EP0001853B2 - Reinigungsmittelmischungen mit verbesserter Bleichwirkung - Google Patents

Reinigungsmittelmischungen mit verbesserter Bleichwirkung Download PDF

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EP0001853B2
EP0001853B2 EP78200259A EP78200259A EP0001853B2 EP 0001853 B2 EP0001853 B2 EP 0001853B2 EP 78200259 A EP78200259 A EP 78200259A EP 78200259 A EP78200259 A EP 78200259A EP 0001853 B2 EP0001853 B2 EP 0001853B2
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water
carbon atoms
alkyl
sodium
compositions
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EP0001853A1 (de
EP0001853B1 (de
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Rory James Maxwell Smith
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites

Definitions

  • This invention relates to detergent compositions, and, in particular, to detergent compositions adapted for fabric washing.
  • compositions based, on certain crystalline aluminosilicates and having specifically defined low levels of polyphosphonate sequestering agents and specific in-use pH characteristics have excellent all round detergency performance and especially good cleaning performance on oxidizable-type stains.
  • these benefits are delivered in the absence of per-bleach components so that the invention makes it possible to reduce or to eliminate such materials entirely.
  • the instant compositions have optimum bleach effectiveness at about the same pH as these enzyme materials making it possible to secure excellent bleaching and enzyme performance from a single composition.
  • Polyphosphonates have already been suggested for use in detergent compositions containing aluminosilicate.
  • German Offenlegungsschrift 2,544,035, 2,539,071, 2,527,388, 2,559,631 and Austrian Patent No. 338,947 all disclose the use of various polyphosphonates notably as dispersing agents in aluminosilicate built products.
  • the present invention provides a detergent composition
  • a detergent composition comprising from 2-75% of an anionic, nonionic, zwitterionic or amphoteric surfactant, from 5-60% of a water insoluble crystalline aluminosilicate builder of formula where M is a calcium-exchange cation, z and y are integers of at least 6; the molar ratio of z:y is in the range from 1:1 to 0.5:1 and x is an integer from 15 to 264, said aluminosilicate material having a particle size diameter from 0.1 micron to 10 microns and an ion exchange capacity of at least 200 mg eg of CaC0 3 per gram, together with a polyphosphonate component, wherein the polyphosphonate compound has the formula wherein each R 1 is CH 2 P0 3 H 2 or a water soluble salt thereof, and m has the value 0, 1 or 2, the polyphosphonate being present in an amount of from 0.01-4% by weight of the composition, and in that the composition
  • Laundry detergent compositions of the same type wherein citric acid and its water soluble salts are used as a pH regulating agent are described in EP-A-1310 (Prior date 26.09.77, Appl. date 13.09.78, Publ. dat 04.04.79).
  • the detergent active component of the present compositions can be anionic, nonionic ampholytic or zwitterionic in nature or can be mixtures thereof.
  • the detergent compositions of the invention contain the active system in an amount of from 2% to 75% by weight.
  • the active systems is generally in the range from 4% to 30%, more preferably from 6% to 15% of the compositions.
  • higher active contents for example 20% to 70% are normally employed.
  • Water-soluble salts of the higher fatty acids are useful as the anionic detergent component of the compositions herein.
  • This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from 8 to 24 carbon atoms and preferably from 10 to 20 carbon atoms. Soaps can be made by direct saponification of fats and soils or by the neutralisation of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • a highly preferred class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 8 to 22, especially from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl” is the alkyl portion of acyl groups).
  • Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C S -C 1s ) carbon atoms produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in USP 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C " , 8 LAS.
  • a preferred alkyl ether sulfate surfactant component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of 12 to 16 carbon atoms, preferably from 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from 1 to 4 mols of ethylene oxide.
  • anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon. atoms.
  • Other useful anionic detergent compounds herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing .from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from 8 to 24, especially 14 to 18 carbon atoms, and (3-aikyioxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms
  • Anionic surfactant mixtures can also be employed, for example 5:1 to 1:5 mixtures of an alkyl benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical and mixtures thereof, the cation being an alkali metal preferably sodium; and from 2% to 15% by weight of an alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having an alkali metal cation, preferably sodium.
  • Nonionic detergents are also useful as the detergent component of the instant composition.
  • Such nonionic detergent materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic detergents include:
