung nicht.
Um den ästhetischen Eindruck der erfindungsgemäßen Mittel zu verbessern, können sie mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfmdlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasern. um diese nicht anzufärben.In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation. In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and are not sensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity towards textile fibers. so as not to stain them.
Als Schauminhibitoren, die in den erfindungsgemäßen Mitteln eingesetzt werden können, kommen beispielsweise Seifen, Paraffine oder Silikonöle in Betracht, die gegebenenfalls auf Trägermaterialien aufgebracht sein können.Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
Geeignete Antiredepositionsmittel. die auch als soil repellents bezeichnet werden, sind beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose mit einem Anteil an Methoxygruppen von 15 bis 30 Gew.- % und an Hydroxypropylgruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylenglycolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Insbesondere bevorzugt von diesen sind die sulfonierten Derivate der Phthalsäure- und Terephthalsäure- Polymere.Suitable anti-redeposition agents. which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and on Polymers of phthalic acid and / or terephthalic acid or of 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.
Optische Aufheller können den erfindungsgemäßen Mitteln zugesetzt werden, um Vergrauungen und Vergilbungen der behandelten Textilien zu beseitigen. Diese Stoffe ziehen auf die Faser auf und bewirken eine Aufhellung und vorgetäuschte Bleichwirkung, indem sie unsichtbare Ultraviolettstrahlung in sichtbares längerwelliges Licht umwandeln, wobei das aus dem Sonnenlicht absorbierte ultraviolette Licht als schwach bläuliche Fluoreszenz abgestrahlt wird und mit dem Gelbton der vergrauten bzw. vergilbten Wäsche reines Weiß ergibt. Geeignete Verbindungen stammen beispielsweise aus den Substanzklassen der 4,4'-Diamino-2,2'-stilbendisulfonsäuren (Flavonsäuren), 4,4'- Distyryl-biphenylen, Methylumbelliferone, Cumarine, Dihydrochinolinone, 1,3- Diarylpyrazoline, Naphthalsäureimide, Benzoxazol-, Benzisoxazol- und Benzimidazol- Systeme sowie der durch Heterocyclen substituierten Pyrenderivate. Die optischen
Aufheller werden üblicherweise in Mengen zwischen 0,05 und 0,3 Gew.-%, bezogen auf das fertige Mittel, eingesetzt.Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances absorb on the fiber and bring about a brightening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole , Benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles. The optical Brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished agent.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Wiederaufziehen des Schmutzes zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise Leim, Gelatine, Salze von Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden. z.B. abgebaute Stärke, Aldehydstärken usw. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Celluloseether wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxy-methylcellulose und deren Gemische in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetztGraying 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. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of 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. However, 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 are preferably used in amounts of 0.1 to 5% by weight, based on the composition
Da textile Flächengebilde, insbesondere aus Reyon, Zellwolle, Baumwolle und deren Mischungen, zum Knittern eigen können, weil die Einzelfasern gegen Durchbiegen, Knicken, Pressen und Quetschen quer zur Faserrichtung empfindlich sind, können die erfindungsgemäßen Mittel synthetische Knitterschutzmittel enthalten. Hierzu zählen beispielsweise synthetische Produkte auf der Basis von Fettsäuren, Fettsäureestern, Fettsäureamiden, -alkylolestern, -alkylolamiden oder Fettalkoholen, die meist mit Ethylenoxid umgesetzt sind, oder Produkte auf der Basis von Lecithin oder modifizierter Phosphorsäureester.Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
Zur Bekämpfung von Mikroorganismen können die erfindungsgemäßen Mittel antimikrobielle Wirkstoffe enthalten. Hierbei unterscheidet man je nach antimikrobiellem Spektrum und Wirkungsmechanismus zwischen Bakteriostatika und Bakteriziden, Fungistatika und Fungiziden usw. Wichtige Stoffe aus diesen Gruppen sind beispielsweise Benzalkoniumchloride, Alkylarlylsulfonate, Halogenphenole und Phenolmercuriacetat, wobei bei den erfmdungemäßen Mitteln auch gänzlich auf diese Verbindungen verzichtet werden kann.
