EP0087914B1 - Composition détergente - Google Patents

Composition détergente Download PDF

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Publication number
EP0087914B1
EP0087914B1 EP19830300931 EP83300931A EP0087914B1 EP 0087914 B1 EP0087914 B1 EP 0087914B1 EP 19830300931 EP19830300931 EP 19830300931 EP 83300931 A EP83300931 A EP 83300931A EP 0087914 B1 EP0087914 B1 EP 0087914B1
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EP
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Prior art keywords
carbon atoms
alkyl
surfactant
composition
composition according
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German (de)
English (en)
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EP0087914A1 (fr
Inventor
Charles F. Bleil
John B. Welch, Iii
Lawrence A. Gilbert
Benny S. Yam
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D1/60—Sulfonium or phosphonium compounds
    • 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
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • 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
    • 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
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • 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
    • 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
    • C11D1/75—Amino oxides

Definitions

  • This invention relates to detergent compositions containing specific alkyl sulfate, specific sulfonate and cationic detergent surfactans for use in washing textiles.
  • the compositions can be in any form, such as granules, liquids, tablets or pastes.
  • the detergent compositions within the invention contain a detergency builder and/or a nonionic surfactant and/or a fatty acid soap and/or enzymes.
  • Cationic surfactants have been incorporated in detergent compositions for purposes other than cleaning; for example, for a germicidal or sanitization benefit, a fabric softening benefit or a static control benefit. More recently it has been disclosed that cationic surfactants in combination with anionic and/or nonionic surfactants are effective for cleaning purposes.
  • Patent 4,235,759 discloses liquid detergent compositions that are superior in detergency containing an alkyl polyoxyalkylene ether sulfate anionic surfactant and a mono- long chain alkyl quaternary ammonium cationic surfactant wherein the molar ratio of anionic surfactant:cationic surfactant is from 8:1 to 1:1.
  • U.S. Patent 4,321,165, Smith et al discloses solid detergent compositions containing from 2% to 60% of a surfactant system consisting of a water-soluble anionic surfactant, an alkoxylated alcohol nonionic surfactant and a water-soluble quaternary ammonium cationic surfactant wherein the ratio of anionic surfactant:cationic surfactant is from 5:1 to 1:3 and the ratio of nonionic surfactant:cationic surfactant is from 100:1 to 2:3. It is disclosed that such compositions have improved greasy soil removal capabilities.
  • European Patent Application 0,026,529, Spadini et al discloses detergent compositions containing from 3% to 40% of an anionic surfactant, from 0.5% to 15% of a mono-long chain alkyl quaternary ammonium compound or an aliphatic amine and from 1.5% to 45% of an impalpable smectite-type clay wherein the molar ratio of the nitrogenous compound:anionic surfactant is less than 1. It is stated that such compositions clean well and also act as textile softeners.
  • U.S. Patent 4,333,862, Smith et al discloses liquid detergent compositions containing from about 10% to about 82% of an anionic surfactant, from about 10% to about 82% of an alkoxylated alcohol nonionic surfactant and from about 4% to about 35% of a water-soluble quaternary salt cationic surfactant. It is disclosed that such combinations exhibit improved cleaning performance on greasy and oily soils.
  • Another object of the present invention is to provide detergent compositions that provide such benefits over a wide range of washing temperatures.
  • the present invention comprises a detergent composition containing, by weight:
  • This invention comprises detergent compositions containing an essential three component detergent surfactant system consisting of specific alkyl sulfate, specific sulfonate and cationic detergent surfactants.
  • This specific three component surfactant system is an extremely effective detergent. It is particularly effective on organic soils, for example, lipid, greasy and oily soils. Also, the use of such system results in an unusually low level of soil redeposition. Soil redeposition results when soil that is removed from the textiles into the wash liquor during the wash process is redeposited onto the textiles.
  • the detergent compositions within the invention provide the desired superior performance over a broad range of wash water conditions.
  • the wash water temperature can range from 5°C to 95°C.
  • the initial pH of the wash liquor i.e., the detergent composition and wash water mixture, should be greater than 8 and most preferably should be from 9 to 11.
  • the detergent compositions within the invention can be in any form, such as granules, liquids, tablets or pastes, but the granular compositions are preferred.
  • the granules can range in density from .15 grams/cubic centimeter to .8 grams/cubic centimeter.
