EP0021491A1 - Waschmittelzusammensetzung, die ein nicht-ionisches/kationisches Tensid-Gemisch und ein Builder-Gemisch enthält - Google Patents
Waschmittelzusammensetzung, die ein nicht-ionisches/kationisches Tensid-Gemisch und ein Builder-Gemisch enthält Download PDFInfo
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- EP0021491A1 EP0021491A1 EP80200524A EP80200524A EP0021491A1 EP 0021491 A1 EP0021491 A1 EP 0021491A1 EP 80200524 A EP80200524 A EP 80200524A EP 80200524 A EP80200524 A EP 80200524A EP 0021491 A1 EP0021491 A1 EP 0021491A1
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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
- C11D3/2075—Carboxylic acids-salts thereof
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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
- C11D1/835—Mixtures of non-ionic with cationic compounds
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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
- C11D3/02—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
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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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/37—Polymers
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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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3711—Polyacetal carboxylates
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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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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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
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- This invention relates to detergent compositions containing a nonionic/cationic surfactant mixture and, as an improved builder mixture, a combination of aluminosilicate and polycarboxylate builder materials. These compositions deliver excellent particulate soil removal performance and greasy/oily soil removal benefits, along with fabric softening, static control, color fidelity and dye transfer inhibition benefits.
- Compositions which utilize mixtures of selected nonionic and cationic surfactants, but without the particular builders described herein, are defined in European Patents No. 0000234., Cockrell, published January 10, 1979, No. 0000235, Murphy, published January 1 0, 1979, and No. 0004121, Murphy, published September 19, 1 979, all of which are incorporated herein by reference.
- builder materials of improving detergency levels of soaps and synthetic detergents permit the attainment of better cleaning performance than is possible when so-called unbuilt compositions are used.
- Such builders permit the attainment of better cleaning performance than is possible when so-called unbuilt compositions are used.
- the behavior and mechanisms by which builders perform their function are only partially understood. It is known that good builders must be able to sequester most of the calcium and/or magnesium ions in the wash water since these ions are detrimental to the detergency process.
- it is difficult to predict which compounds possess useful combinations of builder properties because of the complex nature of detergency and the countless factors which contribute both to overall performance results and the requirements of environmental acceptability.
- STP sodium tripolyphosphate
- Inorganic builders other than STP are generally not satisfactory for use as a builder in detergent formulations because of their poor builder properties.
- Sodium aluminosilicates, commonly known as zeolites have been proposed for use in detergent formulations since they are able to soften water by removing calcium ions; but they are not very effective in removing magnesium ions from water.
- new detergent compositions with cleaning properties superior or equivalent to phosphate-built detergents, but which do not contain phosphates, and which achieve environmental acceptability by being readily biodegradable.
- new detergent compositions with a cationic/nonionic surfactant mixture and, as an improved builder mixture, a combination of aluminosilicate and polycarboxylate builder materials. These compositions provide cleaning performance superior to that of phosphate-built compositions and also provide other fabric care benefits, such as softening and static control.
- the present invention encompasses a detergent composition, which contains from 0 to about 5% phosphate materials, comprising:
- This invention comprises the discovery of an improved builder mixture for use in detergent compositions containing selected nonionic/cationic surfactant mixtures.
- the builder mixture a combination of aluminosilicate and polycarboxylate builder materials, delivers excellent particulate soil removal performance and greasy/oily soil removal benefits. These compositions also provide fabric softening, static control, color fidelity and dye transfer inhibition benefits.
- the detergent compositions are particularly good in 10-40°C water, especially when the particle size diameter of the aluminosilicate material is from about 0.5 to about 2 microns.
- the essential elements in the detergent composition of this invention are: anonionic/cationic surfactant mixture, and a mixture of aluminosilicate and polycarboxylate builder materials.
- nonionic:cationic surfactant ratios of from about 5:1 to about 20:1; while optimum removal of particulate soils is obtained with compositions having nonionic:cationic surfactant ratios of from about 2:1 to about 9:1, especially from about 3:1 to about 6.5:1, most especially from about 3.5:1 to about 5.5:1, with these ratios being particularly effective where the cationic surfactant used is of the di-long chain variety disclosed and claimed in European Patent Mo. 0004121, Murphy, published September 19, 1979, and incorporated herein by reference.
- compositions of the present invention are preferably formulated so as to have a pH of at least about 7 in the laundry solution, at conventional usage concentrations, in order to optimize their overall cleaning performance, to aid in their manufacturing and processing, and to minimize the possibility of washing machine corrosion.
- Alkalinity sources such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, and sodium bicarbonate, may be included in the compositions for this purpose.
- Some of the cationic/nonionic systems of the present invention may attain optimum removal of greasy/ oily soils at higher pHs, while attaining optimum particulate removal at relatively lower pHs. In these systems, overall performance may be enhanced by varying the pH of the wash solution during the laundering process.
- compositions have a pH of at least about 8 in the laundry solution in order to optimize the removal of greasy/ oily and body soils.
- these preferred compositions should also have the ability to maintain a pH in the laundry-solution of from about 8 to 11 throughout the washing operation (reserve alkalinity).
- a reserve alkalinity may be obtained by incorporating compounds which buffer at pHs of from about 8 to 11, such as monoethanolamine, diethanolamine, and triethanolamine.
- compositions of the present invention are also essentially free of oily hydrocarbon materials and solvents, such as mineral oil, paraffin oil and kerosene, since these materials, which are themselves oily by nature, load the washing liquor with excessive oily material, thereby diminishing the cleaning effectiveness of the compositions themselves.
- Nonionic surfactants having HLBs of from about 5 to about 17, preferably from about 8.5 to about 14, more preferably from about 10 to about 13.5, which are conventionally used in detergent compositions, may be used in the compositions of the present invention.
- Such surfactants include the condensation product of 1 mole of a saturated or unsaturated, straight or branched chain carboxylic acid having from about 10 to about 18 carbon atoms with from about 5 to about 50 moles of alkylene (particularly ethylene) oxide; the condensation product of 1 mole of saturated or unsaturated, straight or branched chain alcohol having from about 10 to about 24 carbon atoms with from about 5 to about 50 moles of alkylene (especially ethylene) oxide;.
- polyethylene glycols having a molecular weight of from about 400 to about 30,000; and the condensation product of 1 mole of alkyl phenol wherein the alkyl chain contains from about 8 to about 18 carbon atoms with from about 4 to about 50 moles of alkylene (especially ethylene) oxide.
- nonionic surfactants useful in the present invention is found in U.S. Patent 3,862,058, Nirschl and Gloss, issued January 21, 1975, incorporated herein by reference.
- Preferred nonionic surfactants for use in the compositions of the present invention because of their excellent biodegradability and performance characteristics, have the formula R(OC 2 H 4 ) n OH, wherein R is a primary or secondary, straight or branched alkyl chain containing an average of from about 8 to about 22, preferably from about 10 to about 20, carbon atoms, and n is an average of from.about 2 to about 12, preferably from about 2 to about 9, especially from about 2 to about 7. Where di-long chain cationic materials are used in the compositions of the present invention, it is especially preferred that the R group in the nonionic surfactant contain from about 10 to about 16 carbon atoms.
- the nonionic surfactants described herein have an HLB (hydrdphilic-lipophilic balance) of from about 5 to about 17, preferably from about 8.5 to about 14, and most preferably from about 10 to about 13.5.
- HLB hydrophilic-lipophilic balance
- a preferred class of surfactants utilizes alcohols which contain about 20% of 2-methyl branched isomers, and are commercially available under the trade name Neodol, from the Shell Chemical Company.
- Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C 10 alcohol with 3 moles of ethylene oxide,.the condensation product of C 12-13 alcohol with about 3 moles of ethylene oxide, and the same product which is stripped to remove substantially all lower ethoxylate and nonethoxylated fractions, the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide, the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C 12 alcohol with 5 moles of ethylene oxide, the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of C 12-13 alcohol with 9 roles of ethylene oxide, the condensation product of C 14-15 alcohol with 3 moles of ethylene oxide, the condensation product of C 14-15 alcohol with 4 moles of ethylene oxide, the condensation product of C 14-15 alcohol with 9
- catiohic surfactants used are of the di-long chain variety and that the nonionic surfactant be selected from the group consisting of the condensation product of C 14-15 alcohol with 2.25 moles of ethylene oxide, the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide, the condensation product of C 12-15 alcohol with 7 moles of ethylene oxide, the con- densa tion product of C12-15 alcohol with 9 moles of ethylene oxide, the condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, and the same product which is stripped so as to remove lower ethoxylate and nonethoxylated fractions, the condensation product of C9-11 alcohol with '8 moles of ethylene oxide, which is stripped so as to remove lower.ethoxylate and nonethoxylated fractions, the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of coconut alcohol with 6 moles of ethylene oxide, the condensation product of tallow alcohol with 9 moles of ethylene
- compositions of the present invention may contain mixtures of nonionic surfactants falling within the above preferred nonionic surfactant definition, such as a mixture of the condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide with the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide, in a ratio of from about 4:1 to about 1:4.
- the present invention may also contain mixtures of nonionic surfactants, some of which do not fall within the above preferred nonionic surfactant definition (such as alcohol ethoxylates having an average of greater than about 12 ethylene oxide groups per molecule), and in such mixtures it is preferred that at least one of the nonionic surfactants contained in the mixture falls within the above preferred nonionic surfactant definition and that this preferred nonionic surfactant (or mixture of surfactants) be included in an amount such that it falls within the nonionic/cationic ratio range required herein.
- nonionic surfactant mixture contains a nonionic surfactant (or surfactants ⁇ which falls outside of the above preferred nonionic surfactant definition
- the ratio of the surfactant (or surfactants) within the definition to those outside the definition be within the range of from about 1:1 to about 10:1.
- preferred nonionic surfactant mixtures also contain alkyl glyceryl ethers.
- Particularly preferred are glyceryl ethers having the formulae: wherein R is an alkyl or alkenyl group of from about 8 to about 18, preferably from about 8 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbon atoms in the alkyl chain, and n is from 1 to about 6.
- R is an alkyl or alkenyl group of from about 8 to about 18, preferably from about 8 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbon atoms in the alkyl chain
- n is from 1 to about 6.
- These compounds may be used together with the nonionic surfactant component of the present invention, in a ratio of nonionic surfactant to glyceryl ether of from about 1:1 to about 4:1, particularly about 7:3.