Um unerwünschte, durch Sauerstoffeinwirkung und andere oxidative Prozesse verursachte Veränderungen an den Mitteln und/oder den behandelten Textilien zu verhindern, können die Mittel Antioxidantien enthalten. Zu dieser Verbindungsklasse gehören beispielsweise substituierte Phenole, Hydrochinone, Brenzcatechine und aromatische Amine sowie organische Sulfide, Polysulfide, Dithiocarbamate. Phosphite und Phosphonate.To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely with the agents according to the invention. In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates. Phosphites and phosphonates.
Ein erhöhter Tragekomfort gewaschener Textilien kann aus der zusätzlichen Verwendung von Antistatika resultieren, die den erfindungsgemäßen Mitteln zusätzlich beigefügt werden können. Antistatika vergrößern die Oberflächenleitfähigkeit und ermöglichen damit ein verbessertes Abfließen gebildeter Ladungen. Äußere Antistatika sind in der Regel Substanzen mit wenigstens einem hydrophilen Molekülliganden und geben auf den Oberflächen einen mehr oder minder hygroskopischen Film. Diese zumeist grenzflächenaktiven Antistatika lassen sich in stickstoffhaltige (Amine, Amide, quartäre Ammoniumverbindungen), phosphorhaltige (Phosphorsäureester) und schwefelhaltige (Alkylsulfonate, Alkylsulfate) Antistatika unterteilen. Externe Antistatika sind beispielsweise in den Patentanmeldungen FR 1 156 513, GB 873 214 und GB 839 407 beschrieben. Die hier offenbarten Lauryl- (bzw. Stearyl-) dimethylbenzylammoniumchloride eignen sich als Antistatika für Textilien bzw. als Zusatz zu Waschmitteln, wobei zusätzlich ein Avivageeffekt erzielt wird.An increased wearing comfort of washed textiles can result from the additional use of antistatic agents, which can additionally be added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1 156 513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.
Zur Verbesserung des Wasserabsorptionsvermögens, der Wiederbenetzbarkeit der behandelten Textilien und zur Erleichterung des Bügeins können in den erfindungsgemäßen Mitteln beispielsweise Silikonderivate eingesetzt werden. Diese verbessern zusätzlich das Ausspülverhalten der erfindungsgemäßen Mittel durch ihre schauminhibierenden Eigenschaften. Bevorzugte Silikonderivate sind beispielsweise Polydialkyl- oder Alkylarylsiloxane, bei denen die Alkylgruppen ein bis fünf C-Atome aufweisen und ganz oder teilweise fluoriert sind. Bevorzugte Silikone sind Polydimethylsiloxane, die gegebenenfalls derivatisiert sein können und dann aminofunktionell oder quaterniert sind bzw. Si-OH-, Si-H- und/oder Si-Cl-Bindungen aufweisen. Die Viskositäten der bevorzugten Silikone liegen bei 25°C im Bereich zwischen 100 und 100.000 mPas, wobei die Silikone in Mengen zwischen 0,2 und 5 Gew.- %, bezogen auf das gesamte Mittel eingesetzt werden können.
Schließlich können die erfindungsgemäßen Mittel auch UV -Absorber enthalten, die auf die behandelten Textilien aufziehen und die Lichtbeständigkeit der Fasern verbessern. Verbindungen, die diese gewünschten Eigenschaften aufweisen, sind beispielsweise die durch strahlungslose Desaktivierung wirksamen Verbindungen und Derivate des Benzophenons mit Substituenten in 2- und/oder 4-Stellung. Weiterhin sind auch substituierte Benzotriazole, in 3-Stellung Phenylsubstituierte Acrylate (Zimtsäurederivate), gegebenenfalls mit Cyanogruppen in 2-Stellung, Salicylate, organische Ni-Komplexe sowie Naturstoffe wie Umbelliferon und die körpereigene Urocansäure geeignet.To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing, silicone derivatives, for example, can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, it being possible for the silicones to be used in amounts between 0.2 and 5% by weight, based on the total agent. Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.