  • the detergent compositions within the invention provide the desired superior performance on organic soils because the alkyl sulfate detergent surfactant and the sulfonate surfactant each form an electro-neutral complex with the cationic surfactant.
  • the mechanism of organic soil removal is believed to be based upon the surfactant adsorbing to the soil surface to reduce the soil/water interfacial tension to such an extent that the mechanical action of the washing process removes soil from the textile surface. Since the complexes formed are electrically neutral and, therefore, do not repel each other, they can pack densely when they adsorb onto the soil surface. This results in a much lower soil/water interfacial tension and thereby extremely effective soil removal.
  • both the alkyl sulfate detergent surfactant and the sulfonate detergent surfactant must be present.
  • experimental evidence indicates that it is essential that the molar ratio of cationic surfactant to sulfonate detergent surfactant be less than 1.5. Otherwise, the desired superior performance is not obtained.
  • the cationic surfactant is an essential component of the compositions within the invention. Without the cationic surfactant, the electro-neutral complex cannot be formed with the alkyl sulfate detergent surfactant and/or the sulfonate detergent surfactant and, therefore, the desired superior performance is not obtained.
  • Cationic surfactants within the invention can be saturated or unsaturated.
  • the cationic surfactants within the invention are selected from
  • Preferred cationic surfactants are:
  • nitrogenous surfactants which are described in (i) when Q is N, (ii), (iii) and (iv) are the preferred cationic surfactants.
  • (i), (ii), (iii), and (iv) refer to the compounds in the Summary of the Invention.
  • alkyl quaternary ammonium surfactants which are described in (i), and, in particular, the mono- long chain alkyl and alkoxy quaternary ammonium surfactants, which are described in (i) when R 5 is selected from the same groups as R 4.
  • the most preferred cationic surfactants are the chloride, bromide and methylsulfate salts of C 8-12 alkyltrimethyl ammonium surfactants, C 8-12 alkylhydroxyethyldimethyl ammonium surfactants, C 8-12 alkylmethyldihydroxyethyl ammonium surfactants, C 10 - 14 alkoxytrimethyl ammonium surfactants, C 10 - 14 alkoxydihydroxyethylmethyl ammonium surfactants and C 10-14 alkoxyhydroxyethyldimethyl ammonium surfactants.
  • the salts of the cationic surfactants can be prepared by precomplexing the cationic surfactant directly with an anionic detergent surfactant within the invention rather than having such complex be formed in the wash liquor.
  • the preferred cationic surfactants are:
  • Such cationic surfactants are preferred under cold water washing conditions because when they are utilized in combination with the alkyl sulfate detergent surfactant and the sulfonate detergent surfactant the electro-neutral complex formed does not crystallize or become highly viscous. It has been observed that the electro-neutral complex formed under cold water washing conditions with a cationic surfactant such as C 12 alkyl trimethyl ammonium chloride results in such complex being crystalline or highly viscous and, thereby, is rendered less effective.
  • nitrogenous surfactants which are described in (i) and (ii) when Q is N, (iii), (iv) and (v) are the preferred cationic surfactants for use under cold water washing conditions.
  • alkyl quaternary ammonium surfactants which are described in (i) and (ii).
  • the most preferred cationic surfactants are the chloride, bromide and methylsulfate salts of the alkyl quaternary ammonium surfactants which are described in (i) when each R is an alkyl group containing from 4 to 10 carbon atoms wherein the sum of the carbon atoms of [R 2 (OR 3 ) m ] 2 is from 10 carbon atoms and to 14 carbon atoms and preferably from 10 to 12 carbon atoms; each m and y are 1 or 0, preferably 0; and each R 4 is selected from methyl and hydroxyethyl.
  • each R' is selected from an alkyl group containing at least one carbon atom and ring structures formed by joining each R 7 containing five or six carbon atoms wherein the sum of the carbon atoms of [(R I O) m R'1 2 is from 10 to 16 carbon atoms and preferably from 10 to 14 carbon atoms; each m and y are 1 or 0, preferably 0; and each R 4 is selected from methyl and hydroxyethyl.
  • cationic surfactants derived from aliphatic amines have a pKa at least 1/2 unit above the initial pH of the wash liquor. Otherwise, the desired superior performance is not achieved. It is believed that such a pKa and pH limitation ensures that a substantial portion of such amines are protonated and, thus, exist in cationic form and, therefore, are able to complex with the alkyl sulfate detergent surfactant and sulfonate detergent surfactant.