  • Semi-polar nonionic detergents include water-soluble amine oxides containing one alkyl moiety of from 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of 10 to 23 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from 10 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Ampholytic detergents include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group. Further use of zwitterionic detergents are discussed in US Patents Nos. 3,925,262 and 3,929,678.
  • a highly preferred mixture of surfactants is an anionic/nonionic mixture, especially a mixture of a C S- C 22 alkyl benzene sulfonate and a C 10 -C 20 alkanol ethoxylated with from 3 to 30 moles of ethylene oxide per mole of alkanol.
  • Highly preferred mixtures include C 12 alkyl benzene sulfonate and C 14 ⁇ C 15 alcohol-(7)-ethoxylate, in ratios of from 5:1 to 1:3, preferably 3:1 to 1:1.
  • a fatty acid soap is added to the above-described mixture, preferably a C 10- C 20 soap at a level of from 1 % to 5%.
  • Polyphosphonates useful in the present invention have the formula wherein each R 1 is CH 3 P0 3 H 2 or a water soluble salt thereof and -m has the value 0, 1 or 2.
  • the polyphosphonate is present in an amount of from 0.01% to 4% by weight of the composition preferably in an amount of from 0.1% to 2% by weight.
  • Examples of compounds within this class are aminotri(methylenephosphonic acid), ethylene diamine tetra (methylenephosphonic acid) and diethylene triamine penta (methylene phosphonic acid).
  • Preferred polyphosphonates can also be defined in terms of their calcium and iron sequestering ability as reflected in their calcium and iron logarithmic stability constants, pK ca++ and pK Fe 3+. These are defined by reference to the equilibrium. where M is the metal cation and A is the polyphosphonate anion predominating in aqueous solution at the in-use pH of the detergent composition.
  • the polyphosphonate has a pKpK ca++ of less than 6, more preferably less than 5 and especially less than 4.
  • the value of pK Fe 3+ is preferably greater than 6, more preferably greater than 9, and especially greater than 12.
  • Literature values of stability constants are taken where possible, (see Stability Constants of Metal-lon Complexes, Special Publication No. 25, the Chemical Society, London). Otherwise, the stability constant is defined at 25°C and 0.1 molar KCI, using a glass electrode method of measurement as described in Complexation in Analytical Chemistry by Anders Ringbom (1963).
  • the pH regulating agent is selected from sodium or potassium bicarbonates.
  • the pH regulating agent is present in an amount sufficient to provide a pH in 1% aqueous solution of the detergent composition, in the range from 7 to 9.5, preferably from 7 to 9, especially from 7.5 to 8.5. Generally, from 5 to 25% especially from 10 to 20% of the regulating agent is sufficient for this purpose.
  • the aluminosilicate ion exchange materials used herein are prepared by a process which results in the formation of materials which are particularly suitable for use as detergency builders and water softeners. Specifically, the aluminosilicates herein have both a higher calcium ion exchange capacity and a higher exchange rate than similar materials previously suggested as detergency builders. Such high calcium ion exchange rate and capacity appear to be a function of seveal interrelated factors which result from the method of preparing said aluminosilicate ion exchange materials.
  • these ion exchange builder materials are in the "sodium form".
  • a second essential feature of the ion exchange builder materials herein is that they be in a hydrated form ie. contain 10% to 28%, preferably 10% to 22% of water. Highly preferred aluminosilicates herein frequently contain from 18% to 22% water in their crystal matrix. It has been found, for example, that less highly hydrated aluminosilicates eg. those containing about 6% water, do not function effectively as ion exchange builders when employed in the context of a laundry detergent composition.
  • a third essential feature of the ion exchange builder materials herein is their particle size range. Proper selection of small particle sizes results in fast, highly efficient builder materials.
  • the method set forth below for preparing the aluminosilicates herein takes into consideration all of the foregoing essential elements.
  • First, the method avoids contamination of the aluminosilicate product by cations other than sodium. For example, product washing steps involving acids or bases other than sodium hydroxide are avoided.
  • Second, the process is designed to form the aluminosilicate in its most highly hydrated form. Hence, high temperature heating and drying are avoided.
  • the process is designed to form the aluminosilicate materials in a finely-divided state having a narrow range of small particle sizes. Of course, additional grinding operations can be employed to still further reduce the particle size. However, the need for such mechanical reduction steps is substantially lessened by the process herein.
  • aluminosilicates herein are prepared according to the following procedure:
  • the mixture of step (c) is cooled to a temperature below 25°C, preferably in the range from 17°C to 23°C, and maintained at that temperature for a period from 25 hours to 500 hours, preferably from 75 hours to 200 hours.
  • step (d) The mixture resulting from step (d) is cooled to a temperature of 50°C and thereafter filtered to collect the desired aluminosilicate solids. If the low temperature ( ⁇ 25°C) crystallization technique is used, then the precipitate is filtered without additional preparatory steps.
