EP0075994A2 - Mischungen von Alkylpolysaccharid, Aminoxid-Tensiden und Fettsäureseife enthaltende Detergenszusammensetzungen - Google Patents
Mischungen von Alkylpolysaccharid, Aminoxid-Tensiden und Fettsäureseife enthaltende Detergenszusammensetzungen Download PDFInfo
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- EP0075994A2 EP0075994A2 EP82201170A EP82201170A EP0075994A2 EP 0075994 A2 EP0075994 A2 EP 0075994A2 EP 82201170 A EP82201170 A EP 82201170A EP 82201170 A EP82201170 A EP 82201170A EP 0075994 A2 EP0075994 A2 EP 0075994A2
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
Definitions
- This invention relates to surfactant combinations which provide good detergency and, optionally, good fluorescer effectiveness and/or suds control and/or corrosion inhibition in a laundry context.
- Such compositions can be either built or unbuilt, granular or liquid, and can contain the usual auxiliary ingredients common to such compositions.
- Alkylpolyglycosides which are surfactants have been disclosed in U.S. Patents 3,598,865; 3;721,633; and 3,772,269. These patents also disclose processes for making alkylpolyglycoside surfactants and built liquid detergent compositions containing these surfactants.
- U.S. Patent 3,219,656 discloses alkylmonoglu- cosides and suggests their utility as foam stabilizers for other surfactants.
- Various polyglycoside surfactant structures and processes for making them are disclosed in U.S. Patents 3,640,998; 3,839,318; 3,314,936; 3,346,558; 4,011,389; 4,223,129. All of the above patents are incorporated herein by reference.
- This invention relates to the discovery of certain combinations of surfactants which provide unusually good detergency, especially in cool water, for a variety of fabric types. Specifically this invention relates to detergent compositions comprising:
- a highly preferred variation also comprises from about 0.01 to about 2.0% of an anionic fluorescer (optical brightener).
- the nonionic detergent surfactant is selected from the group consisting of amine oxide detergent surfactants, amide detergent surfactants and mixtures thereof, and the composition additionally comprises from about 1% to about 10% of an unsaturated soap containing from about 16 to about 22 carbon atoms, and, preferably, from about 0% to about 10% of a synthetic anionic detergent surfactant.
- the alkylpolysaccharides are those having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e. g., a polyglycoside, hydrophilic group containing from about 11 ⁇ 2 to about 10, preferably from about 11 ⁇ 2 to about 3, most preferably from about 1.6 to about 2.7 saccharide units.
- Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g.
- glucose, galactose and galactosyl moieties can substitute for the glucosyl moieties.
- the hydrophobic group is attached at the 2, 3, 4 etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
- the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6 positions on the preceding saccharide units.
- a polyalkoxide chain joining the hydrophobic moiety and the polysaccharide moiety.
- the preferred alkoxide is ethylene oxide.
- Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16 carbon atoms.
- the alkyl group is a straight chain saturated alkyl group.
- the alkyt group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to about 10, preferably less than 5, most preferably 0, alkoxide moieties.
- Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses, and/or galactoses.
- Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
- the preferred alkylpolyglycosides have the formula wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0 ; and x is from 11 ⁇ 2 to about 10, preferably from about 11 ⁇ 2 to about 3, most preferably from about 1.6 to about 2.7.
- the glycosyl is preferably derived from glucose.
- the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the I-position).
- the additional glycosyl units are attached between their I-position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
- the content of alkylmonoglycoside is low, preferably less than about 60%, more preferably less than about 50%-Surprisingly, anionic fluorescers which are normally relatively ineffective in the presence of conventional ethoxylated nonionic detergent surfactants at high levels in the absence of substantial levels of anionic detergent surfactants, are very effective when the alkylpolyglycoside surfactants are present.
- the ratio of alkylpolyglycoside detergent surfactant to nonionic detergent surfactant should be greater than about l:4 preferably greater than about 1:3, most preferably greater than about 1:1.