  • the level of cationic surfactant within the invention is related to the level of sulfonate detergent surfactant.
  • the molar ratio of cationic surfactant:sulfonate detergent surfactant is at most 1.5 and preferably less than 1. It is desirable to have some molar excess sulfonate detergent surfactant present because it is effective at stripping fabric softeners that have been deposited on the textile surface in previous wash cycles.
  • the weight of the equimolar complex capable of being formed between the cationic surfactant and sulfonate detergent surfactant is preferably at least 2%, more preferably above 5% and most preferably above 10% of the total level of anionic detergent surfactant present. Such excess of anionic detergent surfactant is preferred to ensure proteinaceous and particulate soil removal and the suspension in the wash liquor of the soil removed from the textiles.
  • the level of cationic surfactant within the invention is from 1/4% to 12%, preferably from 1/2% to 8% and most preferably from 1/2% to 6%.
  • the alkyl sulfate detergent surfactant is an essential component of the detergent compositions within the invention. Detergent compositions without the alkyl sulfate detergent surfactant do not provide the desired superior performance. Such compositions provide poor particulate soil removal and increased soil redeposition. It is believed that the alkyl sulfate detergent surfactant, in addition to forming the electro-neutral complex with the cationic surfactant, is particularly efficacious for such purposes. Furthermore, only specific alkyl sulfate detergent surfactants provide the desired superior performance. Performance is quite poor with an alkyl sulfate detergent surfactant in which the alkyl chain contains more than 15 carbon atoms in a linear portion of the chain extending from the head group and/or more than four ethoxy groups.
  • the alkyl sulfate detergent surfactants of the present invention are of the general formula: wherein R is an alkyl chain having from 8 to 18 carbon atoms, saturated or unsaturated, wherein the longest linear portion of the alkyl chain extending from the head group is 15 carbon atoms or less on the average, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation and x is from 0 to about 4.
  • the preferred substituted ammonium cations are the mono- and diethanol ammonium cations.
  • the alkyl sulfate detergent surfactants are not ethoxylated.
  • the preferred alkyl sulfate detergent surfactants are the sodium and potassium salts of C 12 - 15 primary and C 12 - 18 secondary alkyl sulfates.
  • the most preferred alkyl sulfate detergent surfactants are the sodium and potassium salts of C 12-15 linear and methyl branched alkyl sulfates.
  • the preferred alkyl sulfate detergent surfactants are the secondary and shorter alkyl chain alkyl sulfate detergent surfactants within the invention.
  • the level of alkyl sulfate detergent surfactant within the present invention is from 2% to 50%, preferably from 3% to 30% and most preferably from 5% to 20%.
  • a sulfonate detergent surfactant is an essential component of the compositions within the invention. Compositions without the sulfonate detergent surfactants within the invention do not give the desired superior performance.
  • sulfonate detergent surfactants can be used in the compositions of the ihvention. However, it is believed that the alkyl chain portion of such surfactants should be saturated. For example, a-olefin sulfonates, which have an unsaturated carbon bond, do not provide the desired superior performance.
  • Suitable sulfonate detergent surfactants are C 9 _, 5 alkyl benzene sulfonates, C S - 24 paraffin sulfonates, C 8-18 alkyl glyceryl ether sulfonates, esters of a-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group and C 1 - s alkyl or aryl sulfonates containing an ether, ester or amide linkage to a C 7 - 15 alkyl chain.
  • the preferred sulfonate detergent surfactants are the secondary alkyl benzene sulfonates having from 9 to 15, preferably from 11 to 13 carbon atoms in the alkyl chain.
  • Suitable paraffin sulfonates contain from 8 to 24 carbon atoms and preferably from 12 to 18 carbon atoms.
  • the alkyl glyceryl ether sulfonates are those ethers of C 8-18 alcohols, e.g., those derived from tallow and coconut oil.
  • Suitable esters of a-sulfonated fatty acids contain from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group.
  • Suitable alkyl sulfonates with an ether, ester or amide linkage have the general formula: wherein R' is an alkyl chain having 7 to 15 carbon atoms, R 8 is an alkyl chain having from 1 to 6 carbon atoms or a benzyl group and A is selected from
  • the shorter alkyl chain sulfonate detergent surfactants are preferred.
  • the level of sulfonate detergent surfactant within the invention is such that the molar ratio of cationic surfactant:sulfonate detergent surfactant is less than 1.5 and preferably less than 1.