Um die durch Schwermetalle katalysierte Zersetzung bestimmter Waschmittel- Inhaltsstoffe zu vermeiden, können Stoffe eingesetzt werden, die Schwermetalle komplexieren. Geeignete Schwermetallkomplexbildner sind beispielsweise die Alkalisalze der Ethylendiamintetraessigsäure (EDTA) oder der Nitrilotriessigsäure (NTA) sowie Alkalimetallsalze von anionischen Polyelektrolyten wie Polymaleaten und Polysulfonaten. Eine bevorzugte Klasse von Komplexbildnern sind die Phosphonate, die in bevorzugten Flüssigwaschmitteln in Mengen von 0,01 bis 1,5 Gew.-%, vorzugsweise 0,02 bis 1 Gew.- % und insbesondere von 0,03 bis 0,5 Gew.-% enthalten sind. Zu diesen bevorzugten Verbindungen zählen insbesondere Organophosphonate wie beispielsweise 1- Hydroxyethan-l,l-diphosphonsäure (HEDP), Aminotri(methylenphosphonsäure) (ATMP), Diethylentriamin-penta(methylenphosphonsäure) (DTPMP bzw. DETPMP) sowie 2- Phosphonobutan-l,2.4-tricarbonsäure (PBS-AM), die zumeist in Form ihrer Ammoniumoder Alkalimetallsalze eingesetzt werden. Besonders bevorzugte Flüssigwaschmittel enthalten l-Hydroxyethan-l,l-diphosphonsäure in Form ihrer Ammonium- oder Alkalimetallsalze.In order to avoid the decomposition of certain detergent ingredients catalyzed by heavy metals, substances can be used which complex heavy metals. Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates. A preferred class of complexing agents are the phosphonates, which are used in preferred liquid detergents in amounts of 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular 0.03 to 0.5% by weight. -% are included. These preferred compounds include in particular organophosphonates such as, for example, 1-hydroxyethane-l, l-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-l, 2.4 tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. Particularly preferred liquid detergents contain l-hydroxyethane-l, l-diphosphonic acid in the form of their ammonium or alkali metal salts.
Die Herstellung der erfindungsgemäßen Mittel kann durch einfaches Vermischen der Bestandteile in Rührkesseln erfolgen, wobei Wasser, gegebenenfalls vorhandene nichtwäßrige Lösungsmittel und Tenside zweckmäßigerweise vorgelegt werden und die weiteren Bestandteile portionsweise hinzugefügt werden. Ein gesondertes Erwärmen bei der Herstellung ist nicht erforderlich, wenn es gewünscht ist, sollte die Temperatur der Mischung 80°C nicht übersteigen.
BeispieleThe agents according to the invention can be prepared by simply mixing the constituents in stirred kettles, water, any non-aqueous solvents and surfactants which may be present being expediently introduced and the further constituents being added in portions. A separate heating during production is not necessary, if it is desired, the temperature of the mixture should not exceed 80 ° C. Examples
Durch Mischen der einzelnen Bestandteile wurde die erfindungsgemäßen Flüssigwaschmittel El bis E4 hergestellt, deren Zusammensetzung in Tabelle 1 angegeben ist.The liquid detergents E1 to E4 according to the invention, the composition of which is given in Table 1, were prepared by mixing the individual constituents.