- Nonionic surfactants including those having an HLB of from about 5 to about 17, are well known in the detergency art. They are included in the compositions of the present invention together with the, e.g., alkylpolyglycoside surfactants defined hereinbe-. fore. They may be used singly or in combination with one or more of the preferred alcohol ethoxylate nonionic surfactants, described below, to form nonionic surfactant mixtures useful in combination with the alkylpolyglycosides. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. No. 3,332,880, Kessler et al, issued July 25, 1967, each of which is incorporated herein by reference. Nonlimiting examples of suitable nonionic surfactants which may be used in the present invention are as follows:
- Preferred semi-polar nonionic detergent surfactants are the amine oxide detergent surfactants having the formula wherein R 3 is an alkyl, hydroxy alkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms, R 4 is an alkylene or hydroxy alkylene group containing from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to about 3 and each R 5 is an alkyl or hydroxy alkyl group containing from I to about 3 carbon atoms or a polyethylene oxide group containing from one to about 3 ethylene oxide groups and said R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom to form a ring structure.
- Preferred amine oxide detergent surfactants are C 10-18 alkyl dimethyl amine oxide, C 8-18 alkyl dihydroxy ethyl amine oxide, and C 8-12 alkoxy ethyl dihydroxy ethyl amine oxide.
- Nonionic detergent surfactants (1)-(4) are conventional ethoxylated nonionic detergent surfactants.
- Preferred alcohol ethoxylate nonionic surfactants for use in the compositions of the present invention are biodegradable and have the formula wherein R is a primary or secondary alkyl chain 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, particularly from about 2 to about 9.
- the nonionics have an HLB (hydrophilic- lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 15. HLB is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc., 1966, pages 606-613, incorporated herein by reference.
- n is from 3 to 7.
- Primary linear alcohol ethoxylates e.g., alcohol ethoxylates produced from organic alcohols which contain about 20% 2-methyl branched isomers, commercially rupt- able from Shell Chemical Company under the tradename Neodol are preferred from a performance standpoint.
- 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 tallow alcohol with 9 moles of ethylene oxide; 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 C12 alcohol with 5 moles of ethylene oxide; the condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, and the same condensation product which is stripped so as to remove substantially all lower ethoxylate and nonethoxylated fractions; the condensation product of C 12-13 alcohol with 2.3 moles of ethylene oxide, and the same condensation product which is stripped so as to remove substantially all lower ethoxylate and nonethoxylated fractions; the condensation product of C 12-13 alcohol with 9 moles of ethylene oxide; the condensation product of C 14-15 alcohol with 2.25 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
- compositions of the present invention may contain mixtures of the preferred alcohol ethoxylate nonionic surfactants together with other types of nonionic surfactants.
- One of the preferred nonionic surfactant mixtures contains at least one of the preferred alcohol ethoxylate nonionics, and has a ratio of the preferred alcohol ethoxylate surfactant (or surfactants) to the other nonionic surfactant (or surfactants) of from about 1:1 to about 5:1.
- surfactant mixtures useful in the present invention include a mixture of the condensation product of C 14-15 alcohol with 3 moles of ethylene oxide (Neodol 45-3) and the condensation product of C 14-15 alcohol with 9 moles of ethylene oxide (Neodol 45-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1; a mixture of the condensation product of C 10 alcohol with 3 moles of ethylene oxide -together with the condensation product of a secondary C 15 alcohol with 9 moles of ethylene oxide (Tergitol 15-S-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 4:1; a mixture of Neodol 45-3 and Tergitol 15-S-9, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1; and a mixture of Neodol 45-3 with the condensation product of
- Preferred nonionic surfactant mixtures may also contain alkyl glyceryl ether compounds together with the preferred alcohol ethoxylate surfactants.
- Particularly preferred are glyceryl ethers having the formula wherein R 9 is an alkyl or alkenyl group of from about 8 to about 18, preferably about 8 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbons in the alkyl chain, and n is from 0 to about 6, together with the preferred alcohol ethoxylates, described above, in a ratio of alcohol ethoxylate 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. Pat. No. 4,098,713, Jones, issued July 4, 1978; which is incorporated herein by reference.
- the ratio of alkylpolyglycoside detergent surfactant to nonionic detergent surfactant is from about 10:1 to about I:10, preferably from about 3:1 to about 1:3.
- the detergent compositions herein also contain from 0% to about 90%, preferably from about 5% to about 50%, and more preferably from about 10% to about 35% of a detergent builder.