  • the weight of the equimolar complex capable of being formed between the cationic surfactant and sulfonate detergent surfactant is preferably at least above 2%, more preferably above 5% and most preferably above 10% of the total anionic surfactant present.
  • the level of sulfonate detergent surfactant of the detergent compositions within the present invention is from .5% to 50%, preferably from 2% to 30% and most preferably from 3% to 20%.
  • the detergent compositions within the invention contain a detergency builder.
  • the level of detergency builder of the detergent compositions is from 0% to 70%, preferably from 10% to 60% and most preferably from 20% to 50% of a detergency builder.
  • the preferred detergency builders are the water-soluble sequestrants such as tripolyphosphates, hexametaphosphates and higher polymerization species, citrates, nitrilotriacetates and water-soluble polyacetals as disclosed in U.S. Patents 4,144,266 and 4,246,495, and mixtures thereof.
  • the most preferred detergency builders are tripolyphosphates, nitrilotriacetates and water-soluble polyacetals and mixtures thereof.
  • Water-soluble inorganic or organic electrolytes are suitable builders.
  • the electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequestering agents.
  • the builder can also be water-insoluble calcium ion exchange materials; however, nonlimiting examples of suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates, silicates, sulfates and chlorides. Specific examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates, carbonates, percarbonates, orthophosphates, pyrophosphates and sulfates.
  • suitable organic alkaline detergency builders include: (1) water-soluble aminocarboxylates and aminopolyacetates, for example, sodium and potassium glycinates, ethylenedi- aminetetraacetates and N - (2 - hydroxyethyl))nitrilodiacetates and diethylenetriaminepentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; (3) water-soluble polyphosphonates, including sodium, potassium, and lithium salts of ethane-1-hydroxy-1, 1-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid,
  • a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent 814,874, issued November 12, 1974.
  • detergent compositions containing sodium aluminosilicates having the formula: wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5: 1, and X is an integer from 15 to 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least 23.7 ppm/minute/gram.
  • a preferred material is:
  • the nonionic surfactant is nonionic surfactant
  • compositions of the invention can contain a nonionic surfactant.
  • nonionic surfactants for use herein comprise those typical nonionic surfactants well known in the detergency arts.
  • the preferred nonionic surfactants are fatty acid amide surfactants, amine oxide surfactants and ethoxylated alcohols.
  • Suitable fatty acid amide surfactants are ammonia amides, monoethanol amides, diethanol amides and ethoxylated amides.
  • Particularly preferred amides are those where the alkyl group contains from 10 to 16 carbon atoms, such as coconut alkyl monoethanol or diethanol amide.
  • the amine oxide surfactants of the present invention comprise compounds and mixtures of compounds having the formula wherein R 1 is an alkyl, hydroxyalkyl, alkoxyhydroxypropyl radical, alkoxyhydroxyethyl, alkyl amido or alkyl carboxylate in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R 2 and R 3 are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, or together are a heterocyclic, e.g., morpholino structure in which the nitrogen is part of the heterocyclic ring and n is from 0 to 10.
  • R 1 is an alkyl, hydroxyalkyl, alkoxyhydroxypropyl radical, alkoxyhydroxyethyl, alkyl amido or alkyl carboxylate in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms
  • R 2 and R 3 are methyl
  • amine oxide surfactants include: dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethyl- stearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis - (2 - hydroxyethyl)dodecylamine oxide, bis(2 - hydroxyethyl) - 3 - dodecoxy - 2 - hydroxypropylamine oxide, (2 - hydroxypropyl)methyltetradecylamine oxide, di- methyloleylamine oxide, dimethyl - (2 - hydroxydodecyl)amine oxide, C a - 20 alkyl(alpha - dimethylamine oxide) carboxylate, and the corresponding decyl,
  • the ethoxylated alcohols for use herein have the formula wherein R is an alkyl, hydroxy alkyl, alkylene, hydroxy alkylene acyl, or hydroxy acyl group containing from 8 to 22 carbon atoms or an alkylbenzene group wherein the alkyl group contains from 6 to 15 carbon atoms or mixtures thereof;
  • X is a number from 2 to 30; and
  • R 1 is selected from H, alkyl groups containing from 2 to 4 carbon atoms, acyl groups containing from 2 to 4 carbon atoms and mixtures thereof.
  • the HLB of these nonionic surfactants is preferably from 5 to 20, most preferably from 8 to 14.