Tabelle 1: Flüssigwaschmittel [Gew.-%]Table 1: Liquid detergent [% by weight]
Turpina 4 NL: Hydroxyethan- 1 , 1 -diphosphonsäure, Tetra-Na-Salz Protease I: BLAP® 260 Protease II: Savinase® 16.0 L (Novo Nordisk) Amylase: Termamyl® L 300 (Novo Nordisk) Cellulase: Carezyme® 4500 L (Novo Nordisk)Turpina 4 NL: hydroxyethane-1,1-diphosphonic acid, tetra-Na salt Protease I: BLAP® 260 Protease II: Savinase® 16.0 L (Novo Nordisk) Amylase: Termamyl® L 300 (Novo Nordisk) Cellulase: Carezyme® 4500 L. (Novo Nordisk)
Die Flüssigwaschmittel wiesen Viskositäten imBereich von 2400 mPas bis 3200 mPas auf. Zur Prüfung ihrer Lagerstabilität wurden sie 16 Wochen bei unterschiedlichen klimatischen Bedingungen gelagert und ihr Aussehen visuell beurteilt. Sie zeigten sowohl bei Sommerklima (25 - 40°C) wie auch bei Herbstklima (10 - 30°C) oder bei Winterklima (0 - 10°C) gute Stabilität. Die enzymatische Aktivität nahm dabei nicht signifikant ab.
The liquid detergents had viscosities in the range from 2400 mPas to 3200 mPas. To test their storage stability, they were stored for 16 weeks in different climatic conditions and their appearance was assessed visually. They showed good stability both in the summer climate (25 - 40 ° C) and in the autumn climate (10 - 30 ° C) or in the winter climate (0 - 10 ° C). The enzymatic activity did not decrease significantly.
Claims
1. Enzymhaltiges, wäßriges, höherviskoses Flüssigwaschmittel, enthaltend Tensid und 0,1 Gew.-% bis 5 Gew.-% an polymerem Verdickungsmittel sowie weitere übliche Inhaltsstoffe von Wasch- und Reinigungsmitteln, dadurch gekennzeichnet, daß es Tensid auf Saccharidbasis, mindestens ein Enzym aus der Gruppe umfassend Cellulase. Amylase und Protease sowie ein Enzymstabilisatorsystem aus den Bestandteilen a) Borverbindung und/oder Natriumformiat und b) mehrwertigem Alkohol enthält.1. Enzyme-containing, aqueous, higher-viscosity liquid detergent, containing surfactant and 0.1 wt .-% to 5 wt .-% of polymeric thickener and other usual ingredients of detergents and cleaning agents, characterized in that it contains surfactant based on saccharide, at least one enzyme from the group comprising cellulase. Amylase and protease and an enzyme stabilizer system from the components a) boron compound and / or sodium formate and b) polyhydric alcohol.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es eine gegebenenfalls gentechnisch veränderte Protase aus Bacillus lentus und/oder Savinase® enthält.2. Composition according to claim 1, characterized in that it contains an optionally genetically modified protase from Bacillus lentus and / or Savinase®.
3. Mittel nach Anspruch 2, dadurch gekennzeichnet, daß es zusätzlich Amylase enthält.3. Composition according to claim 2, characterized in that it additionally contains amylase.
4. Mittel nach Anspruch 2 oder 3, dadurch gekennzeichnet, daß es zusätzlich Cellulase enthält.4. Composition according to claim 2 or 3, characterized in that it additionally contains cellulase.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Tensid auf Saccharidbasis aus den Alkylglykosiden und den Polyhydroxyfettsäureamiden sowie deren Mischungen ausgewählt wird.5. Composition according to one of claims 1 to 4, characterized in that the surfactant based on saccharide is selected from the alkyl glycosides and the polyhydroxy fatty acid amides and mixtures thereof.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Gehalt an Tensiden auf Saccharid-Basis 0,5 bis 25 Gew.-%, vorzugsweise 1 bis 10 Gew.-% und insbesondere 1,5 bis 5 Gew.-%, jeweils bezogen auf das gesamte Mittel, beträgt.6. Composition according to one of claims 1 to 5, characterized in that the content of surfactants based on saccharide 0.5 to 25 wt .-%, preferably 1 to 10 wt .-% and in particular 1.5 to 5 wt. -%, in each case based on the total average.