- a detergent builder include, by way of example, a crystalline aluminosilicate ion exchange material of the formula wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.5 and x is from about 10 to about 264.
- Amorphous hydrated aluminosilicate materials useful herein have the empirical formula wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate.
- the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
- the preferred crystalline aluminosilicate ion exchange materials are further characterized by a particle size di 2 meter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. More, preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
- particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope-
- the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaCO 3 water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg. eq./g. to about 352 mg. eq./g.
- the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
- Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
- the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange capacity of at least about 50 mg. eq. CaCO 3 /g. (12 mg. Mg ++ /g.) and a Mg ++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
- Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
- the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
- a method for producing aluminosilicate ion exchange materials is discussed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976, incorporated herein by reference.
- Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
- the crystalline aluminosilicate ion exchange material has the formula wherein x is from about 20 to about 30, especially about 27.
- detergency builders include water-soluble neutral or alkaline salts.
- water-soluble salts include the compounds commonly known as detergent builder materials.
- Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates, and polycarboxylates.
- alkali metal especially sodium, salts of the above.
- inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric meta- phate having a degree of polymerization of from about 6 to 21, and orthophosphate.
- polyphosphonate builders are the sodium and potassium salts of ethylene-1,1-diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-, 1,1,2-triphosphonic acid.
- Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
- nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
- Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates.
- polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
- Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo- hexanehexacarboxylate, cis-cyclopentanetetracarboxylate phloro- glucinol trisulfonate, water-soluble polyacrylates (having molecular weights of from about 2,000 to about 200,000 for example), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
- polyacetal carboxylates for use herein are the polyacetal carboxylates described in U.S. Pat. 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Pat. 4,246,495, issued March 27, 1979 to Crutchfield et al, both incorporated herein by reference.
- These 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.
- detergency builder materials useful herein are the "seeded builder" compositions disclosed in Belgian Patent No. 798,856, issued Oct. 29, 1973, incorporated herein by reference. Specific examples of such seeded builder mixtures are: 3:1 wt. mixtures of sodium carbonate and calcium carbonate having 5 micron particle diameter; 2.7:1 wt: mixtures of sodium sesquicarbonate and calcium carbonate having a particle diameter of 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonate and calcium hydroxide having a particle diameter of 0.01 micron; and a 3:3:1 wt. mixture of sodium carbonate, sodium aluminate and calcium oxide having a particle diameter of 5 microns.
- the detergent compositions herein can contain from about 1% to about 15%, preferably from about 2% to about 8%, of an organic surfactant selected from the group consisting of anionic, zwitterionic, ampholytic, and cationic surfactants, and mixtures thereof.
- an organic surfactant selected from the group consisting of anionic, zwitterionic, ampholytic, and cationic surfactants, and mixtures thereof.
- surfactants useful herein are listed in U.S. Pat. 3,664,961, Norris, issued May 23, 1972, and U.S. Pat. 3,919,678, Laughlin et al, issued Dec. 30, 1975, both incorporated herein by reference.
- Useful cationic surfactants also include those described in U.S. Pat. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. 4,239,659, Murphy, issued Dec. 16, 1980, both incorporated herein by reference.
- the following are representative examples of surfactants useful in
- Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- the preferred soap as discussed hereinbefore and hereinafter, especially in combination with semipolar or amide nonionic detergent surfactants, is at least partially unsaturated.
- the unsaturated fatty acid soap of this invention contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration. Preferably the number of carbon atoms in the unsaturated fatty acid soap is from about 16 to about 18.
- the unsaturated soap in common with other anionic detergent and other anionic materials in the detergent compositions of this invention, has a cation which renders the soap water-soluble and/or dispersible.
- Suitable cations include sodium, potassium, ammonium, monoethanolammonium, diethanolamonium, triethanolammonium, tetramethylammonium, etc. cations.
- Sodium ions are preferred although in liquid formulations ammonium, and triethanolammonium cations are useful.
- a level of at least about 1% of the unsaturated fatty acid soap is desirable to provide a noticeable reduction in sudsing and corrosion.
- Preferred levels of unsaturated fatty acid soap are from about 1% to about 15%, preferably from about 1% to about 10%, most preferably from about 2% to about 5%.