  • nonionic surfactants are: (1) the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol, and (2) the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the level of nonionic surfactant that can be present is from 0% to 50%, preferably from .5% to 10% and most preferably from 1% to 5%.
  • compositions of this invention can contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936,537, Baskerville et al.
  • Such components include color speckles, bleaching agents, bleach activators, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
  • water soluble salts of fatty acids can be added as part of the surfactant system. Surprisingly, they are most effective under cold water wash conditions. Suitable water soluble salts of fatty acids have from 8 to 18 carbon atoms. The preferred water soluble salts of fatty acids are the sodium, potassium and magnesium salts of C 12 - 14 fatty acids. They can be present at levels up to 10%.
  • Enzymes are believed to be particularly effective in the detergent compositions of this invention.
  • the enzyme-containing detergent compositions are particularly effective on enzyme sensitive stains such as grass and blood while maintaining greasy and oily soil detergency.
  • Suitable enzymes are those, for example, disclosed in U.S. Patent 4,176,079, Guerry et al (November 27,1979).
  • the enzymes are included at a level of from .02% to 3%, preferably from .1% to 1%.
  • Nonlimiting examples of bleaching agents are sodium perborate (as the monohydrate or tetrahydrate), sodium percarbonate and other perhydrates, at levels from 5% to 35% by weight of the composition, and activators therefor, such as tetraacetylethylenediamine, tetraacetylglycouril and others known in the art, and stabilizers therefor, such as magnesium silicate, and ethylenediaminetetraacetate.
  • Peroxy carboxylic acids for example, such as those disclosed in U.S. Patent 4,091,544, Hutchins (May 30, 1975), are especially useful.
  • Preferred optional ingredients include suds modifiers particularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures.
  • silicone suds controlling agents 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 siloxane having the formula: wherein x is from 20 to 2,000 and R and R 1 are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
  • the polydimethylsiloxanes (R and R 1 are methyl) having a molecular weight within the range of from 200 to 2,000,000, and higher, are all useful as suds controlling agents.
  • Additional suitable silicone materials wherein the side chain groups R and R 1 are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpoly-siloxanes 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 trimethylsilanated) silica having a particle size in the range from 10 to 20 nm and a specific surface area above 50 m 2 /gm intimately admixed with dimethyl silicone fluid having a molecular weight in the range from 500 to 200,000 at a weight ratio of silicone to silanated silica of from 19:1 to 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 4,073,118, Gault et al, issued February 21, 1978.
  • DB-544 commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • Suds modifiers as described above are used at levels of up to approximately 2%, preferably from 0.1 to 1>% by weight of the surfactant.
  • 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 preferred suds control components for use in the subject compositions, and are described in detail in U.S. Patent 4,056,481, Tate, issued November 1, 1977.
  • microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
  • Preferred microcrystalline waxes have a melting point from 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 25°C by ASTM-D1321.
  • Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petroleum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax.
  • Alkyl phosphate esters represent an additional preferred suds control agent for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphate, which can contain di- and trioleyl phosphate.
  • 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 50 mole percent of dialkyl phosphate and up to 5 mole percent of trialkyl phosphate.
  • a laundry load consisting of one set of the swatches along with six clean terry cloth towels and one terry cloth towel soiled with a mixture of particulate soil and oily soil was placed in a mini-wash system.
  • the load was then washed with a quantity of Composition A that corresponds to detergent concentrations utilized in conventional automatic wash processes.
  • the mini-wash system with such a load simulates a conventional automatic washing process.
  • the wash water had a temperature of 35°C and contained 59 ppm water hardness.
  • This wash process was repeated two more times, once with the second set of swatches and Composition B and once with the third set of swatches and Composition C.
  • Each of the four swatch types was then comparison graded against its identical counterpart that had been washed with a different detergent composition to determine relative soil removal.
  • a grading scale of -4 to 4 was used, with -4 indicating much less soil removal, 0 indicating no difference and 4 indicating much more soil removal.
  • Compositions A and C provided significantly more soil removal than Composition B, which did not contain the essential cationic surfactant.
  • compositions A, B and C provided significantly more soil removal than Composition D which did not contain a sulfonate detergent surfactant within the invention.
  • Composition F provided significantly more soil removal than Composition E. Thus, it appears that sodium C 16 alkyl-4-sulfate cannot "substitute" for a sulfonate detergent surfactant within the invention.
  • AHWUF Hunter Whiteness Units Filtered
  • composition B had somewhat more soil redeposition than Composition A. This is due to the decreased level of alkyl sulfate detergent surfactant of Composition B.
  • Composition A provided significantly more soil removal than Compositions B and C. It is believed that this is because Compositions B and C did not contain an alkyl sulfate detergent surfactant. Therefore, the alkyl sulfate detergent surfactant is also essential for soil removal.
  • Soil removal capability of Composition A was compared to that of Composition B by determining the Cleaning Index by the same procedure as described in Example I. Such comparison was also made between Compositions C and D. The results were as follows:
  • Composition A provided significantly more soil removal than Composition B and Composition C provided significantly more soil removal than Composition D. This result is due to that the length of the longest portion of the alkyl sulfate detergent surfactant of Compositions B and D is too long.
  • Composition C provided significantly more soil removal than Compositions A and B. It is believed that this is because Compositions A and B did not contain a sufficient level of C 13 LAS in order to form a sufficient level of cationic surfactant-alkyl sulfonate detergent surfactant complex.
  • Composition A which contains an optional nonionic surfactant, provided only marginally significantly more soil removal than Composition B.
  • Composition B which contains an amine surfactant, did not remove significantly less soil than Composition A, which contains an alkylammonium surfactant.
  • composition within the invention that contains a water soluble salt of a fatty acid:
  • This composition provides the desired superior performance on conventional soils in addition to being extremely effective on enzyme-sensitive stains.
  • composition within the invention that contains a water soluble salt of a fatty acid:

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Claims (17)

1. Une composition détergente comprenant, en poids:
a) 2% à 50% d'un agent de surface détergent hydrosoluble à base d'un alkylsulfate aliphatique répondant à la formule:
Figure imgb0095
dans laquelle R est une chaîne alkyle avec 8 à 18 atomes de carbone où la portion alkyle linéaire la plus longue de la chaîne à partir du groupe de tête ne comporte pas plus de 15 atomes de carbone en moyenne; M est un cation compatible et x est de 0 à 4;
b) 1/4% à 12% d'un agent de surface cationique choisi parmi:
i) des composés répondant à la formule générale
Figure imgb0096
dans laquelle Q est N, P ou S; z est 1 si Q est S et 2 si Q est N ou P; R2 est choisi parmi des groupes alkyle et alkylbenzyle ayant 4 à 16 atomes de carbone, à l'exclusion du groupe benzyle; chaque R3 est choisi parmi -CH2CH2-, -CH2-CH(CH3)-, ―CH2CH(CH2CH)―, -CH2CH2CH2- et leurs mélanges; chaque R4 est choisi parmi H lorsque y n'est pas 0, des groupes alkyle en Ci à C4, hydroxyalkyle en C1 à C4, benzyle, des structures cycliques formées par la réunion des deux groupes R4 et
Figure imgb0097
où chaque R6 est H ou un hexose dans lequel au moins un R6 est H; R5 est choisi parmi [R2(OR3)n], [R4(OR3)y] et des structures cycliques formées par la réunion de l'un quelconque des atomes carbone de R2 et de R5 où le nombre total des atomes de carbone de R2 plus R5 n'est pas supérieur à 18, le noyau benzénique étant traité comme l'équivalent de 2 atomes de carbone et dans laquelle, si R4 possède moins de 4 atomes de carbone, R2 renferme alors 8 à 16 atomes de carbone, à l'exclusion du groupe benzyle; chaque y est de 0 à 3, m est de 0 à 3 et X est un anion compatible;
ii) des composés répondant à la formule générale
Figure imgb0098
Figure imgb0099
dans laquelle Q, R3, R", y, m et X sont tels que définis précédemment; n est 2 si R est S et 3 si Q est N ou P; chaque R' est choisi parmi un groupe alkyle ou alkylbenzyle contenant au moins 1 atome de carbone, à l'exclusion du groupe benzyle et lesdits groupes R7 peuvent être réunis pour donner naissance à des structures penta- ou hexagonales et dans laquelle la somme des atomes de carbone de [(R3O)mR7]2 s'étend de 9 atomes de carbone à 16 atomes de carbone lorsque m est 0 et de 10 atomes de carbone à 18 atomes de carbone lorsque m est de 1 à 3, le noyau benzénique étant traité comme l'équivalent de 2 atomes de carbone et a est de 0 à 3;
iii) des amines aliphatiques répondant à la formule générale:
Figure imgb0100
dans laquelle R2, R3, R4, R5, m et y sont tels que définis précédemment et le pKa de l'amine est supérieur d'au moins 1/2 unité au pH initial d'une solution de lavage contenant une solution aqueuse de la composition, ledit pH initial se situant dans la gamme de 8 à 11;
iv) des composés répondant à la formule générale
Figure imgb0101
dans laquelle R2, R3, R4, R5, m, y et X sont tels que définis précédemment;
v) des composés répondant à la formule générale
Figure imgb0102
dans laquelle R2, R3, R4, R5, m et y sont tels que définis précédemment et le pKa du composé est supérieur d'au moins 1/2 unité au pH initial d'une solution de lavage contenant une solution aqueuse de la composition, ledit pH initial se situant dans la gamme de 8 à 11; et leurs mélanges;
c) 1/2% à 50% d'un agent de surface détergent à base d'un sulfonate choisi parmi les sels hydrosolubles d'acides alkyl C9 à C15 benzène sulfoniques, d'acides paraffine C8 à C24 sulfoniques, d'acides alkyl CB à C24 glycéryl éther sulfoniques, d'esters d'acides gras alpha sulfonés contenant 6 à 20 atomes de carbone dans le groupe acide gras et 1 à 10 atomes de carbone dans le groupe ester et d'acides alkyl C1 à C6 ou arylsulfoniques contenant une liaison éther, ester ou amide en une chaîne alkyle en C7 à C15;
d) 0% à 50% d'un agent de surface non ionique et
e) 0% à 70% d'un adjuvant de détergence, le rapport molaire de (b):(c) étant inférieur à 1,5.
2. Composition détergent selon la revendication 1, dans laquelle l'agent de surface cationique (b) est choisi parmi:
i) des composés répondant à la formule générale
Figure imgb0103
dans laquelle Q est N, P ou S; z est 1 si Q est S et 2 si Q est N ou P; R2 est un groupe alkyle ou alkylbenzyle ayant 8 à 16 atomes de carbone dans la chaîne alkyle; chaque R3 est ―CH2CH2CH2―; chaque R4 est choisi parmi H lorsque y n'est pas 0, des groupes alkyle en C1 à C4, hydroxyalkyle en C1 à C4, benzyle, des structures cycliques formées par la réunion des deux groupes R4 et
Figure imgb0104
où R6 est H ou un hexose; R5 est identique à R4 ou est une chaîne alkyle dans laquelle le nombre total des atomes de carbone de R2 plus R5 n'est pas supérieur à 18; chaque y est de 0 à 3, m est de 0 à 3 et X est un anion compatible; et
ii) des amines aliphatiques répondant à la formule:
Figure imgb0105
dans laquelle R2, R3, R4, R5, m et y sont tels que définis précédemment et le pKa est supérieur d'au moins 1/2 unité au pH initial de la solution de lavage contenant une solution aqueuse de la composition, ledit pH initial se situant dans la gamme de 8 à 11;
iii) des composés répondant à la formule générale:
Figure imgb0106
dans laquelle R2, R3, R4, R5, m, y et X sont tels que définis précédemment;
iv) des composés répondant à la formule générale:
Figure imgb0107
dans laquelle R2, R3, R4, R5, m et y sont tels que définis précédemment et le pKa est supérieur d'au moins une 1/2 unité au pH initial de la solution de lavage contenant une solution aqueuse de la composition, ledit pH initial se situant dans la gamme de 8 à 11; et leurs mélanges.
3. Composition selon l'une ou l'autre des revendications 1 et 2, dans laquelle l'agent de surface détergent à base d'alkylsulfate représente 3% à 30%, de préférence 5% à 20%, l'agent de surface cationique représente 1/2% à 8%, de préférence 1/2% à 6% et l'agent de surface détergent à base de sulfonate représente 2% à 30%, de préférence 3% à 20%.
4. Composition selon l'une quelconque des revendications 1 à 3, dans laquelle l'agent de surface détergent à base d'alkylsulfate est choisi parmi des prim. alkyl C12―C15 et sec. alkyl C12―C18 sulfates de métaux alcalins, d'ammonium et d'ammonium substituté.
5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle l'agent de surface cationique est choisi parmi
Figure imgb0108
et
Figure imgb0109
6. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle l'agent de surface cationique répond à la formule:
Figure imgb0110
7. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle l'agent de surface cationique est choisi parmi les chlorures, bromures, méthylsulfates d'alkyl C8―C12 triméthylammonium en tant qu'agents de surface, d'alkyl Ca-C12 hydroxyéthyldiméthylammonium en tant qu'agents de surface, d'alkyl C8―C12 méthyldihydroxyéthylammonium en tant qu'agents de surface, d'alcoxy C1o-C14 di- hydroxyéthylméthylammonium en tant qu'agents de surface et d'alcoxy C1o-C14 hydroxyéthyldiméthylammonium en tant qu'agents de surface.
8. Composition selon l'une quelconque des revendications 1 à 7, dans laquelle l'agent de surface détergent à base de sulfonate est un sec. alkyl benzènesulfonate ayant 9 à 15, de préférence 11 à 13 atomes de carbone dans la chaîne alkyle.
9. Composition selon l'une quelconque des revendications 1 à 8, dans laquelle le rapport molaire de (b):(c) est inférieur à 1:1.
10. Composition selon l'une quelconque des revendications 1 à 9, dans laquelle le poids du complexe équimolaire capable de se former entre l'agent de surface cationique et l'agent de surface détergent à base de sulfonate est d'au moins 2%, de préférence d'au moins 5% de la teneur totale en agent de surface anionique.
11. Composition selon l'une quelconque des revendications 1 à 10, dans laquelle l'adjuvant de détergence représente 10% à 60%, de préférence 20% à 50% en poids de la composition.
12. Composition selon la revendication 11, dans laquelle l'adjuvant de détergence est choisi parmi des tripolyphosphates, des hexamétaphosphates et des espèces polymérisées supérieures, des citrates, des nitrilotriacétates, des polyacétals hydrosolubles et leurs mélanges.
13. Composition selon l'une quelconque des revendications 1 à 12, dans laquelle l'agent de surface non ionique représente 0,5% à 10%, de préférence 1% à 5% en poids de la composition.
14. Composition selon la revendication 13, dans laquelle l'agent de surface non ionique est choisi parmi des agents de surface détergents à base d'amide d'acide gras, d'oxyde d'amine et d'alcool éthoxylé.
15. Composition selon l'une quelconque des revendications 1 à 14, dans laquelle les enzymes sont présentes à une dose de 0,02% à 3% en poids de la composition.
16. Composition selon l'une quelconque des revendications 1 à 15, dans laquelle les sels d'acides gras hydrosolubles sont présents à des doses atteignant 10%.
17. Composition selon la revendication 16, dans laquelle les sels d'acides gras hydrosolubles possèdent 8 à 18 atomes de carbone, de préférence 12 à 14 atomes de carbone.
EP19830300931 1982-03-01 1983-02-23 Composition détergente Expired EP0087914B1 (fr)

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EP0121949A1 (fr) * 1983-02-15 1984-10-17 THE PROCTER & GAMBLE COMPANY Mélange de détergent anionique/cationique avec une structure irrégulière
US4507219A (en) * 1983-08-12 1985-03-26 The Proctor & Gamble Company Stable liquid detergent compositions
GB8722540D0 (en) * 1987-09-24 1987-10-28 Unilever Plc Composition for softening fabrics
US5466394A (en) * 1994-04-25 1995-11-14 The Procter & Gamble Co. Stable, aqueous laundry detergent composition having improved softening properties
ZA974222B (en) * 1996-05-17 1998-12-28 Procter & Gamble Detergent composition
MA25183A1 (fr) * 1996-05-17 2001-07-02 Arthur Jacques Kami Christiaan Compositions detergentes
ZA974226B (en) * 1996-05-17 1998-12-28 Procter & Gamble Detergent composition
GB2315765A (en) * 1996-08-01 1998-02-11 Procter & Gamble Detergent compositions for laundering clothes with low levels of sulphate and silicates
BR9714770A (pt) * 1997-05-16 2001-12-11 Procter & Gamble Composições detergentes
WO1999043775A1 (fr) * 1998-02-26 1999-09-02 Henkel Kommanditgesellschaft Auf Aktien Systeme de tensioactifs s'utilisant dans des detergents et nettoyants pulverulents a granulaires ou liquides
GB0218634D0 (en) † 2002-08-10 2002-09-18 Unilever Plc Detergent compositions
US11591546B2 (en) 2017-01-20 2023-02-28 Ecolab Usa Inc. Cleaning compositions employing extended chain anionic surfactants

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