- Glyceryl ethers of the type useful in the present invention are disclosed in U.S. Patent 4,098,713,
- nonionic surfactants useful herein comprises a mixture of "surfactant” and "co-sur- factant", containing at least one nonionic surfactant falling within the definition of the nonionic surfactants preferred herein, as described in British Patent No. 1.462.134, Collins, published on January 19, 1977, the-disclosure of which is incorporated herein by reference.
- each R 1 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxyl groups, and optionally interrupted by up to four structures selected from the group consisting of: and mixtures thereof, and which contains from about 8 to 22 carbon atoms, and which may additionally contain up to 2 0 ethylene oxide groups, and m is a number from 1 to 3.
- R 2 is an alkyl or hydroxy alkyl group containing from 1 to 4 carbon: atoms, or a benzyl group with no more than one R in a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon positions on the Y group are filled by hydrogens.
- Y is selected from the group consisting of: wherein p is from 1 to 12, wherein each p is from 1 to 12, wherein each p is from 1 to 12, and
- L is 1 or 2, with the Y groups being separated by a moiety selected from the group consisting of R and R 2 analogs (preferably alkylene or alkenylene) having from one to about twenty-two carbon atoms and 2 free carbon single bonds when L is 2.
- Z is a water-soluble anion such as halide, methyl sulfate, sulfate, or nitrate anion, particularly preferred anions being chloride, bromide, iodide, sulfate, or methyl sulfate, in a number to give electrical neutrality of the cationic component.
- the particular cationic component to be included in a given system depends to a large extent upon the particular nonionic component to be used; it is selected such that it is at least water-dispersible when mixed with the nonionic surfactant.
- the cationic surfactant is chosen, in light of the particular nonionic surfactant used, in order to satisfy the cloud point requirements of the detergent composition, discussed below. Mixtures of these cationic materials may also be used in the compositions of the present .invention.
- Preferred cationic surfactants are those having critical micelle concentrations of less than about 500 ppm, especially less than about 100 ppm.
- L is equal to 1
- p is from 1 to 12, preferably from 1 to 10
- Y is or mixtures thereof.
- L may be equal to two, thereby yielding cationic components containing two cationic charge centers.
- An example of a di-cationic component is given below:
- Other cationic materials which are useful in the compositions of the present invention include phosphonium and sulfonium materials.
- a particularly preferred type of cationic component which is described in Japan Patent No. 79-39413, L etton, published March 26, 1979, incorporated herein by reference, has the formula wherein R 1 is C 1 to C 4 alkyl or hydroxyalkyl; R 2 is C 5 to C 30 straight or branched chain alkyl, alkenyl, alkylbenzyl or alkyl phenyl, or wherein s is from 0 to 5; R 3 is C 1 to C 20 alkylene or alkenylene; a is 0 or 1, n is 0 or 1, and n is 1 when a is 1; m is from 1 to 5; Z and Z are each selected from the group consisting of and wherein at least one of said Z 1 or Z 2 groups is and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably chloride, bromide,
- the preferred choline-derivative cationic substances may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material.
- the choline- derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize trimethylamine, forming the desired cationic component.
- each R 1 is a C 1 to C 4 alkyl or hydroxyalkyl group, preferably a methyl group.
- Each R 2 is either hydrogen or C 1 to C 3 alkyl, preferably hydrogen.
- R 3 is a C 4 to C 30 straight or branched chain alkyl or alkenyl, preferably a C 8 to C 18 alkyl group, most preferably a C 12 alkyl group.
- R 4 - is-a C 1 to C 10 alkylene or alkenylene. group.
- n is from 2 to 4, preferably 2; y is from 1 to 20, .
- Z 2 is selected from the group consisting of and at least one of Z 1 and Z 2 groups is selected from the group consisting of X is an anion which makes the compound at least water dispersible, and is selected from the group consisting of halides, methyl sulfate, sulfate, and nitrate, particularly chloride, bromide iodide, methyl sulfate and sulfate.. Mixtures of the above structures can also be used.
- Cationic surfactants of this type are disclosed in European Patent No. 0004121, Murphy, pubhshed September 19, 1 979, incorporated herein by reference.
- Preferred cationic surfactants are those having the formulae: wherein the R 1 and R 2 groups contain an average of from about 16 to about 22 carbon atoms, preferably is alkyl groups, and-most preferably contain an average of from about 16 to about 18 carbon atoms,.
- R 3 and R 4 are C 1 to C 4 alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected from the group consisting of halide, hydroxide, methyl sulfate, or acetate anions.
- Preferred cationic surfactants include ditallowalkyl- dimethyl (or diethyl or dihydroxyethyl) ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyl (C 16 ) (also known as distearyl), dimethyl (or diethyl, or dihydroxyethyl) ammonium chloride, dioctadecylalkyl (C 18 ) dimethylammonium chloride, dieicosylalkyl (C 20 ) dimethylammonium chloride, methyl-(l)-tallowalkylamiao ethyl (2) tallowalkylimidazolinium methyl sulfate (commercially available as Varisoft 475 from Ashland Chemical Company), or mixtures of those surfactants.
- Particularly preferred cationic surfactants are ditallowalkyldimethylammonium chloride, ditallowalkyldimethylammonium methyl sulfate, methyl(1)tallowalkylamidoethyl(2)tallowalkylimidazolinium methyl sulfate, and mixtures of those surfactants, with ditallowalkyldimethylammonium chloride being especially preferred.
- Another particularly useful class of cationic surfactant is that in which the two long chains of the cationic surfactant contain a significant amount of unsaturation, such as where at least about 20%, preferably at least about 30%, of the long chains contain at least one double bond.
- Compounds of this type have the formula wherein R 1 and R2 contain an average of from about 16 to about 22 (most preferably from about 16 to about 18) carbon atoms, and at least about 20% of these chains contain at : least one double bond; R 3 and R 4 are C 1 to C 4 alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected from the group consisting of halide, hydroxide, methyl sulfate, or acetate anions.
- a preferred cationic surfactant is di-partially hydrogenated tallow dimethylammonium halide (especially chloride or methyl sulfate), which is also known as disoftened- tallowalkyldimethylammonium halide.
- a commercially available compound of this type is Adogen 470, sold by Ashland Chemical Company, wherein about 30% of the tallow chains are oleyl in character.
- Compositions made with these cationics showed several significant advantages over those made with more conventional cationics (such ditallowalkyldimethylammonium chloride), particularly those compositions show improved particulate soil removal, especially at low wash temperatures, improved static control, and remain in a stable single phase at temperatures down to about 40°F.
- compositions of the present invention may be formulated using the guidance provided by the reduced monomer concentration of the cationic component (CR) in the laundry solution. Specifically, the selection of a C R value for a given nonionic and cationic surfactant-pair will determine the ratio in which to combine those surfactants. A given nonionic/cationic surfactant pair will give its best particulate or grease/oil removal' performance when it is formulated to have a C R value which falls within-the ranges defined herein.
- the reduced monomer concentration of a surfactant is obtained by dividing the'concentration of the surfactant monomer present in the laundry solution by the critical micelle concentration (CMC) of that surfactant. As used in this application, CMCs are determined at 105°F in water containing 7 grains/gallon of mixed ( 2:1 ; Ca:M g) hardness, unless otherwise stated.
- the C R value of the nonionic/cationic surfactant mixture be in the range of from about 0.002 to about 0.2, especially from about 0.002 to about 0.15, most preferably from about 0.002 to about 0.08.
- the nonionic/cationic surfactant mixture have a C R of from 0.005 to about 0.2, especially from about 0.008 to about 0.15, most preferably from about 0.01 to about 0.1. It is in the area of overlap (i.e., C R equals about 0.005 to about 0.2) of these C R ranges that the compositions of the present invention yield both optimum particulate and greasy/oily soil removal.
- compositions which give the best performance on greasy/oily soils also satisfy specific cloud point requirements, given below, and detailed in European Patent No. 0000235, Murphy,, published January 10, 1979, incorporated herein by reference.
- these preferred compositions have nonionic/cationic mixtures which exhibit a cloud point between about 10°C and 70°C, more preferably between about 20°C and 70°C, especially between about 30°C and about 50°C.
- the compositions will exhibit their best grease/oil,removal performance when the temperature of the wash solution in which they are used falls within about 20°C, preferably within about 15°C, and most preferably within about 10°C, of the cloud point of the nonionic/ cationic surfactant mixture..
- cloud point means the temperature at which a graph plotting the light scattering intensity of the composition versus wash solution temperature begins to sharply increase to its maximum value, under the following experimental conditions:
- the detergent compositions herein contain from about 5% to about 99%, preferably from about 20% to about 60%, by weight of-a detergency builder mixture.
- the builder mixture consists essentially of:
- the weight ratio of the aluminosilicate material to the polycarboxylate-material is from about 1:4 to about 4:1, more preferably from about 1:3 to about 2:1.
- the aluminosilicate materials for use herein are those commonly known as Zeolites A, X, and P(B).
- the zeolites should contain at least 10% water of hydration and should have a particle size diameter of from about 0.01 microns to about 25 microns, preferably from about 0.1 microns to about 10 microns, more preferably from about 0.5 microns to about 2 microns.
- Aluminosilicate materials are more fully described in U.S. Patent 4,096,081, Phenicie.et al, issued June 20, 1978, and German Patent No.27 04 003, Ohren, published on August 18, 1 977, the disclosures of which are incorporated herein by reference.
- amorphous aluminosilicate materials suitable for use herein are fully described in U.S. Patent Application No. 4.180 485, Llenado, published December 25, 1979 ., incorporated herein by reference-Examples of suitable polycarboxylate builder materials for use herein are (1) water-soluble aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, (2) the water-soluble salts of phytic acid, e.g., sodium and potassium phytates, disclosed in U.S. Patent No. 2,739,942, Eckey, issued March 27, 1956, incorporated herein by reference; (3) the polycarboxylate materials described in U.S. Patent 3,364,103; and (4) water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference.
- a useful detergent builder which may be employed in the present invention comprises a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain .from the site of attachment of the next carboxyl-containing radical.
- Specific examples of the above-described builders include polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with themselves.
- polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
- European Patent No 80200102.4, Rodriguez et al.,filed-on'February 7, 1980, incorporated herein by reference discloses a builder system containing these polyacetal carboxylates along with aluminosilicate builder materials, for use in detergent compositions, which preferably contain nonionic/cationic surfactants.
- Preferred polycarboxylate builders for use in the ' present invention are sodium or potassium nitrilotriacetate or citrate, or mixtures thereof.
- the compositions of this invention contain from 0 to about 5% phosphate materials, and are preferably substantially free of phosphate materials.
- the detergent compositions additionally contain from about 2 to about 25%, preferably from about 2 to about 16%, and most preferably from about 2 to about 10% of a fatty amide surfactant, such as ammonia amides (e.g., coconutalkyl ammonia amide, diethanol amides, and ethoxylated amides).
- a fatty amide surfactant such as ammonia amides (e.g., coconutalkyl ammonia amide, diethanol amides, and ethoxylated amides).
- ammonia amides e.g., coconutalkyl ammonia amide, diethanol amides, and ethoxylated amides.
- the ratio of the cationic/ nonionic mixture to the amide component in the composition is in the 'range of from about 5:1 to about 50:1, preferably from about 8:1 to about 25:1.
- the addition of the amide component is in the 'range of from about 5:1 to about 50:
- amides are C 8 -C 20 monoethanol amides, C 8 -C 20 diethanol amides, and amides having the formula wherein R is a C 8 -C 20 alkyl group, and mixtures thereof.
- Particularly preferred amides are those where the alkyl group contains from about 10 to about 16 carbon atoms, such as coconut alkyl monoethanol or diethanol amide.
- Such compounds are commercially available under the tradenames Superamide GR, from Onyx Chemical Co., Jersey City, N.J., Superamide F-3 from Ryco, Inc., Conshohocken, Pa., and Gafamide CDD-518, available from GAF Corp., New York, N.Y.
- These amide components may also be added in small amounts, i.e., from about 2% to about 5%, to act as suds modifiers. Specifically, they tend to boost the sudsing in an active system which exhibits relatively low sudsing, and depress the sudsing in.an active system which exhibits. relatively high sudsing.
- compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their conventional art-established levels, as long as these ingredients are compatible with the nonionic and cationic components required herein.
- the compositions may contain up to about 15%, preferably up to about 5%, and most preferably from about 0.001 to about 2%, of a suds suppressor component.
- Typical suds suppressors useful in the compositions of the present invention include, but are not limited to, those described below.
- silicone-type suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al., incorporated herein by reference.
- the silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
- the silicone material can be described as a siloxane having the formula: wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
- Polydimethylsiloxanes (R and R' are methyl, having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds controlling agents.
- Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of such. ingredients include diethyl-, dipropyl-, dibutyl-, methylethyl-, phenylmethyl-polysiloxanes and the like.
- Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred_to hereinbefore, and solid silica.
- a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl- silanated) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m 2 /gm intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2.
- the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active, detergent- impermeable carrier..
- Particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, described in U.S. Patent 4,075,118, Gault et al, issued February 21, 1978, incorporated herein by reference.
- An example of such a compound is DB-544, commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
- Microcrystalline waxes having a melting point in the range from 35°C-115°C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use in the subject compositions, and are described in detail in U.S. Patent 4,056,481, Tate, issued November 1, 1977, incorporated herein by reference.
- the microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
- Preferred ⁇ microcrystalline waxes have a melting point from about 65°C to 100°C, a molecular weight in the range from 400-1,000; and a penetration value of at least 6, measured at 77°F by ASTM-D1321.
- Alkyl phosphate esters represent an additional preferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and mono-oleyl phosphates, which can contain di-and trioleyl phosphates.
- alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g. monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
- adjunct components which may be included in the compositions of the present invention, in their conventional art-established levels for use (i.e., from about 0 to about 40%), include semi-polar nonionic (such as amine oxides), anionic, zwitterionic and ampholytic cosurfactants; detergency builders; bleaching agents; bleach activators; soil release agents (particularly copolymers of ethylene terephthalate and polyethylene oxide terephthalate, such as Milease T sold by ICI, United States, as disclosed in U.S.
- semi-polar nonionic such as amine oxides
- anionic, zwitterionic and ampholytic cosurfactants such as amine oxides
- detergency builders such as amine oxides
- bleaching agents such as amine oxides
- bleach activators such as Milease T sold by ICI, United States, as disclosed in U.S.
- Patent 4,132,680 Nicol, issued January 2, 1979, incorporated herein.by reference
- soil suspending agents corrosion inhibitors; dyes; fillers; optical brighteners; germicides; pH adjusting agents; alkalinity sources; hydrotropes; enzymes; enzyme-stabilizing agents; perfumes; solvents; carriers; suds modifiers; opacifiers; and the like.
- certain conventional components such as cosurfactants and other detergency builders, as well as fabric softening and static control. agents, will not generally be necessary in a particular formulation,. giving the compositions of the present invention a potential cost advantage over conventional detergent/ softener compositions..
- compositions of the present invention give such outstanding clay removal performance across the range of water hardness conditions, for environmental reasons the compositions of the present invention contain less than about 5% phosphate materials.
- Preferred compositions are substantially or totally free of such phosphate materials., without decreasing the performance of the compositions- Preferred compositions of the present invention are also substantially free of carboxymethylcellulose in order to optimize the clay removal performance of the system.
- compositions of the present invention may contain anionic materials, such as anionic surfactants and hydrotropes (e.g., alkali metal toluene sulfonates), it is preferred that particular anionic materials be contained in amounts sufficiently small such that not more than about 10%, preferably not more than about 5%, of the cationic surfactant, contained in the laundry solution, is complexed by the anionic material. Such a compleaxing of the anionic material with the cationic surfactant, decreases the overall cleaning and fabric conditioning performance of the composition. Suitable anionic materials may be selected based on their strength of complexation with the cationic material included in the composition (as indicated by their dissociation constant).
- an anionic material when it has a dissociation constant of at least about 1 x 10 -3 (such as sodium toluene.sulfonate), it may be contained in an amount up to about 40%, by weight, of the cationic surfactant; where the anionic material has a dissociation constant of at least about 1 x 10 -5 , but less than about 1 x 10 3, it may be contained in an amount up to about 15%, by weight, of the cationic surfactant; and where the anionic material has a dissociation constant of less than about 1 x 10 -5 (such as sodium C 11.8 linear alkylbenzene sulfonate), it may be contained only in amounts up to about 10%, by weight, of the cationic surfactant.
- Preferred compositions are substantially free of such anionic materials.
- cosurfactants and detergency builders which may be used in the compositions of the present invention are found in U.S. Patent No. 3,717,630, Booth, issued February 20, 1973, and European Patent No. 0000235, Murthy, published Uantiary 10, 1979, both of which are incorporated herein by reference.
- these components, particularly the anionic surfactants should be checked with the particular nonionic/cationic surfactant system chosen, and used in an amount, so as to be certain that they will be compatible with the nonionic/cationic surfactant system.
- compositions of the present invention may be produced in a variety of forms, including liquid, solid, granular, paste, powder or substrate compositions.
- Preferred substrate articles may be formulated according to U.S. Patent No. 41170.565, Murphy, -published on October 9, 1979, incorporated herein by reference.
- the compositions of the present invention are formulated as liquids and contain up to about 20% of a lower alkyl (C l to C4) alcohol, particularly ethanol. Liquid compositions containing lower levels of such alcohols (i.e., about 7 to 12%) tend to exhibit less phase separation than compositions containing higher alcohol levels.
- Granular compositions herein may also contain up to about 15% by weight of alkali metal silicates, especially sodium silicate (2.0 ratio), to increase flowability and physical stability of the granules.
- compositions of the present invention are used in the laundering process by forming an aqueous solution containing.from about 0.01 (100 parts per million) to about 0.3% (3,000 parts per million), preferably from about 0.02 to about 0.2%, and most preferably from about 0.03 to about 0.15%, of the detergent compositions defined herein, and agitating the soiled fabrics in that solution. The fabrics are then rinsed and dried.
- the compositions of the present invention yield outstanding particulate and greasy/oily soil removal, together with fabric softening, static control; color fidelity, and dye transfer inhibition benefits, without requiring the use of any of the other conventionally used fabric softening and static control laundry additives.
- Identical clay-soiled cotton, polyester/cotton, and polyester swatches were washed in aqueous solutions having dissolved therein: 500 parts per million (ppm) of a surfactant mixture containing 4.5 parts of the nonionic surfactant C 12-13 E 6.5 (condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, commercially available as Neodol 23-6.5 from Shell Chemical Company) and 1 part of the cationic surfactant(dihydrogenated tallowalkyl dimethylammonium chloride); 600 ppm of the builder or builder mixture listed below; and 87 ppm of monoethanol amine.
- ppm 500 parts per million (ppm) of a surfactant mixture containing 4.5 parts of the nonionic surfactant C 12-13 E 6.5 (condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, commercially available as Neodol 23-6.5 from Shell Chemical Company) and 1 part of the cationic surfactant(d
- the swatches were washed for 10 minutes in a miniature agitator containing 1-1/2 gallons of washing liquor at 100°F and artificial water hardness (2 moles Ca ++ to 1 mole Mg ++ ) at levels of 2, 7 and 12 grains per gallon.
- the swatches comprised approximately 4% by weight of the washing liquor.
- the swatches were spun dry and rinsed with 1-1/2 gallons of water, at 100°F, having the same water hardness as that of the water they were washed in.
- the swatches were then dried in a miniature electric dryer.
- a Hunter Reflectometer was used to obtain a reflectance reading (in Hunter Whiteness Units) for each of the laundered swatches. A higher reflectance reading indicates greater cleaning effectiveness.
- the results were as follows:
- nonionic surfactant in Composition A is replaced, in whole or in part, by the condensation product of C 14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide; the- condensation product of C 12-15 alcohol with 9 moles of ethylene oxide; the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C 12-15 alcohol with 7 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; a 1:1 by weight mixture of the condensation product of C 12-15 alcohol with 7 moles of ethylene oxide and the condensation product of C14-15 alcohol with 7 moles of ethylene oxide; and other mixtures of those surfactants.
- the weight ratio of the aluminosilicate material to the polycarboxylate material is from about. 1:10 to about 10:1, especially when from about 1:4 to about 4:1.
- the cleaning advantages are most readily apparent at high water hardness levels, such as above 7 grains/gallon.
- aluminosilicate material is any hydrated Zeolite A, X or P(B), having a particle size diameter of from about 0.01 microns to about 25 microns, especially from about 0.1 microns to about 10 microns.
- Substantially similar cleaning performance is obtained when the number of segments (n) in the polyacetal carboxylate builder averages at least 4, but especially when n averages between 10 and 200.
- composition delivered excellent particulate soil removal performance, as demonstrated in Example I. Further, the composition provided greasy/oily soil removal benefits.
- the following detergent composition was produced: : 1 Condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, commercially available as Neodol 23-6.5 from Shell Chemical Company.
- composition delivered excellent particulate soil removal performance, as demonstrated in Example I. Further, the composition provided greasy/oily soil removal benefits.
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US4970479A | 1979-06-18 | 1979-06-18 | |
US49704 | 1979-06-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0021491A1 true EP0021491A1 (de) | 1981-01-07 |
Family
ID=21961238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80200524A Withdrawn EP0021491A1 (de) | 1979-06-18 | 1980-06-09 | Waschmittelzusammensetzung, die ein nicht-ionisches/kationisches Tensid-Gemisch und ein Builder-Gemisch enthält |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0021491A1 (de) |
JP (1) | JPS5638396A (de) |
CA (1) | CA1131092A (de) |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2125814A (en) * | 1982-07-05 | 1984-03-14 | Lion Corp | Additive composition for granular detergent |
FR2565244A1 (fr) * | 1984-06-01 | 1985-12-06 | Colgate Palmolive Co | Composition detergente assouplissant les tissus, renforcee par un adjuvant de detergence et procede de lavage |
FR2565246A1 (fr) * | 1984-06-01 | 1985-12-06 | Colgate Palmolive Co | Composition detergente organique synthetique antistatique, son procede de fabrication et procede de lavage |
FR2565243A1 (fr) * | 1984-06-01 | 1985-12-06 | Colgate Palmolive Co | Composition detergente organique synthetique non ionique en particules, renforcee par des adjuvants de detergence et ses procedes de fabrication |
FR2586425A1 (fr) * | 1985-08-20 | 1987-02-27 | Colgate Palmolive Co | Compositions detergentes liquides contenant des agents stabilisants en suspension et un additif du type uree et procedes pour nettoyer des tissus les utilisant |
US4720399A (en) * | 1984-06-01 | 1988-01-19 | Colgate-Palmolive Company | Process for manufacture of particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders |
US4725455A (en) * | 1984-06-01 | 1988-02-16 | Colgate-Palmolive Company | Process for manufacturing particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and polyphosphate builders |
US4853259A (en) * | 1984-06-01 | 1989-08-01 | Colgate-Palmolive Company | Process for manufacturing particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders |
EP0384070A2 (de) * | 1988-11-03 | 1990-08-29 | Unilever Plc | Zeolith P, sein Herstellungsverfahren und seine Verwendung in Waschmitteln |
EP0385562A2 (de) * | 1989-01-03 | 1990-09-05 | Amway Corporation | Waschmittel für Wäsche |
EP0502675A2 (de) * | 1991-03-05 | 1992-09-09 | Unilever Plc | Detergenszusammensetzungen |
WO1994007978A1 (de) * | 1992-09-28 | 1994-04-14 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung pulverförmiger oder granularer detergensgemische |
US5374370A (en) * | 1988-11-03 | 1994-12-20 | Unilever Patent Holdings B.V. | Type B aluminosilicates with low Si:Al ratio for detergent use |
WO1995027030A1 (en) * | 1994-03-31 | 1995-10-12 | The Procter & Gamble Company | Detergency composition comprising zeolite map and protease enzyme |
WO1996026257A1 (en) * | 1995-02-23 | 1996-08-29 | Unilever Plc | Cleaning composition comprising saturated dialkyl cationic surfactants |
US6235704B1 (en) | 1997-07-30 | 2001-05-22 | Basf Aktiengesellschaft | Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives |
WO2003087285A1 (en) * | 2002-04-16 | 2003-10-23 | Unilever Plc | Fabric treatment composition |
WO2010070088A1 (de) | 2008-12-18 | 2010-06-24 | Basf Se | Tensidgemisch enthaltend verzweigte kurzkettige sowie verzweigte langkettige komponenten |
WO2011003904A1 (de) | 2009-07-10 | 2011-01-13 | Basf Se | Tensidgemisch mit kurz- und langkettigen komponenten |
WO2011080540A1 (en) * | 2009-12-30 | 2011-07-07 | Ecolab Inc. | Phosphate substitutes for membrane-compatible cleaning and/or detergent compositions |
WO2011117350A1 (de) | 2010-03-25 | 2011-09-29 | Basf Se | Elektrochemisches textilwaschverfahren |
US9435073B2 (en) | 2010-03-25 | 2016-09-06 | Basf Se | Electrochemical textile-washing process |
US11441105B2 (en) | 2017-12-15 | 2022-09-13 | Rhodia Operations | Composition containing lanthanide metal complex |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0000234A1 (de) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Waschmittel mit niedrigem Phosphatgehalt zum Waschen von Geweben |
EP0000235A1 (de) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Waschmittel mit niedrigem Phosphatgehalt zum Waschen von Geweben |
EP0000595A1 (de) * | 1977-06-29 | 1979-02-07 | THE PROCTER & GAMBLE COMPANY | Waschmittel mit niedrigem Phosphatgehalt zum Waschen von Geweben |
-
1980
- 1980-06-09 EP EP80200524A patent/EP0021491A1/de not_active Withdrawn
- 1980-06-16 CA CA354,079A patent/CA1131092A/en not_active Expired
- 1980-06-18 JP JP8270380A patent/JPS5638396A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0000234A1 (de) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Waschmittel mit niedrigem Phosphatgehalt zum Waschen von Geweben |
EP0000235A1 (de) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Waschmittel mit niedrigem Phosphatgehalt zum Waschen von Geweben |
EP0000595A1 (de) * | 1977-06-29 | 1979-02-07 | THE PROCTER & GAMBLE COMPANY | Waschmittel mit niedrigem Phosphatgehalt zum Waschen von Geweben |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2125814A (en) * | 1982-07-05 | 1984-03-14 | Lion Corp | Additive composition for granular detergent |
US4725455A (en) * | 1984-06-01 | 1988-02-16 | Colgate-Palmolive Company | Process for manufacturing particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and polyphosphate builders |
CH673192GA3 (de) * | 1984-06-01 | 1990-02-28 | ||
FR2565243A1 (fr) * | 1984-06-01 | 1985-12-06 | Colgate Palmolive Co | Composition detergente organique synthetique non ionique en particules, renforcee par des adjuvants de detergence et ses procedes de fabrication |
FR2565244A1 (fr) * | 1984-06-01 | 1985-12-06 | Colgate Palmolive Co | Composition detergente assouplissant les tissus, renforcee par un adjuvant de detergence et procede de lavage |
US4720399A (en) * | 1984-06-01 | 1988-01-19 | Colgate-Palmolive Company | Process for manufacture of particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders |
FR2565246A1 (fr) * | 1984-06-01 | 1985-12-06 | Colgate Palmolive Co | Composition detergente organique synthetique antistatique, son procede de fabrication et procede de lavage |
US4853259A (en) * | 1984-06-01 | 1989-08-01 | Colgate-Palmolive Company | Process for manufacturing particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders |
FR2586425A1 (fr) * | 1985-08-20 | 1987-02-27 | Colgate Palmolive Co | Compositions detergentes liquides contenant des agents stabilisants en suspension et un additif du type uree et procedes pour nettoyer des tissus les utilisant |
US5374370A (en) * | 1988-11-03 | 1994-12-20 | Unilever Patent Holdings B.V. | Type B aluminosilicates with low Si:Al ratio for detergent use |
EP0384070A2 (de) * | 1988-11-03 | 1990-08-29 | Unilever Plc | Zeolith P, sein Herstellungsverfahren und seine Verwendung in Waschmitteln |
EP0384070A3 (de) * | 1988-11-03 | 1991-01-16 | Unilever Plc | Zeolith P, sein Herstellungsverfahren und seine Verwendung in Waschmitteln |
US5512266A (en) * | 1988-11-03 | 1996-04-30 | Unilever Patent Holdings Bv | Aluminosilicates and detergent composition |
EP0385562A2 (de) * | 1989-01-03 | 1990-09-05 | Amway Corporation | Waschmittel für Wäsche |
EP0385562A3 (de) * | 1989-01-03 | 1991-08-28 | Amway Corporation | Waschmittel für Wäsche |
EP0502675A3 (en) * | 1991-03-05 | 1993-01-07 | Unilever Plc | Detergent compositions |
EP0502675A2 (de) * | 1991-03-05 | 1992-09-09 | Unilever Plc | Detergenszusammensetzungen |
WO1994007978A1 (de) * | 1992-09-28 | 1994-04-14 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung pulverförmiger oder granularer detergensgemische |
WO1995027030A1 (en) * | 1994-03-31 | 1995-10-12 | The Procter & Gamble Company | Detergency composition comprising zeolite map and protease enzyme |
WO1996026257A1 (en) * | 1995-02-23 | 1996-08-29 | Unilever Plc | Cleaning composition comprising saturated dialkyl cationic surfactants |
US6235704B1 (en) | 1997-07-30 | 2001-05-22 | Basf Aktiengesellschaft | Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives |
US6998380B2 (en) | 2002-04-16 | 2006-02-14 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Fabric treatment composition |
WO2003087285A1 (en) * | 2002-04-16 | 2003-10-23 | Unilever Plc | Fabric treatment composition |
WO2010070088A1 (de) | 2008-12-18 | 2010-06-24 | Basf Se | Tensidgemisch enthaltend verzweigte kurzkettige sowie verzweigte langkettige komponenten |
WO2011003904A1 (de) | 2009-07-10 | 2011-01-13 | Basf Se | Tensidgemisch mit kurz- und langkettigen komponenten |
WO2011080540A1 (en) * | 2009-12-30 | 2011-07-07 | Ecolab Inc. | Phosphate substitutes for membrane-compatible cleaning and/or detergent compositions |
WO2011117350A1 (de) | 2010-03-25 | 2011-09-29 | Basf Se | Elektrochemisches textilwaschverfahren |
US9435073B2 (en) | 2010-03-25 | 2016-09-06 | Basf Se | Electrochemical textile-washing process |
US11441105B2 (en) | 2017-12-15 | 2022-09-13 | Rhodia Operations | Composition containing lanthanide metal complex |
Also Published As
Publication number | Publication date |
---|---|
CA1131092A (en) | 1982-09-07 |
JPS5638396A (en) | 1981-04-13 |
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