- the unsaturated fatty acid soap is preferably present at a level that will provide a level of from about 15 ppm to about 200 ppm, preferably from about 25 ppm to about 125 ppm in the wash solution at recommended U.S. usage levels and from about 30 ppm to about 1000 ppm, preferably from about 50 ppm to about 500 ppm for European usage levels.
- Mono-, di-, and triunsaturated fatty acids are all essentially equivalent so it is preferred to use mostly monounsaturated soaps to minimize the risk of rancidity.
- Suitable sources of unsaturated fatty acids are well known. For example, see Bailey's Industrial Oil and Fat Products, Third Edition, Swern, published by interscience Publisher (1964), incorporated herein by reference.
- the level of saturated soaps is kept as low as possible, preferably less than about 60%, preferably less than about 50% of the total soap is saturated soap.
- low levels of saturated soaps can be used. Tallow and palm oil soaps can be used.
- Useful synthetic anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- Such synthetic anionic detergent surfactants are desirable additives at a level of from about 1% to about 10% to increase the overall detergency effect and, if desired, increase the level of suds.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S.
- Preferred anionic detergent surfactants are the alkyl polyethoxylate sulfates, particularly those in which the alkyl contains from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 and wherein the polyethoxylate chain contains from about I to about 15 ethoxylate moieties preferably from about ! I to about 3 ethoxylate moieties. These anionic detergent surfactants are particularly desirable for formulating heavy-duty liquid laundry detergent compositions.
- anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about I to about 10 units of ethylene oxide per molecule and wherein the alkyl -group contains from about 10 to about 20 carbon atoms.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about I to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about I to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniurn compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
- auxiliary surfactants herein include linear alkylbenzene sulfonates containing from about II to 14 carbon atoms in the alkyl group; tallowalkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about t4 to 18 carbon atoms and wherein the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms; and alkyldimethylammonium propane sulfonates and alkyldimethyl- ammonim hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon atoms.
- Specific preferred surfactants for use herein include: sodium, potassium, mono-, di-, and triethanolammonium C 14-15 alkyl polyethoxylate 1-3 sulfates; sodium linear C 11-13 alkylbenzene sulfonate; triethanolamine C 11-13 alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with about 4 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammoniopropane-1-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)-hexanoate; and coconut alkyldimethyl amine
- adjunct components which may be included in the compositions of the present invention, in their conventional art- established 'levels for use (i.e., from 0 to about 90%), include solvents, bleaching agents, bleach activators, soil-suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents (monoethanolamine, sodium carbonate, sodium hydroxide, etc.), enzymes, enzyme-stabilizing agents, perfumes, fabric softening components, static control agents, and the like.
- Fatty acid amide detergent surfactants useful herein include those having the formula: wherein R 6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1-4 alkyl, C 1-4 hydroxy alkyl, and -(C 2 H 4 O) x H where x varies from about I to about 3.
- Preferred amides are C 8-20 ammonia amides, monoethanolammonium, diethanolamides, and isopropanol amides.
- a special advantage of the combination of detergent surfactants herein is their superior compatibility with anionic fluorescent or optical brighteners.
- Nonionic surfactants especially ethoxylated nonionic detergent surfactants, normally diminish the effectiveness of such brighteners.
- the alkylpolyglycoside surfactant With the addition of the alkylpolyglycoside surfactant, the brightener effectiveness is dramatically improved, especially on cotton. From about 0.01 to about 2%, preferably from about 0.1 to about 1% optical brightener can be used.
- Suitable brighteners include the following:
- compositions of the present invention can be manufactured and used in a variety of forms such as solids, powders, granules, pastes, and liquids.
- the compositions can be used in the current U.S. laundering processes by forming aqueous solution containing from about 0.01% to about 1%, preferably from about 0.05% to about 0.5%, and most preferably from about 0.05% to about 0.25% of the composition in water and agitating the soiled fabrics in that aqueous solution. The fabrics are then rinsed and dried. When used in this manner the preferred compositions of the present invention yield exceptionally good detergency on a variety of fabrics.
