EP0001853A1 - Reinigungsmittelmischungen mit verbesserter Bleichwirkung - Google Patents
Reinigungsmittelmischungen mit verbesserter Bleichwirkung Download PDFInfo
- Publication number
- EP0001853A1 EP0001853A1 EP78200259A EP78200259A EP0001853A1 EP 0001853 A1 EP0001853 A1 EP 0001853A1 EP 78200259 A EP78200259 A EP 78200259A EP 78200259 A EP78200259 A EP 78200259A EP 0001853 A1 EP0001853 A1 EP 0001853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- composition according
- water
- carbon atoms
- aluminosilicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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.
- the present invention provides a detergent composition
- a detergent composition comprising
- the detergent active component of the present compositions can be anionic, nonionic ampholytic or zwitterionic in nature or can be mixtures thereof.
- the deteryent compositions of the invention coutain the active system in an amount of from about 2% to about 75% by weight.
- the active systens is generally in the range from about 4% to about 30%, more preferably from about 6% to about 15% of the compositions.
- higher active contents for example about 20% to about 70% are normally employed.
- a typical- listing of anionic, nonionic, zwitterionic and amphoteric surfactants useful herein appears in USP 3,925,678 incorporated herein by reference. The following list of detergent compounds which can be used in the instant compositions is representative of such materials.
- Water-seluble 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 about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and soils or by the neutralization of free fatty acids. Particularly use- ful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, ie. 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 about 8 to about 22, especially from about 10 to about 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 8 -C 18 ) 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 about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, eg. 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 11.8 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 about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 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 about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
- Other useful anionic detergent compounds herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulronates containing from about 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and ⁇ -alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and
- 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 about 2% to about 15% by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon atoms in the 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 prouduced 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 about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of about 10 to 23 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from about 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 inclde derivatives of aliphatic quaternary ammon lum, phosphonium and sulfonium compounds in which the aliphatic moieties can be straight chain or bnranched, and wherein one of the aliphatic substituents contains from about 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 8 -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%.
- Preferred polyphosphonates are those of the general formula where n is at least 2, M is an alkali metal, ammonium or substituted ammonium cation and Z is a connecting organic moiety having an effective covalency equal to n.
- Z is a hydrocarbyl or a hydrocarbyl substituted amino radical.
- the polyphosphonate can be derived from acids selected from the group consisting of those of the formulae: wherein R 1 and R 2 are hydrogen or CH 2 OH; n is an integer of from 3. to 10; R 3 is hydrogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing from 2 to about 20 carbon atoms, aryl (e.g., phenyl and naphthyl), phenylethenyl, benzyl, halogen (e.g.
- R 4 is hydrogen, lower alkyl (e.g., chlorine, bromine and fluorine), hydroxyl, -CH 2 CCOH, -CH 2 PO 3 H 2 , or -CH 2 CH 2 PO 3 H 2 .
- Operable polyphosphonates of the above formula (i) include propane-1,2,3-triphosphonic acid; butane-1,2,3,4-tetraphosphonic acid, hexane-1,2,3,4,5,6-hexaphosphonic acid; hexane-1-hydroxy-2,3,4,5,6-pentaphosphonic acid; hexane-1,6- dihydroxy-2,3,4,5-tetraphosphonic acid; pentane-1,2,3,4,5-pentaphosphonic acid; heptane-1,2,3,4,5,6,7-heptaphosphonic acid; octane-1,2,3,4,5,6,7,8-octaphosphoic acid; nonane-1,2,3,4,5,6,7,8,9-nonaphosphonic acid; decane-1,2,3,4,5,6,-7,8,9,10-decaphosphonic acid; and the salts of these acids, e.g., sodium, potassium, calcium, magnesium, ammonium, triethanolammonium, diethaanelammoni
- operable polyphosphonates encompassed by the above formula (ii) are ethane-1-hydroxy-1, 1-diphosphonic acid; methanediphosphonic acid; methanehydroxydiphosphonic acid; ethane-1,1,2-triphosphonic acid; propane-1,1,3,3-tetraphosphonic acid; ethane-2-phenyl-1,1, diphosphonic acidiethane-2-naphthyl-1, 1-diphosphonic acid; methanophenyl- diphosphonic acid; ethane-1-amino-1, 1-diphosphonic acid methanedichlorodiphosphonic acid; nonane-5,5-diphosphonic acid; n-pentane-1,1-diphosphonic acid; methanedifluorodiphos- phonic acid; methanedibromediphosphenic acid; propane-2,2- diphosphonic acid; ethane-2-carboxy-1, 1-diphosphonic acid; propane-1-hydroxy-1,
- the polyphosphonates arc free of hydroxyl groups.