7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das polymere Verdickungsmittel eine Mischung aus gegebenenfalls abgewandeltem natürlichem Polymer und vollsynthetischem Polymer ist.7. Composition according to one of claims 1 to 6, characterized in that the polymeric thickener is a mixture of optionally modified natural polymer and fully synthetic polymer.
8. Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es 0,2 bis 4 Gew.-%, vorzugsweise 0,3 bis 3 Gew.-% und insbesondere 0,4 bis 1,5 Gew.-%, eines Polysaccharids als Verdickungsmittel enthält. 8. Composition according to one of claims 1 to 7, characterized in that it is 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0.4 to 1.5 wt .-%, contains a polysaccharide as a thickener.
9. Mittel einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es, jeweils bezogen auf das gesamte Mittel 0,2 Gew.-% bis 4 Gew.-%, vorzugsweise 0,3 Gew.-% bis 3 Gew.-% und insbesondere 0,4 Gew.-% bis 1,5 Gew.-%, Xanthan enthält.9. Agent according to one of claims 1 to 8, characterized in that it, based in each case on the total agent 0.2 wt .-% to 4 wt .-%, preferably 0.3 wt .-% to 3 wt .-% and in particular contains 0.4% to 1.5% by weight of xanthan.
10. Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es 0,2 Gew.-% bis 4 Gew.-%, insbesondere 0,4 Gew.-% bis 3 Gew.-% vollsynthetisches polymeres Verdickungsmittel enthält.10. Composition according to one of claims 1 to 9, characterized in that it contains 0.2 wt .-% to 4 wt .-%, in particular 0.4 wt .-% to 3 wt .-% of fully synthetic polymeric thickener.
1 1. Mittel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß es eine Viskosität von 500 mPas bis 5000 mPas, vorzugsweise von 1000 mPas bis 4000 mPas und insbesondere von 2000 mPas bis 3500 mPas aufweist. 1 1. Agent according to one of claims 1 to 10, characterized in that it has a viscosity of 500 mPas to 5000 mPas, preferably from 1000 mPas to 4000 mPas and in particular from 2000 mPas to 3500 mPas.
Priority Applications (1)
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AU77895/00A AU7789500A (en) | 1999-11-03 | 2000-10-20 | Enzyme-containing high-viscosity liquid detergents |
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DE19953057.2 | 1999-11-03 | ||
DE1999153057 DE19953057A1 (en) | 1999-11-03 | 1999-11-03 | Enzyme-containing, higher-viscosity liquid detergents |
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CA (1) | CA2325159A1 (en) |
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WO2007145964A2 (en) * | 2006-06-05 | 2007-12-21 | The Procter & Gamble Company | Enzyme stabilizer |
BE1027322B1 (en) * | 2019-05-29 | 2021-01-12 | Realco | Cleaning and degreasing composition for the treatment of hard surfaces |
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EP1807498B2 (en) † | 2004-11-02 | 2019-02-20 | Henkel AG & Co. KGaA | Process for the preparation of granulates / agglomerates for detergent compositions |
DE102008038479A1 (en) * | 2008-08-20 | 2010-02-25 | Henkel Ag & Co. Kgaa | Detergents or cleaners with increased detergency |
EP2322593A1 (en) * | 2009-11-12 | 2011-05-18 | The Procter & Gamble Company | Liquid laundry detergent composition |
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WO2007145964A2 (en) * | 2006-06-05 | 2007-12-21 | The Procter & Gamble Company | Enzyme stabilizer |
WO2007145964A3 (en) * | 2006-06-05 | 2009-09-24 | The Procter & Gamble Company | Enzyme stabilizer |
BE1027322B1 (en) * | 2019-05-29 | 2021-01-12 | Realco | Cleaning and degreasing composition for the treatment of hard surfaces |
Also Published As
Publication number | Publication date |
---|---|
DE19953057A1 (en) | 2001-05-10 |
AU7789500A (en) | 2001-05-14 |
CA2325159A1 (en) | 2001-05-03 |
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