- a laundry detergent preferably, an aqueous heavy-duty liquid, contains (a) from about 1% to about 20% (preferably from about 4% to about 10%) of the alkylpolyglycoside detergent surfactant; (b) from about 1% to about 10% (preferably from about 2% to about 6%) of an amine oxide detergent surfactant (c) from 1% to about 10% (preferably from about 1% to about 6%) of a water-soluble soap of an unsaturated fatty acid containing from about 16 to about 22 carbon atoms; (d) from 0% to about 40% (preferably from about 10% to about 30%) of a water-soluble detergency builder, preferably selected from the group consisting of pyrophosphates, nitrilotriacetates, and mixtures thereof; (e) from about 0% to about 10% (preferably from about 0% to about 5%) of water-soluble synthetic anionic detergent surfactant; and, preferably, and (f) the balance water.
- a water-soluble detergency builder
- Such detergent compositions provide excellent detergency, do not damage washing machines unacceptably, and can be formulated to provide different sudsing patterns by varying the amount and types of synthetic anionic detergent surfactant and the amount of unsaturated soap.
- Preferably such formulas do not contain more than about 5% conventional ethoxylated nonionic surfactants. Sodium, potassium, ammonium, and alkanolammonium cations are preferred.
- Test Condition 95°F water having 6 grains of mixed hardness and a miniwasher.
- the alkylpolyglycoside surfactant has an unexpected problem with cleaning polyester.
- the alkylpolyglycosides are considered nonionic surfactant replacements, but, surprisingly, they achieve their best laundry results in combination with nonionic surfactants, especially those that are optimized for cleaning relatively hydrophobic surfaces.
- the alkyl polyglycosides in these examples were derived from glucose. Similar results are obtained with the other alkyl glycosides described herein.
- the unexpectedly poor showing of the alkylpolyglycoside with respect to this stain can be improved and/or synergistic improvement obtained by addition of the nonionic surfactant, depending upon the ratio used.
- Test Condition 60°F water having 9 grains of mixed hardness and miniwasher.
- the mixed surfactant system of this invention provides equivalent or superior clay removal across a variety of fabric types as compared to more conventional anionic surfactants.
- the surfactant mixture was 13% of the formula and the builder was sodium nitrilotriacetate at 18%.
- the test conditions were 2100 ppm of the composition, 95°F, 6 grains of mixed hardness.
- the invention vs. unbuilt commercial heavy-duty liquid detergent composition (HDL).
- TEST CONDITION 450 ppm actives, 95°F water having 6 grains mixed hardness and a mini washer.
- Composition of the invention C 12-13 alkylpolyethoxylate 3 / C 12-15 alkylpolyglycoside 2-3 at a ratio of 1:1.
- the alkylpolyglycosides improve the performance of very water soluble (high HLB) nonionics.
- Combinations of alkyl polyglucosides and semi-polar nonionic and/or amide detergent surfactants are compatible with unsaturated soap, but not with saturated soap.
- compositions 1-3 and 5 were lower sudsing than formula 4 and were more compatible with washing machine surfaces (less corrosive).
- Composition 3 formed an unsightly soap scum in the rinse water despite the presence of materials known to inhibit formation of such scums.
- Composition 3 also formed a thick gel rather than a free flowing, clear liquid. It is clear that there must not be a substantial excess of saturated soap over unsaturated. The soap must be at least about 40% unsaturated soap.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82201170T ATE25105T1 (de) | 1981-09-28 | 1982-09-22 | Mischungen von alkylpolysaccharid, aminoxidtensiden und fettsaeureseife enthaltende detergenszusammensetzungen. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US30655681A | 1981-09-28 | 1981-09-28 | |
US306556 | 1981-09-28 | ||
US37169082A | 1982-04-26 | 1982-04-26 | |
US371690 | 1995-01-12 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0075994A2 true EP0075994A2 (de) | 1983-04-06 |
EP0075994A3 EP0075994A3 (en) | 1984-03-07 |
EP0075994B1 EP0075994B1 (de) | 1987-01-21 |
EP0075994B2 EP0075994B2 (de) | 1992-11-04 |
Family
ID=26975232
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19820201170 Expired EP0075994B2 (de) | 1981-09-28 | 1982-09-22 | Mischungen von Alkylpolysaccharid, Aminoxid-Tensiden und Fettsäureseife enthaltende Detergenszusammensetzungen |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0075994B2 (de) |
BR (1) | BR8205647A (de) |
CA (1) | CA1201953A (de) |
DE (1) | DE3275202D1 (de) |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0092877A2 (de) * | 1982-04-26 | 1983-11-02 | THE PROCTER & GAMBLE COMPANY | Reinigungsmittelzusammensetzungen |
GB2159530A (en) * | 1984-06-01 | 1985-12-04 | Colgate Palmolive Co | Particulate built nonionic synthetic detergent composition |
US4627931A (en) * | 1985-01-29 | 1986-12-09 | A. E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
EP0216301A2 (de) * | 1985-09-25 | 1987-04-01 | Henkel Kommanditgesellschaft auf Aktien | Flüssiges reinigungsmittel |
US4668422A (en) * | 1985-05-31 | 1987-05-26 | A. E. Staley Manufacturing Company | Liquid hand-soap or bubble bath composition |
GB2185991A (en) * | 1986-01-30 | 1987-08-05 | Colgate Palmolive Co | Liquid laundering composition with detergent softening properties |
EP0238635A1 (de) * | 1985-09-26 | 1987-09-30 | Staley Mfg Co A E | Nichtionogene waschmittelzusammensetzung für feine textilien. |
GB2192405A (en) * | 1984-06-01 | 1988-01-13 | Colgate Palmolive Co | Particulate built nonionic detergent composition |
EP0403948A1 (de) * | 1989-06-22 | 1990-12-27 | Henkel Kommanditgesellschaft auf Aktien | Flüssigwaschmittel |
US5021195A (en) * | 1988-02-10 | 1991-06-04 | Lever Brothers Company | Structured aqueous detergent compositions containing salting-out electrolytes and surfactants and methods of forming them |
EP0463912A1 (de) * | 1990-06-22 | 1992-01-02 | Colgate-Palmolive Company | Zusammensetzung für ein Toilettenseifenstück mit einem Alkylpolyglykosid-Detergens |
EP0474915A1 (de) * | 1990-09-13 | 1992-03-18 | Hüls Aktiengesellschaft | Waschmittel |
EP0662511A2 (de) * | 1993-12-30 | 1995-07-12 | Hüls Aktiengesellschaft | Verfahren zur Umwandlung hexagonal flüssig-kristalliner wässriger Tensidphasen |
EP0780464A2 (de) | 1995-12-21 | 1997-06-25 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung hellfarbiger, niedrigviskoser Tensidkonzentrate |
US5705462A (en) * | 1993-10-29 | 1998-01-06 | Henkel Kommanditgesellschaft Auf Aktien | Bar soaps containing ether sulfates and oligoglycosides |
US5925747A (en) * | 1994-10-04 | 1999-07-20 | Henkel Kommanditgesellschaft Auf Aktien | Pumpable water-containing surfactant concentrates |
US5932535A (en) * | 1995-12-21 | 1999-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of light-colored, low-viscosity surfactant concentrates |
US6177396B1 (en) * | 1993-05-07 | 2001-01-23 | Albright & Wilson Uk Limited | Aqueous based surfactant compositions |
US6235703B1 (en) | 1996-04-02 | 2001-05-22 | Lever Brothers, Division Of Conopco, Inc. | Surfactant blends, processes for preparing them and particulate detergent compositions containing them |