- polyphosphonates are the amino poly(alkylene phosphonates),particularly those having the general formula wherein n is anintegral number from O to 14, and each R is individually hydrogen or CH 2 PO 3 H 2 or a water-soluble salt thereof, provided that at least half of the radicals represented by R are CH 2 Po 3 H 2 radicals or water-soluble salts thereof.
- polyphosphonate having the general formula wherein each R 1 is CH 2 PO 3 H 2 or a water-soluble salt thereof and m is from 0 to 2.
- Examples of compounds within this class are aminotri-(methylenephosphonic 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 pK Ca++ of less than about 6, more preferably less than about 5 and especially less than about 4.
- the value of pK Fe 3+ is preferably greater than about 6, more preferably greater than about 9, and especially greater than about 12.
- Literature values of stability constants are taken where possible, (see Stability Constants of Metal-Ion Complexes, Special Publication No 25, the Chemical Society, London). Otherwise, the stability constant is defined at 25 0 C and at 0.1 molar KCl, using a glass electrode method of measurement as described in Complexation in Analytical Chemistry by Anders Ringbcm (1963)
- the pH regulating agent can be selected from inorganic or organic acids or acid salts or mixtures of such materials.
- a preferred inorganic agent is sodium or potassium bicarbonate.
- Suitable organic agents include lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgium Patents 821,368, 821,369 and 821,370; succinic acid, malonic acid (ethylenedioxy) diacetic acid, maleic acid, diglyollic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citraconic acid carboxymethyloxysuccinic acid, lactoxysuccinic acid, and 2-oxa-1,1,3-propane tricarboxylic acid; oxydisuccinic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,3,3-propane tetracarboxylic acid and 1,1,2,3-propane tetracarboxylic acid; cyclopentane-c
- 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 about 7 to 9.5, preferably from about 7 to 9, especially from about 7.5 to 8.5. Generally, from about 5 to 25%, especially from about 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 dctergcncy builders. Such high calcium ion exchange rate and capacity appear to be a function of several interrelated factors which result from the method of preparing said aluminosilicate icn 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 about 18% to about 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 accoraing to the followin pocedung:
- the mixture of step (c) is cooled to a temperature below about 25°C, preferably in the range from 17°C to 23°C, and maintained at that temperature for a period from about 25 hours to about 500 hours, preferably from about 75 hours to about 200 hours.
- step (d) The mixture resulting from step (d) is cooled to a temperature of about 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 additonal 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 about 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 sythetic aluminosilicate ion exchange material having the formula Na 12 (AlO 2 :SiO 2 ) 12 .27 H 2 0.
- the mixture was cooled to 50°C, filtered, and the filter cake washed twice with 1001bs. of deionized water.
- the case was dried at a temperatureof 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 sythetic 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 arc charaederized by a cubic crystal structure and may additionally be distinguished from other aluminosilicates on the basis of the X-ray powder diffraction equipment.
- 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.
- Water-insoluble aluminosilicates having a molar ratio of (AlO 2 ): (SiO 2 ) smaller than 1, ie. in between 1.0 and about 0.5, preferably in between 1.0 and about 0.8, can be prepared in a similar manner.
- aliminosilicates having a molar ratio:AlO 2 :SiO 2 ⁇ 1 suitable for use in the instant compositions include: and 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 about 6% or less water do not function effectively for the intended purpose in laundering context.
- the water-insol able, inorganic aluminosilicate ion exchange materials prepared in the foregoing manner are characterized by a particle size diameter from about 0.1 micron to about 10 microns.
- Preferred ion exchange materials have a particle size diameter from about 0.2 micron to about 10 microns.
- the term "partocle 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 dring 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 carboxymethyl-cellulose, carboxyhydroxymethylcellulose, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the present invetnion.
- 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 or 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 copolyer, 70:30 acrylic acid/hydroxy ethyl maleate copolymer, 1:1 styrane/ 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 about 6% by weight, and highly preferred compositions comprise no more than about 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 depressent, 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% siiica/silicone (85% by weight sila- nated 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 depresant mixtures of this type are described in British patent application 10734/74, incorporated herein by reference.