  • the filter cake can optionally be washed free of excess base (deionized water wash preferred to avoid cation contamination).
  • the filter cake is dried to a moisture content of 18% to 22% by weight using a temperature below 150°C to avoid excessive dehydration. Preferably, the drying is performed at 100°C-105°C.
  • the sodium aluminate was dissolved in the water with stirring and the sodium hydroxide added thereto.
  • the temperature of the mixture was maintained at 50°C and the sodium silicate was added thereto with stirring.
  • the temperature of the mixture was raised to 90°C-100°C. and maintained within this range for 1 hour with stirring to allow formation of a synthetic aluminosilicate ion exchange material having the formula Na, 2 (AIO Z :Si0 2 ), 2 .27 H 2 0.
  • the mixture was cooled to 50°C, filtered, and the filter cake washed twice with 100 kg. of deionized water.
  • the case was dried at a temperature of 100°C-105°C to a moisture content of 18%-22% by weight to provide the aluminosilicate builder material.
  • This synthetic aluminosilicate ion exchange material is known under the commercial denomination ZEOLITE A; in the dehydrated form it can be used as a molecular sieve and catalyst carrier.
  • the synthetic aluminosilicate known commercially as ZEOLITE X is also suitable for use in the present invention, as are the amorphous synthetic aluminosilicates.
  • the aluminosilicates prepared in the foregoing manner are characterized by a cubic crystal structure and may additionally be distinguished from other aluminosilicates on the basis of the X-ray powder diffraction equipment.
  • Scintillation detection with a strip chart recorder was used to measure the diffraction from the spectrometer. Calculation of the observed d-values was obtained directly from the spectrometer chart. The relative intensities were calculated with lo as the intensity of the strongest line or peak.
  • the synthetic aluminosilicate ion exchange material having the formula prepared as described hereinbefore had the following X-ray diffraction pattern:
  • the above diffraction pattern substantially corresponds to the pattern of ASTM powder diffraction card file #11-590.
  • aliminosilicates having a molar ratio: AlO 2 :SiO 2 ⁇ 1 suitable for use in the instant compositions include: Although completely hydrated aluminosilicate ion exchange materials are preferred herein, it is recognised that the partially dehydrated aluminosilicates having the general formula given hereinbefore are also excellently suitable for rapidly and effectively reducing the water hardness during the laundering operation. Of course, in the process of preparing the instant aluminosilicate ion exchange material, reaction-crystallization parameter fluctuations can result in such partially hydrated materials. As pointed out previously, aluminosilicates having 6% or less water do not function effectively for the intended purpose in a laundering context.
  • the water-insoluble, inorganic aluminosilicate ion exchange materials prepared in the foregoing manner are characterized by a particle size diameter from 0.1 micron to 10 microns.
  • Preferred ion exchange materials have a particle size diameter from 0.2 micron to 10 microns.
  • the term "particle size diameter” herein represents the number-average particle size diameter of a given ion exchange material as determined by conventional analytical technique such as, for example, microscopic determination, scanning electron microscope (SEM).
  • Preferred detergent compositions of the present invention contain from 10% to 50% of the aluminosilicate, more preferably from 15% to 25%.
  • compositions of the invention can be supplemented by all manner of detergent components, either by including such components in the aqueous slurry for spray drying or by admixing such components with the compositions of the invention after the drying step.
  • Soil suspending agents at about 0.1 % to 10% by weight such as water-soluble salts of carboxymethylcellulose, carboxy- hydroxymethylcellulose, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the present invention.
  • Dyes, pigment optical brighteners, and perfumes can be added in varying amounts as desired.
  • Enzymes suitable for use herein include those discussed in U.S. Patents 3,519,570 and 3,553,139 to McCarty and McCarty et al issued 7 July, 1970 and 5 January, 1971 respectively. Particularly preferred are proteolytic enzymes having maximum intrinsic enzyme activity in the range from about pH 8 to about pH 9, especially preparations derived from B. subtilis such as ALCALASE (Registered Trade Mark) manufactured by Novo Industri A.S. Copenhagen, Denmark, and MAXATASE (Registered Trade Mark) manufactured by GIST-BROCADES N.V. Delft. These can be used in levels from about 0.1 to about 2% by weight of the composition.
  • ALCALASE Registered Trade Mark
  • MAXATASE Registered Trade Mark
  • Bleaches such as perborates and percarbonates and activators therefor can also be added to the instant composition, although it is a feature of the invention that such materials can be reduced in level or eliminated entirely.
  • per-bleaches can be present in amounts up to about 15%, especially up to about 10% by weight of the compositions.
  • An optional but highly desirable ingredient of the present compositions is from 0.1% to 3% of a polymeric material having a molecular weight of from 2000 to 2,000,000 and which is a copolymer of maleic acid or anhydride and a polymerisable monomer selected from compounds of formula: wherein R 1 is CH 3 or a C 2 to C 12 alkyl group; wherein R 2 is H or CH 3 and R 3 is H, or a C 1 to C 10 alkyl group; wherein each of R 4 and R 5 is H or an alkyl group such that R 4 and R 5 together have 0 to 10 carbon atoms; and (vi) mixtures of any two or more thereof, said copolymers being optionally wholly or partly neutralised at the carboxyl groups by sodium or potassium.
  • polycarboxylates in the above classes are polymaleic acid/acrylic acid copolymer, 70:30 acrylic acid/hydroxy ethyl maleate copolymer, 1:1 styrene/maleic acid copolymer, propylene/maleic acid copolymer, isobutylene/maleic acid copolymer, diisobutylene/maleic acid copolymer, methylvinylether/maleic acid copolymer, ethylvinylether/maleic acid copolymer, ethylene/ maleic acid copolymer and vinyl pyrrolidone/maleic acid copolymer.
  • the preferred material is a methylvinylether/maleic acid copolymer having an average molecular weight from 12000 to 1,500,000.
  • Inorganic alkaline detergency builder salts can also be added, although high levels of highly alkaline builder salts and of phosphorus containing builder salts should be avoided.
  • the phosphorus content of the compositions of the invention is preferably less than 6% by weight, and highly preferred compositions comprise no more than 1% by weight of phosphorus.
  • Inorganic builder salts include, for instance, alkali metal carbonates, tetraborates, pentaborates, aluminates, sesquicarbonates, polyphosphates such as sodium tripolyphosphate and pentapolyphosphate, and metaphosphates such as tetrametaphosphate, pentametaphosphate and hexametaphosphate, as well as orthophosphates and pyrophosphates.
  • a further optional component of the present compositions is a suds depressant.
  • Soap is an effective suds depressant, especially C 16 - 22 soaps, for instance those derived by neutralisation of Hyfac (trade name) fatty acids. These are hardened marine fatty acids of chain length predominantly C 18 to C 20 .
  • non- soap suds depressants are preferred.
  • a preferred suds depressant comprises silicones.
  • a very suitable granular (prilled) suds depressant product comprises 7% silica/silicone (85% by weight silanated silica, 15% silicone obtained from Messrs. Dow Corning), 65% sodium tripolyphosphate, 25% tallow alcohol (EO) 25 (ie. condensed with 25 molar proportions of ethylene oxide), and 3% moisture.
  • EO tallow alcohol
  • Also suitable and preferred is a combination of 0.02% to 5% by weight, especially about 0.3% of the composition, of a substantially water insoluble wax or mixture of waxes, melting at from 35°C to 125°C, and having saponification value less than 100, and a suds depressing amount, usually about 2% of the composition, of particulate suds depressant mentioned above. Suds depressant mixtures of this type are described in British Patent Specification No. 1492939.
  • compositions of the invention is a water-soluble cationic surfactant such as those described in European Published Application No. 225.
  • the cationic surfactant when used in combination with anionic and nonionic surfactants in defined ratios and amounts, improves the oil stain detergency performance of the formulation.
  • Preferred cationic surfactants have the general formula wherein R 1 is selected from C 8 _ 20 alkyl, alkenyl and alkaryl groups; R 1 is selected from C 1 - 4 alkyl and benzyl; A is an anion; and m is 1, 2, or 3; provided that when m is 2, R' has less than 15 carbon atoms, and when m is 3, R 1 has less than 9 carbon atoms.
  • C 12 and C 14 alkyl trimethyl ammonium salts are highly preferred.
  • the components may be mixed together in any order and in powdery or in fluid form, eg. in an aqueous dispersion.
  • the composition may be sprayed dried, drum dried, freeze dried or dried by other means, to provide a granular composition.
  • a moisture content of 3% to 10% is suitable to provide non-sticky free-flowing granules.
  • Liquid detergent compositions of the invention can contain, as optional ingredients, organic carriers or solvents such as lower aliphatic alcohols having from 2 to 6 carbon atoms and 1 to 3 hydroxyl groups; ethers of diethylene glycol and lower aliphatic mono-alcohols having 1 to 4 carbon atoms; and mixtures thereof.
  • Liquid compositions can also contain hydrotropes such as the water-soluble alkylaryl sulfonates having up to 3 carbon atoms in an alkyl group such as sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-, ethylbenzene- and isopropylbenzene sulfonic acids.
  • compositions of the above Examples all provide good detergency performance, particularly on bleachable type soils and stains and at wash low temperatures compared with compositions containing no polyphosphonate material, and compared with compositions containing polyphosphonates but having pH in use outside the claimed range.
  • Enhanced performance is also obtained when myristyl trimethyl ammonium chloride is replaced by lauryl trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, lauryl dichlorobenzyl dimethyl ammonium chloride, and cetyl trimethyl ammonium ethosulphate.
  • Products with enhanced performance are obtained when the sodium alkyl benzene sulphonate is replaced by C 10 ⁇ 22 olefine sulphonates, C 10 ⁇ 20 paraffin sulphonates, and by zwitterionic detergents such as C 10 - 18 alkyl dimethyl ammonium propane sulphonate or hydroxypropane sulphonate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Claims (2)

1. Ein Waschmittel, umfassend 2 bis 75% eines anionischen, nichtionischen, zwitterionischen oder amphoteren oberflächenaktiven Mittels, 5 bis 60% eines wasserunlöslichen kristallinen Aluminosilikatgerüststoffes der Formel
Figure imgb0020
worin M ein Calciumaustauschkation darstellt, z und y ganze Zahlen von mindestens 6 bedeuten; das Molverhältnis von z zu y im Bereich von 1: 1 bis 0,5:1 liegt und x eine ganze Zahl von 15 bis 264 ist, wobei das Aluminosilikatmaterial einen Teilchengrößendurchmesser von 0,1 µm bis 10 um und eine Ionenaustauschkapazität von mindestens 200 mg Äquivalenten CaCO3 pro g aufweist, zusammen mit einem Polyphosphonatbestandteil, dadurch gekennzeichnet, daß die Polyphosphonatverbindung die Formel
Figure imgb0021
aufweist, worin jedes R1 CH2PO3H2 oder ein wasserlösliches Salz davon bedeutet und m den Wert 0, 1 oder 2 hat, wobei das Polyphosphonat in einer Menge von 0,01 bis 4 Gew.-%, bezogen auf das Waschmittel, vorhanden ist, und daß das Waschmittel 5 bis 25 Gew.-% eines pH-regulierenden Mittels ausgewählt aus Natrium- oder Kaliumbicarbonat enthält, so daß eine 1 %ige wäßrige Lösung des Waschmittels einen pH im Bereich von 7,0 bis 9,5 aufweist.
2. Waschmittel nach Anspruch 1, umfassend zusätzlich 0,1 bis 2% eines proteolytischen Enzyms abgeleitet von B. subtilis und 0 bis 15% eines Peroxy-bleichmittels.
EP78200259A 1977-11-07 1978-10-23 Reinigungsmittelmischungen mit verbesserter Bleichwirkung Expired EP0001853B2 (de)