KR100314403B1 (ko) * | 1994-06-22 | 2002-04-06 | 손 경 식 | 액체세정제조성물 |
WO2006128525A2 (en) * | 2005-05-28 | 2006-12-07 | Unilever Plc | Detergent compositions and their use |
CZ301476B6 (cs) * | 2007-06-15 | 2010-03-17 | Vysoká škola chemicko-technologická v Praze | Prací prostredek s vysokou prací úcinností a s nízkou tvorbou inkrustu, obsahující pouze tenzidy vyrobené z obnovitelných surovin |
WO2015101454A1 (en) | 2013-12-30 | 2015-07-09 | Unilever N.V. | Detergent composition |
EP2723214B1 (de) | 2011-06-23 | 2016-12-07 | The Procter and Gamble Company | Produkt zur vorbehandlung und reinigung von verschmutzten stoffen |
WO2023213524A1 (en) | 2022-05-06 | 2023-11-09 | Unilever Ip Holdings B.V. | Detergent composition |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USH269H (en) | 1985-03-11 | 1987-05-05 | A. E. Staley Manufacturing Company | Disinfectant and/or sanitizing cleaner compositions |
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US3219656A (en) * | 1963-08-12 | 1965-11-23 | Rohm & Haas | Alkylpolyalkoxyalkyl glucosides and process of preparation therefor |
US3721633A (en) * | 1969-10-06 | 1973-03-20 | Atlas Chem Ind | Aqueous built liquid detergents containing alkyl glycosides |
US3772269A (en) * | 1969-07-24 | 1973-11-13 | Ici America Inc | Glycoside compositions and process for the preparation thereof |
US3867301A (en) * | 1971-09-11 | 1975-02-18 | Dai Ichi Kogyo Seiyaku Co Ltd | Detergent compositions |
US4070309A (en) * | 1976-07-27 | 1978-01-24 | The Procter & Gamble Company | Detergent composition |
US4247424A (en) * | 1979-10-11 | 1981-01-27 | The Procter & Gamble Company | Stable liquid detergent compositions |
-
1982
- 1982-09-22 EP EP19820201170 patent/EP0075994B2/de not_active Expired
- 1982-09-22 DE DE8282201170T patent/DE3275202D1/de not_active Expired
- 1982-09-27 CA CA000412220A patent/CA1201953A/en not_active Expired
- 1982-09-28 BR BR8205647A patent/BR8205647A/pt unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US3219656A (en) * | 1963-08-12 | 1965-11-23 | Rohm & Haas | Alkylpolyalkoxyalkyl glucosides and process of preparation therefor |
US3772269A (en) * | 1969-07-24 | 1973-11-13 | Ici America Inc | Glycoside compositions and process for the preparation thereof |
US3721633A (en) * | 1969-10-06 | 1973-03-20 | Atlas Chem Ind | Aqueous built liquid detergents containing alkyl glycosides |
US3867301A (en) * | 1971-09-11 | 1975-02-18 | Dai Ichi Kogyo Seiyaku Co Ltd | Detergent compositions |
US4070309A (en) * | 1976-07-27 | 1978-01-24 | The Procter & Gamble Company | Detergent composition |
US4247424A (en) * | 1979-10-11 | 1981-01-27 | The Procter & Gamble Company | Stable liquid detergent compositions |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0092877A3 (en) * | 1982-04-26 | 1985-01-09 | The Procter & Gamble Company | Detergent compositions |
EP0092877A2 (de) * | 1982-04-26 | 1983-11-02 | THE PROCTER & GAMBLE COMPANY | Reinigungsmittelzusammensetzungen |
GB2192405A (en) * | 1984-06-01 | 1988-01-13 | Colgate Palmolive Co | Particulate built nonionic detergent composition |
GB2159530A (en) * | 1984-06-01 | 1985-12-04 | Colgate Palmolive Co | Particulate built nonionic synthetic detergent composition |
US4627931A (en) * | 1985-01-29 | 1986-12-09 | A. E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
US4668422A (en) * | 1985-05-31 | 1987-05-26 | A. E. Staley Manufacturing Company | Liquid hand-soap or bubble bath composition |
EP0216301A2 (de) * | 1985-09-25 | 1987-04-01 | Henkel Kommanditgesellschaft auf Aktien | Flüssiges reinigungsmittel |
EP0216301A3 (en) * | 1985-09-25 | 1988-08-31 | Kommanditgesellschaft Auf Aktien Henkel | Liquid cleaning agent |
EP0238635A4 (de) * | 1985-09-26 | 1988-01-07 | Staley Mfg Co A E | Nichtionogene waschmittelzusammensetzung für feine textilien. |
EP0238635A1 (de) * | 1985-09-26 | 1987-09-30 | Staley Mfg Co A E | Nichtionogene waschmittelzusammensetzung für feine textilien. |
GB2185991B (en) * | 1986-01-30 | 1990-09-26 | Colgate Palmolive Co | Liquid detergent having improved softening properties |
GB2185991A (en) * | 1986-01-30 | 1987-08-05 | Colgate Palmolive Co | Liquid laundering composition with detergent softening properties |
US5021195A (en) * | 1988-02-10 | 1991-06-04 | Lever Brothers Company | Structured aqueous detergent compositions containing salting-out electrolytes and surfactants and methods of forming them |
EP0403948A1 (de) * | 1989-06-22 | 1990-12-27 | Henkel Kommanditgesellschaft auf Aktien | Flüssigwaschmittel |
WO1990015855A1 (de) * | 1989-06-22 | 1990-12-27 | Henkel Kommanditgesellschaft Auf Aktien | Flüssigwaschmittel |
GR910100273A (en) * | 1990-06-22 | 1992-08-25 | Colgate Palmolive Co | A soap bar composition for toilets |
EP0463912A1 (de) * | 1990-06-22 | 1992-01-02 | Colgate-Palmolive Company | Zusammensetzung für ein Toilettenseifenstück mit einem Alkylpolyglykosid-Detergens |
EP0474915A1 (de) * | 1990-09-13 | 1992-03-18 | Hüls Aktiengesellschaft | Waschmittel |
DE4029035A1 (de) * | 1990-09-13 | 1992-03-19 | Huels Chemische Werke Ag | Waschmittel |
US5370816A (en) * | 1990-09-13 | 1994-12-06 | Huels Aktiengesellschaft | Detergent composition containing a mixture of alkyl polyglycosides |
US6177396B1 (en) * | 1993-05-07 | 2001-01-23 | Albright & Wilson Uk Limited | Aqueous based surfactant compositions |
US5705462A (en) * | 1993-10-29 | 1998-01-06 | Henkel Kommanditgesellschaft Auf Aktien | Bar soaps containing ether sulfates and oligoglycosides |
EP0662511A3 (de) * | 1993-12-30 | 1997-11-05 | Hüls Aktiengesellschaft | Verfahren zur Umwandlung hexagonal flüssig-kristalliner wässriger Tensidphasen |
EP0662511A2 (de) * | 1993-12-30 | 1995-07-12 | Hüls Aktiengesellschaft | Verfahren zur Umwandlung hexagonal flüssig-kristalliner wässriger Tensidphasen |
KR100314403B1 (ko) * | 1994-06-22 | 2002-04-06 | 손 경 식 | 액체세정제조성물 |
US5925747A (en) * | 1994-10-04 | 1999-07-20 | Henkel Kommanditgesellschaft Auf Aktien | Pumpable water-containing surfactant concentrates |
EP0780464A2 (de) | 1995-12-21 | 1997-06-25 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung hellfarbiger, niedrigviskoser Tensidkonzentrate |
US5932535A (en) * | 1995-12-21 | 1999-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of light-colored, low-viscosity surfactant concentrates |
US6235703B1 (en) | 1996-04-02 | 2001-05-22 | Lever Brothers, Division Of Conopco, Inc. | Surfactant blends, processes for preparing them and particulate detergent compositions containing them |
WO2006128525A2 (en) * | 2005-05-28 | 2006-12-07 | Unilever Plc | Detergent compositions and their use |
WO2006128525A3 (en) * | 2005-05-28 | 2007-03-08 | Unilever Plc | Detergent compositions and their use |
CZ301476B6 (cs) * | 2007-06-15 | 2010-03-17 | Vysoká škola chemicko-technologická v Praze | Prací prostredek s vysokou prací úcinností a s nízkou tvorbou inkrustu, obsahující pouze tenzidy vyrobené z obnovitelných surovin |
EP2723214B1 (de) | 2011-06-23 | 2016-12-07 | The Procter and Gamble Company | Produkt zur vorbehandlung und reinigung von verschmutzten stoffen |
WO2015101454A1 (en) | 2013-12-30 | 2015-07-09 | Unilever N.V. | Detergent composition |
WO2023213524A1 (en) | 2022-05-06 | 2023-11-09 | Unilever Ip Holdings B.V. | Detergent composition |
Also Published As
Publication number | Publication date |
---|---|
EP0075994B2 (de) | 1992-11-04 |
BR8205647A (pt) | 1983-08-30 |
DE3275202D1 (en) | 1987-02-26 |
EP0075994A3 (en) | 1984-03-07 |
CA1201953A (en) | 1986-03-18 |
EP0075994B1 (de) | 1987-01-21 |
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