- compositions of the invention is a water-soluble cationic surfactant such as those described in European Application No. 78 200 050.9 incorporated herein by reference.
- 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 2 is selected from C I-4 alkyl and benzyl; A is an anion; and m is 1,2, or 3; provided that when m is 2, R 1 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 togather 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 about 3% to about 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 from 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 low wash 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.
- Enhanced performance is also obtained when sodium citrate is replaced by sodium succinate, sodium carboxymethyl- oxysuccinate, sodium 2-oxa-1,1,3-propane-tricarboxylate, sodium lactate, sodium malonate, or sodium diglycollate.
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB4630777 | 1977-11-07 | ||
GB4630777 | 1977-11-07 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0001853A1 true EP0001853A1 (de) | 1979-05-16 |
EP0001853B1 EP0001853B1 (de) | 1982-06-16 |
EP0001853B2 EP0001853B2 (de) | 1986-01-29 |
Family
ID=10440714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78200259A Expired EP0001853B2 (de) | 1977-11-07 | 1978-10-23 | Reinigungsmittelmischungen mit verbesserter Bleichwirkung |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0001853B2 (de) |
DE (1) | DE2861903D1 (de) |
IT (1) | IT1100076B (de) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0006268A1 (de) * | 1978-06-20 | 1980-01-09 | THE PROCTER & GAMBLE COMPANY | Zusammensetzungen zum Waschen und Weichmachen und Verfahren zu deren Herstellung |
FR2437442A1 (fr) * | 1978-09-27 | 1980-04-25 | Unilever Nv | Composition de blanchiment et de nettoyage |
EP0028432A1 (de) * | 1979-11-03 | 1981-05-13 | THE PROCTER & GAMBLE COMPANY | Granulare Waschmittelzusammensetzungen |
EP0050894A1 (de) * | 1980-10-29 | 1982-05-05 | THE PROCTER & GAMBLE COMPANY | Wasserweichmachende Zusammensetzungen auf der Basis von Aluminiumsilikaten und diese enthaltende Detergenszusammensetzungen |
EP0114308A1 (de) * | 1982-12-24 | 1984-08-01 | Henkel Kommanditgesellschaft auf Aktien | Sprühgetrocknetes Mehrkomponenten-Waschmittel |
EP0168373A1 (de) * | 1984-06-06 | 1986-01-15 | Monsanto Europe S.A./N.V. | Detergenszusammensetzungen |
US4666623A (en) * | 1985-02-21 | 1987-05-19 | Monsanto Europe S.A. | Granular aminomethylenephosphonate |
EP0291869A2 (de) * | 1987-05-21 | 1988-11-23 | Henkel Kommanditgesellschaft auf Aktien | Phosphatfreies Waschmittel mit reduzierter Inkrustierungstendenz |
US4861503A (en) * | 1985-11-01 | 1989-08-29 | Lever Brothers Company | Zero-phosphorous detergent powders containing aluminosilicate, succinate and polycarboxylate polymer |
EP0353973A2 (de) * | 1988-07-30 | 1990-02-07 | Icn Biomedicals Limited | Phosphatfreie Waschmittel |
US4929380A (en) * | 1986-06-27 | 1990-05-29 | Henkel Kommanditgesellschaft Aug Aktien | Process for the preparation of a storage-stable liquid detergent composition |
EP0448298A1 (de) * | 1990-03-19 | 1991-09-25 | Unilever Plc | Detergenszusammensetzungen |
EP0520582A1 (de) * | 1991-06-28 | 1992-12-30 | Colgate-Palmolive Company | Sprühgetrocknete Waschmittelzusammensetzungen auf Zeolithbasis und Verfahren zur deren Herstellung |
US5583098A (en) * | 1993-11-24 | 1996-12-10 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions |
US5723428A (en) * | 1993-11-24 | 1998-03-03 | Lever Brothers Company | Detergent compositions and process for preparing them |
WO2009092739A1 (en) * | 2008-01-22 | 2009-07-30 | Thermphos Trading Gmbh | Surface treatment composition containing phosphonic acid compounds |
EP3650525A1 (de) * | 2018-11-07 | 2020-05-13 | Unilever PLC | Waschmittelzusammensetzungen |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2412837A1 (de) * | 1973-04-13 | 1974-10-31 | Henkel & Cie Gmbh | Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens |
DE2531342A1 (de) * | 1975-07-14 | 1977-02-03 | Henkel & Cie Gmbh | Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien |
DE2559631A1 (de) * | 1974-10-04 | 1977-05-18 | Henkel & Cie Gmbh | Verfahren zum waschen von textilien, sowie mittel zur durchfuehrung des verfahrens |
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 |
AT338948B (de) * | 1974-10-10 | 1977-09-26 | Henkel & Cie Gmbh | Pulverformige wasch- und reinigungsmittel und verfahren zu ihrer herstellung |
-
1978
- 1978-10-23 DE DE7878200259T patent/DE2861903D1/de not_active Expired
- 1978-10-23 EP EP78200259A patent/EP0001853B2/de not_active Expired
- 1978-11-07 IT IT29534/78A patent/IT1100076B/it active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2412837A1 (de) * | 1973-04-13 | 1974-10-31 | Henkel & Cie Gmbh | Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens |
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 |
DE2559631A1 (de) * | 1974-10-04 | 1977-05-18 | Henkel & Cie Gmbh | Verfahren zum waschen von textilien, sowie mittel zur durchfuehrung des verfahrens |
AT338948B (de) * | 1974-10-10 | 1977-09-26 | Henkel & Cie Gmbh | Pulverformige wasch- und reinigungsmittel und verfahren zu ihrer herstellung |
DE2531342A1 (de) * | 1975-07-14 | 1977-02-03 | Henkel & Cie Gmbh | Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0006268A1 (de) * | 1978-06-20 | 1980-01-09 | THE PROCTER & GAMBLE COMPANY | Zusammensetzungen zum Waschen und Weichmachen und Verfahren zu deren Herstellung |
FR2437442A1 (fr) * | 1978-09-27 | 1980-04-25 | Unilever Nv | Composition de blanchiment et de nettoyage |
EP0028432A1 (de) * | 1979-11-03 | 1981-05-13 | THE PROCTER & GAMBLE COMPANY | Granulare Waschmittelzusammensetzungen |
EP0050894A1 (de) * | 1980-10-29 | 1982-05-05 | THE PROCTER & GAMBLE COMPANY | Wasserweichmachende Zusammensetzungen auf der Basis von Aluminiumsilikaten und diese enthaltende Detergenszusammensetzungen |
EP0114308A1 (de) * | 1982-12-24 | 1984-08-01 | Henkel Kommanditgesellschaft auf Aktien | Sprühgetrocknetes Mehrkomponenten-Waschmittel |
EP0168373A1 (de) * | 1984-06-06 | 1986-01-15 | Monsanto Europe S.A./N.V. | Detergenszusammensetzungen |
US4652403A (en) * | 1984-06-06 | 1987-03-24 | Monsanto Company | Detergent compositions containing aluminosilicates and aminopoly(methylenephosphonates) |
US4666623A (en) * | 1985-02-21 | 1987-05-19 | Monsanto Europe S.A. | Granular aminomethylenephosphonate |
AU577672B2 (en) * | 1985-02-21 | 1988-09-29 | Solutia Europe Nv/Sa | Aminomethylene phosphonate compound adsorbed on support |
US4861503A (en) * | 1985-11-01 | 1989-08-29 | Lever Brothers Company | Zero-phosphorous detergent powders containing aluminosilicate, succinate and polycarboxylate polymer |
US4929380A (en) * | 1986-06-27 | 1990-05-29 | Henkel Kommanditgesellschaft Aug Aktien | Process for the preparation of a storage-stable liquid detergent composition |
EP0291869A2 (de) * | 1987-05-21 | 1988-11-23 | Henkel Kommanditgesellschaft auf Aktien | Phosphatfreies Waschmittel mit reduzierter Inkrustierungstendenz |
EP0291869A3 (de) * | 1987-05-21 | 1990-07-18 | Henkel Kommanditgesellschaft auf Aktien | Phosphatfreies Waschmittel mit reduzierter Inkrustierungstendenz |
EP0353973A2 (de) * | 1988-07-30 | 1990-02-07 | Icn Biomedicals Limited | Phosphatfreie Waschmittel |
EP0353973A3 (de) * | 1988-07-30 | 1990-10-17 | Icn Biomedicals Limited | Phosphatfreie Waschmittel |
EP0448298A1 (de) * | 1990-03-19 | 1991-09-25 | Unilever Plc | Detergenszusammensetzungen |
AU653408B2 (en) * | 1991-06-28 | 1994-09-29 | Colgate-Palmolive Company, The | Zeolite based spray-dried detergent compositions and process for preparing same |
EP0520582A1 (de) * | 1991-06-28 | 1992-12-30 | Colgate-Palmolive Company | Sprühgetrocknete Waschmittelzusammensetzungen auf Zeolithbasis und Verfahren zur deren Herstellung |
US5583098A (en) * | 1993-11-24 | 1996-12-10 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions |
US5723428A (en) * | 1993-11-24 | 1998-03-03 | Lever Brothers Company | Detergent compositions and process for preparing them |