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GB4630777 1977-11-07
GB4630777 1977-11-07

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EP0001853A1 EP0001853A1 (de) 1979-05-16
EP0001853B1 EP0001853B1 (de) 1982-06-16
EP0001853B2 true EP0001853B2 (de) 1986-01-29

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EP0006268B2 (de) * 1978-06-20 1988-08-24 THE PROCTER & GAMBLE COMPANY Zusammensetzungen zum Waschen und Weichmachen und Verfahren zu deren Herstellung
FI64639C (fi) * 1978-09-27 1983-12-12 Unilever Nv Bleknings- och rengoeringskomposition
DE3066202D1 (en) * 1979-11-03 1984-02-23 Procter & Gamble Granular laundry compositions
US4343713A (en) * 1980-10-29 1982-08-10 The Procter & Gamble Company Particulate composition
DE3248022A1 (de) * 1982-12-24 1984-06-28 Henkel KGaA, 4000 Düsseldorf Spruehgetrocknetes mehrkomponenten-waschmittel
GB8414407D0 (en) * 1984-06-06 1984-07-11 Monsanto Europe Sa Detergent compositions
GB8504489D0 (en) * 1985-02-21 1985-03-27 Monsanto Europe Sa Aminomethylenephosphonate compositions
GB8526999D0 (en) * 1985-11-01 1985-12-04 Unilever Plc Detergent compositions
DE3621536A1 (de) * 1986-06-27 1988-01-07 Henkel Kgaa Fluessiges waschmittel und verfahren zu seiner herstellung
DE3717227A1 (de) * 1987-05-21 1988-12-01 Henkel Kgaa Phosphatfreies waschmittel mit reduzierter inkrustierungstendenz
GB8818215D0 (en) * 1988-07-30 1988-09-01 Flow Lab Phosphate-free detergent
GB9006171D0 (en) * 1990-03-19 1990-05-16 Unilever Plc Detergent compositions
MX9202828A (es) * 1991-06-28 1992-12-01 Colgate Palmolive Co Composiciones detergentes secadas por rociado a base de zeolita y proceso para la preparacion de las mismas.
JPH09505349A (ja) * 1993-11-24 1997-05-27 ユニリーバー・ナームローゼ・ベンノートシヤープ 洗剤組成物
GB9324129D0 (en) * 1993-11-24 1994-01-12 Unilever Plc Detergent compositions and process for preparing them
EP2090646A1 (de) * 2008-01-22 2009-08-19 Thermphos Trading GmbH Oberflächenbehandlungszusammensetzung mit Phosphonsäureverbindungen
EP3650525A1 (de) * 2018-11-07 2020-05-13 Unilever PLC Waschmittelzusammensetzungen

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AT330930B (de) * 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
AT338947B (de) * 1974-07-29 1977-09-26 Henkel & Cie Gmbh Verfahren und mittel zum waschen und reinigen der oberflachen von festen werkstoffen, insbesondere von textilien
AT375395B (de) * 1974-10-04 1984-07-25 Henkel Kgaa Verfahren zum waschen bzw. bleichen von textilien sowie mittel dazu
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DE2531342C2 (de) * 1975-07-14 1985-07-25 Henkel KGaA, 4000 Düsseldorf Verfahren zum Waschen und Reinigen der Oberflächen von festen Werkstoffen und Mittel zur Durchführung des Verfahrens

Also Published As

Publication number Publication date
IT7829534A0 (it) 1978-11-07
EP0001853A1 (de) 1979-05-16
DE2861903D1 (en) 1982-08-05
EP0001853B1 (de) 1982-06-16
IT1100076B (it) 1985-09-28

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