WO2009092739A1 (en) * | 2008-01-22 | 2009-07-30 | Thermphos Trading Gmbh | Surface treatment composition containing phosphonic acid compounds |
EP2090646A1 (de) * | 2008-01-22 | 2009-08-19 | Thermphos Trading GmbH | Oberflächenbehandlungszusammensetzung mit Phosphonsäureverbindungen |
US8551931B2 (en) | 2008-01-22 | 2013-10-08 | Dequest Ag | Surface treatment composition containing phosphonic acid compounds |
RU2527448C2 (ru) * | 2008-01-22 | 2014-08-27 | Италматч Кемикалс СпА | Композиция для обработки поверхности, содержащая соединения фосфоновых кислот |
EP3650525A1 (de) * | 2018-11-07 | 2020-05-13 | Unilever PLC | Waschmittelzusammensetzungen |
Also Published As
Publication number | Publication date |
---|---|
IT1100076B (it) | 1985-09-28 |
EP0001853B1 (de) | 1982-06-16 |
IT7829534A0 (it) | 1978-11-07 |
DE2861903D1 (en) | 1982-08-05 |
EP0001853B2 (de) | 1986-01-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4347168A (en) | Spray-dried granular detergent compositions for improved greasy soil removal | |
US4321165A (en) | Detergent compositions comprising cationic, anionic and nonionic surfactants | |
US4605509A (en) | Detergent compositions containing sodium aluminosilicate builders | |
US4274975A (en) | Detergent composition | |
US3985669A (en) | Detergent compositions | |
EP0001853B2 (de) | Reinigungsmittelmischungen mit verbesserter Bleichwirkung | |
US4072621A (en) | Detergent composition | |
GB1596756A (en) | Detergent compositions | |
EP0006268B2 (de) | Zusammensetzungen zum Waschen und Weichmachen und Verfahren zu deren Herstellung | |
CA2034666C (en) | Detergent composition | |
EP0120659B1 (de) | Reinigungsmittelzusammensetzungen | |
EP0065387B1 (de) | Wäschenachbehandlungsmittel | |
EP0000225A1 (de) | Festes Waschmittel zur verbesserten Beseitigung von fetthaltigem Schmutz | |
EP0137669B1 (de) | Detergenszusammensetzungen | |
EP0193360A2 (de) | Reinigungsmittel | |
JPS6392696A (ja) | 洗濯組成物 | |
GB2236538A (en) | Detergent compositions | |
EP0000215A1 (de) | Waschmittel mit niedrigem Phosphatgehalt zum Waschen von Geweben | |
EP0051986B1 (de) | Reinigungsmittelzusammensetzungen | |
EP0001310A1 (de) | Waschmittelzusammensetzung mit niedrigem Phosphatgehalt zum Waschen von Textilien | |
CA1052658A (en) | Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates | |
GB1580456A (en) | Detergent compositions | |
EP0266931A1 (de) | Körnige Detergentien welche einen hohen Gehalt eines anionischen Tensids enthalten | |
US4617139A (en) | Detergent compositions containing polymers | |
EP0085448B1 (de) | Detergenszusammensetzungen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE DE FR GB NL |
|
17P | Request for examination filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): BE DE FR GB NL |
|
REF | Corresponds to: |
Ref document number: 2861903 Country of ref document: DE Date of ref document: 19820805 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: UNILEVER PLC Effective date: 19830214 |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form | ||
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): BE DE FR GB NL |
|
ET3 | Fr: translation filed ** decision concerning opposition | ||
NLR2 | Nl: decision of opposition | ||
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19891031 Year of fee payment: 12 Ref country code: GB Payment date: 19891031 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19891107 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19891130 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19901012 Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19901023 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19901031 |
|
BERE | Be: lapsed |
Owner name: THE PROCTER & GAMBLE CY Effective date: 19901031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19910501 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19910702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19920630 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |