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(11) | EP 0 075 996 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Detergent compositions containing alkylpolysaccharide and nonionic surfactant mixture and anionic optical brightener Ein Alkylpolysaccharid, eine nichtionische Tensidmischung und einen anionischen optischen Aufheller enthaltende Detergenszusammensetzungen Compositions détergentes contenant un alcylpolysaccharide, un mélange d'agents tensio-actifs non-ioniques et d'agents de blanchiment optiques anioniques |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
Field of the Invention
[0001] 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.
Description of the Prior Art
[0002] 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 alkylmono- glucosides 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 2,974,134; 3,640,998; 3,839,318; 3,314,936; 3,346,558; 4,011,389; 4,223,129.
[0003] Built detergent compositions containing alkylpolysaccharide surfactants are also disclosed in copending published EP-A 0 075 994 and EP-A 0 075 995.
Summary of the Invention
[0005] 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. from 1% to 90%, preferably from 4% to 10% by weight, of an alkylpolysaccharide
detergent surfactant having the formula
where R is an alkyl, alkyl phenyl, alkyl benzyl, or mixtures thereof, said alkyl groups
containing from 8 to 18 carbon atoms, being either saturated or unsatured, and containing
from 0 to 3 hydroxy groups, where each R' is an ethylene-, propylene- or―CH2―CH(OH)―CH2-group, and y is from 0 to 12; and where each Z is a moiety derived from a reducing
saccharide containing 5 to 6 carbon atoms, and x is a number from 1.5 to 10;
B. from 1% to 90% by weight of a nonionic detergent surfactant;
C. from 0% to 90% by weight of a detergency builder; and
D. from 0.01 % to 2% by weight of an anionic optical brightener, the weight ratio of A to B being from 1:10 to 10:1.
[0006] 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. With the addition of the alkylpolyglycoside surfactant, the brightener effectiveness is dramatically improved, especially on cotton.
Description of the Preferred Embodiments
The Alkylpolysaccharide Surfactant
[0007] It has surprisingly been found that cosurfactants interact with the alkylpolysaccharide surfactant of this invention to provide good laundry detergency for a wide range of fabrics. The alkylpolysaccharides are those having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from H to 10, preferably from 1'2 to 3, most preferably from 1.6 to 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. (Optionally 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.
[0008] Optionally, and less desirably, there can be 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 10 to 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl 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.
[0009] 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 12 to 14 carbon atoms; n is 2 or 3, preferably 2; y is from 0 to 10, preferably 0; and x is from H to 10, preferably from H to 3, most preferably from 1.6 to 2.7. The glycosyl is preferably derived from glucose. To prepare compounds 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 1-position). The additional glycosyl units are attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
[0010] Preferably the content of alkylmonoglycoside is low, preferably less than 60%, more preferably less than 50%.
[0011] 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. For brightener effectiveness, the ratio of alkylpolyglycoside detergent surfactant to nonionic detergent surfactant should be greater than 1:4 preferably greater than 1:3, most preferably greater than 1:1.
The Nonionic Detergent Surfactant
Nonionic Surfactant
[0012] Nonionic surfactants, including those having an HLB of from 5 to 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 hereinbefore. 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. Nonlimiting examples of suitable nonionic surfactants which may be used in the present invention are as follows:
(1) The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, and the like. Examples of compounds of this type include nonyl phenol condensed with 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with 15-moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630, marketed by the GAF Corporation, and Triton X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
(2) The condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with 10 moles of ethylene oxide per mole of alcohol; and the condensation product of 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms). Examples of commercially available nonionic surfactants in this type include Tergitol 15-S-9, marketed by Union Carbide Corporation, Neodol 45-9, Neodol 23―6.5, Neodol 45―7, and Neodol 45―4, marketed by Shell Chemical Company, and Kyro EOB, marketed by The Procter & Gamble Company.
(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic surfactants, marketed by Wyandotte Chemical Corporation.
(4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, said moiety having a molecular weight of from 2500 to 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.
(5) Semi-polar nonionic detergent surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
[0013] Preferred semi-polar nonionic detergent surfactants are the amine oxide detergent surfactants having the formula
wherein R is an alkyl, hydroxy alkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms, R4 is an alkylene or hydroxy alkylene group containing from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to 3 and each R5 is an alkyl or hydroxy alkyl group containing from 1 to 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.
[0014] Preferred amine oxide detergent surfactants are C10-18 alkyl dimethyl amine oxide, C8-18 alkyl dihydroxy ethyl amine oxide, and C8-12 alkoxy ethyl dihydroxy ethyl amine oxide.
[0015] Nonionic detergent surfactants (1)-(4) are conventional ethoxylated nonionic detergent surfactants.
[0016] Preferred alcohol ethoxylate nonionic surfactants for use in the compositions of the present invention are biodegradable and have the formula
wherein RS is a primary or secondary alkyl chain of from 8 to 22, preferably from 10 to 20, carbon atoms and n is an average of from 2 to 12, particularly from 2 to 9. The nonionics have an HLB (hydrophilic-lipophilic balance) of from 5 to 17, preferably from 6 to 15. HLB is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc., 1966, pages 606―613. In preferred nonionic surfactants, 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 available from Shell Chemical Company under the tradename Neodol) are preferred from a performance standpoint.
[0017] Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C10 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 C,2 alcohol with 5 moles of ethylene oxide; the condensation product of C12-13 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 C12-13 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 C12-13 alcohol with 9 moles of ethylene oxide; the condensation product of C14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14-15 alcohol with 4 moles of ethylene oxide; the condensation product of C14-15 alcohol with 7 moles of ethylene oxide; and the condensation product of C14-15 alcohol with 9 moles of ethylene oxide.
[0018] The 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. Specific examples of surfactant mixtures useful in the present invention include a mixture of the condensation product of C14-15 alcohol with 3 moles of ethylene oxide (Neodol 45―3) and the condensation product of C14-15 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 C10 alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C15 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 myristyl alcohol with 10 moles of ethylene oxide, in a ratio of lower ethoxylate to higher ethoxylate of from about 1:1 to about 3:1.
[0019] 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 R9 is an alkyl or alkenyl group of from 8 to 18, preferably 8 to 12, carbon atoms or an alkaryl group having from 5 to 14 carbons in the alkyl chain, and n is from 0 to 6, together with the preferred alcohol ethoxylates, described above, in a ratio of alcohol ethoxylate to glyceryl ether of from 1:1 to 4:1, particularly 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.
[0020] The ratio of alkylpolyglycoside detergent surfactant to nonionic detergent surfactant is from 10:1 to 1:10, preferably from 3:1 to 1:3.
The Detergency Builder
[0021] The detergent compositions herein also contain from 0% to 90%, preferably from 5% to 50%, and more preferably from 10% to 35% of a detergent builder. Such builders 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 1.0 to 0.5 and x is from 10 to 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula
wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate.
[0022] The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 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 18% to 22% water in their crystal matrix. The preferred crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter 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 0.2 micron to 4 microns. The term "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 200 mg. equivalent of CaC03 water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg. eq./g. to about 352 mg. eqJg. 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 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.
[0023] The amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange capacity of at least 50 mg. eq. CaCO3/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).
[0024] 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. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula
wherein x is from 20 to 30, especially about 27.
[0026] Other useful 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. Preferred are the alkali metal, especially sodium, salts of the above.
[0027] Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of 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.
[0028] Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of Si02 to alkali metal oxide of from 0.5 to 4.0, preferably from 1.0 to 2.4.
[0029] Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxy- disuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
[0030] Highly preferred polycarboxylate builders herein are set forth in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
[0032] Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxy- methyloxysuccinate, cis-cyclohexaneh exacarboxyl ate, cis-cyclopentanetetracarboxylate phloroglucinol 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.
[0033] Other suitable polycarboxylates 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. 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.
[0034] Other detergency builder materials useful herein are the "seeded builder" compositions disclosed in Belgian Patent No. 798,856, issued Oct. 29, 1973. 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.
Optional Ingredients
[0035] In addition to the detergent surfactants described hereinbefore, the detergent compositions herein can contain from 1% to 15%, preferably from 2% to 8%, of 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, Laughtin et aI, issued Dec. 30, 1975. 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. The following are representative examples of surfactants useful in the present compositions.
[0036] Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. 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.
[0037] The unsaturated fatty acid soap of this invention contains from 16 to 22 carbon atoms, preferably in a straight chain configuration. Preferably the number of carbon atoms in the unsaturated fatty acid soap is from 16 to 18.
[0038] 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, diethanolammonium, triethanolammonium, tetramethylammonium, etc. cations. Sodium ions are preferred although in liquid formulations ammonium, and triethanolammonium cations are useful.
[0039] 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 1% to 15%, preferably from 1% to 10%, most preferably from 2% to 5%. The unsaturated fatty acid soap is preferably present at a level that will provide a level of from 15 ppm to 200 ppm, preferably from 25 ppm to 125 ppm in the wash solution at recommended U.S. usage levels and from 30 ppm to 1000 ppm, preferably from 50 ppm to 500 ppm for European usage levels.
[0040] 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).
[0041] Preferably, 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. However, low levels of saturated soap can be used. Tallow and palm oil soaps can be used.
[0042] 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 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
[0043] Such synthetic anionic detergent surfactants are desirable additives at a level of from 1% to 10% to increase the overall detergency effect and, if desired, increase the level of suds. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Ca-C,8 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 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pats. 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C11-13LAS.
[0044] Preferred anionic detergent surfactants are the alkyl polyethoxylate sulfates, particularly those in which the alkyl contains from 10 to 22 carbon atoms, preferably from 12 to 18 and wherein the polyethoxylate chain contains from 1 to 15 ethoxylate moieties preferably from 1 to 3 ethoxylate moieties. These anionic detergent surfactants are particularly desirable for formulating heavy-duty liquid laundry detergent compositions.
[0045] Other 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 1 to 10 units of ethylene oxide per molecule"and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
[0046] Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 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 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
[0047] 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.
[0048] Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
[0049] Particularly preferred auxiliary surfactants herein include linear alkylbenzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group; tallowalkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from 1 to 4; olefin or paraffin sulfonates containing from 14 to 16 carbon atoms; and alkyldimethylammonium propane sulfonates and alkyldimethylammonium hydroxy propane sulfonates wherein the alkyl group contains from 14 to 18 carbon atoms.
[0050] Specific preferred surfactants for use herein include: sodium, potassium, mono-, di-, and triethanolammonium C14-15 alkyl polyethoxylate,_3 sulfates; sodium linear C"-13 alkylbenzene sulfonate; triethanolamine C11-13 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 4 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammoniopropane-l-sulfonate; 6-(N-dodecylbenryl-N,N-dimethylammonio)-hexanoate; and coconut alkyldimethyl amine oxide.
[0051] Other 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 90%), include solvents, bleaching agents, bleach activators, soil-suspending agents, corrosion inhibitors, dyes, fillers, germicides, pH adjusting agents (monoethanolamine, sodium carbonate, sodium hydroxide, etc.), enzymes, enzyme-stabilizing agents, perfumes, fabric softening components, static control agents, and the like.
[0052] Fatty acid amide detergent surfactants useful herein include those having the formula:
wherein R6 is an alkyl group containing from 7 to 21 (preferably from 9 to 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-4 alkyl, C1-4 hydroxy alkyl, and ―(C2H4O)xH where x varies from 1 to about 3.
[0053] Preferred amides are C8-20 ammonia amides, monoethanolammonium, diethanolamides, and isopropanol amides.
The Optical Brightener
[0055] Suitable brighteners include the following:
bis anilino (R) triazinyl amino stilbene sulfonate having the formula:
wherein M is preferably Na, but can be any compatible cation such as potassium, ammonium,
substituted ammonium, e.g. mono-, di-, and triethanolammonium, etc.; X can be
where R2 is selected from H, phenyl, C1-4 alkyl, or C1-4 hydroxyalkyl; morpholino-, hydroxy;
or mixtures thereof; and R can be H or S03M.
[0056] In represented structures, R and X are:
tetrasodium 4,4'-bis[(4"-bis(2"'-hydroxyethyl)amino-6"-(3""-sulphenyl)amino-1",3",5"-triazin-2"- yl)amino]-2,2'-stilbenedisulfonate;
disodium-4-(6'-sulfonaphtho[1',2',d]triazol-2-yl)-2-stilbenesulfonate;
disodium 4,4'-bis((4"-(2"'-hydroxyethylamino)-6"-anilino-1",3",5"-triazin-2"-yl)amino]-2,2'-stilbene- disulfonate;
disodium 4,4'-bis[(4"-(2"'-hydroxyethoxy)-6"-anilino-1",3",5"-triazin-2"-yl)amino]-2,2'-stilbene- disulfonate;
disodium 4,4'-bis(4-phenyl-1,2,3-triazol-2-yl)-2,2'-stilbenedisulfonate;
sodium 4-(2H-naphtho[1,2-d]triazol-2-yl)stilbene-2-sulfonate;
disodium 4,4'-bis-(2-sulfostyryl)biphenyl;
disodium 4-(2H-6-sulfonaphtho(1,2-d]triazol-2-yl)stilbene-2-sulfonate; and
disodium 3,7-bis(2,4-dimethoxybenzamido)-2,8-dibenzothiophenedisulfonate-5,5-dioxide.
[0057] Other suitable brighteners are disclosed in U.S. Patents 3,537,993 Coward et al; issued November 3, 1970 and 3,953,380 Sundby, issued April 27, 1976.
[0058] The 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 0.01 % to 1 %, preferably from 0.05% to 0.5%, and most preferably from 0.05% to 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.
[0061] Composition of the invention: C12-13 alkylpolyethoxylate3/C12-15 alkylpolyglycoside2-3 at a ratio of 1:1.
Example I
Fluorescer Effectiveness
Example II
Redeposition and Whiteness/Brightness Test
Cotton T-Shirt
[0065] The following results using unbuilt mixtures of surfactants clearly demonstrate the effect of the alkylpolyglycoside in improving anionic brightener effectiveness in the presence of non-ionic surfactants. The data show clearly that at least 40% of the surfactant system should be alkylpolyglycoside. Five to six HWUs are a substantial improvement.
A. from 1% to 90% by weight, of an alkylpolysaccharide detergent surfactant having
the formula
where R is an alkyl, alkyl phenyl, alkyl benzyl, or mixtures thereof, said alkyl groups
containing from 8 to 18 carbon atoms, being either saturated or unsatured, and containing
from 0 to 3 hydroxy groups, where each R' is an ethylene-, propylene- or―CH2―CH(OH)―CH2-group, and y is from 0 to 12; and where each Z is a moiety derived from a reducing
saccharide containing 5 to 6 carbon atoms, and x is a number from 1.5 to 10;
B. from 1% to 90% by weight of a nonionic detergent surfactant;
C. from 0% to 90% by weight of a detergency builder; and
D. from 0.01 % to 2% by weight of an anionic optical brightener, the ratio of A to B being from 1:10 to 10:1.
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, y is from 0 to 10, the glycosyl moiety is derived from glucose, m is 2 or 3 and x is from 1.5 to 3.
bis anilino (R) triazinyl amino stilbene sulfonate having the formula:
wherein M is potassium, ammonium, substituted ammonium, or mixtures thereof; and R
and X are:
tetrasodium 4,4'-bis[(4"-bis(2"'-hydroxyethyl)amino-6"-13""-sulphenyl)amino-1",3",5"-triazin-2"- yl)amino]-2,2'-stilbenedisulfonate;
disodium-4-(6'-sulfonaphtho[1',2',d]triazol-2-yl)-2-stilbenesulfonate;
disodium 4,4'-bis[(4"-(2"'-hydroxyethylamino)-6"-anilino-1",3",5"-triazin-2"-yl)amino]-2,2'-stilbene- disulfonate;
disodium 4,4'-bis[(4"-(2"'-hydroxyethoxy)-6"-anilino-1",3",5"-triazin-2"-yl)amino]-2,2'-stilbene- disulfonate;
disodium 4,4'-bis(4-phenyl-1,2,3-triazol-2-yl)-2,2'-stilbenedisulfonate;
disodium 4,4'-bis-(2-sulfostyryl)biphenyl;
sodium 4-(2H-naphtho[1,2-d]triazol-2-yl)stilbene-2-sulfonate;
disodium 4-(2H-6-sulfonaphtho[1,2-d]triazol-2-yl)stilbene-2-sulfonate; and
disodium 3,7-bis(2,4-dimethoxybenzamido)-2,8-dibenzothiophenedisulfonate-5,5-dioxide and mixtures thereof.
A. 1 Gew.-% bis 90 Gew.-% eines Alkylpolysacchariddetergensgrenzflächenaktiven Mittels
der Formel
worin R ein Alkyl, Alkylphenyl, Alkylbenzyl, oder Gemische davon, ist, wobei die genannten
Alkylgruppen 8 bis 18 Kohlenstoffatome enthalten, entweder gesättigt oder ungesättigt
sind und 0 bis 3 Hydroxygruppen enthalten, worin jeder Rest R' eine Ethylen-, Propylen-
oder-CH2-CH(OH)-CH2-Gruppe ist, und y 0 bis 12 ist; und worin jedes Z ein von einem reduzierenden Saccharid
mit 5 bis 6 Kohlenstoffatomen abgeleiteter Rest ist, und x eine Zahl von 1,5 bis 10
ist;
B. 1 Gew.-% bis 90 Gew.-% eines nichtionischen Detergens-grenzflächenaktiven Mittels;
C. 0 Gew.-% bis 90 Gew.-% eines Detergensgerüststoffes; und
D. 0,01 Gew.-% bis 2 Gew.-% eines anionischen, optischen Aufhellers, wobei das Verhältnis von A. zu B. 1:10 bis 10:1 beträgt.
hat, worin R2 aus der Gruppe ausgewählt ist, die aus Alkyl, Alkylphenyl, Hydroxyalkyl, Hydroxyalkylphenyl, und Mischungen davon, besteht, y 0 bis 10 ist, der Glucosylrest von Glucose abgeleitet ist, n 2 oder 3 ist, und x 1,5 bis 3 ist.
Bis-anilino-(R)-triazinylaminostilbensulfonat der Formel:
worin M Kalium, Ammonium, substituiertes Ammonium, oder Mischungen davon, ist; und
R und X wie folgt sind:
Tetranatrium-4,4'-bis[(4"-bis(2"'-hydroxyethyl)amino-6"-(3""-sulphenyl)amino-1",3",5"-triazin-2"- yl)amino]-2,2'-stilbendisulfonat;
Dinatrium-4-(6'-sulfonaphtho[1',2',d]triazol-2-yl)-2-stilbensulfonat;
Dinatrium-4,4'-bis[(4"-(2"'-hydroxyethylamino)-6"-anilino-1",3",5"-triazin-2"-yl)amino]-2,2'-stilben- disulfonat;
Dinatrium-4,4'-bis((4"-(2"'-hydroxyethoxy)-6"-anilino-1",3",5"-triazin-2"-yl)amino]-2,2'-stilben- disulfonat;
Dinatrium-4,4'-bis(4-phenyl-1,2,3-triazol-2-yl)-2,2'-stilbendisulfonat;
Dinatrium-4,4'-bis-(2-sulfostyryl)biphenyl;
Natrium-4-(2H-naphtho(1,2-d]triazol-2-yl)stilben-2-sulfonat;
Dinatrium-4-(2H-6-sulfonaphtho[1,2,d]triazol-2-yl)stilben-2-sulfonat; und
Dinatrium-3,7-bis(2,4-dimethoxybenzamido)-2,8-dibenzothiophendisulfonat-5,5-dioxid, und Mischungen davon, besteht.
A. 1% à 90% en poids d'un agent de surface détergent à base d'un alkylpolysaccharide
répondant à la formule
dans laquelle R est un alkyle, un alkylphényle, un alkylbenzyle ou leurs mélanges,
lesdits groupes alkyles contenant de 8 à 18 atomes de carbone étant saturés ou insaturés
et contenant 0 à 3 groupes hydroxyles, chaque R' est un groupe éthylène, propylène
ou -CH2-CH(OH)-CH2-, y est de 0 à 12, chaque Z est une portion provenant d'un saccharide
réducteur contenant 5 à 6 atomes de carbone et x est un nombre entier de 1,5 à 10;
B. 1% à 90% en poids d'un agent de surface détergent non ionique;
C. 0% à 90% en poids d'un adjuvant de détergence, et
D. 0,01% à 2% en poids d'un azurant optique anionique, le rapport de A à B s'étendant de 1:10 à 10:1.
dans laquelle R2 est choisi dans le groupe composé d'un alkyle, d'un alkylphényle, d'un hydroxyalkyle, d'un hydroxyalkylphényle et de leurs mélanges, y est de 0 à 10, la portion glucosyle provient du glucose, n est 2 ou 3 et x s'étend de 1,5 à 3.
d'un bis-anilino(R) triazinyl amino stilbènesulfonate de formule
où M est le potassium, l'ammonium, un ammonium substitué ou leurs mélanges et R et
X sont
le 4,4'-bis[(4"-bis(2"'-hydroxyéthyl)amino-6"-(3""-sulfényl)amino-1",3",5"-triazine-2"-yl)amino]-2,2'-stilbènedisulfonate tétrasodique;
le 4-(6'-sulfonaphto[1',2',d]triazol-2-yl]-2-stilbènesulfonate disodique;
le 4,4'-bis[(4"-(2"'-hydroxyéthylamino)-6"-anilino-1",3",5"-triazine-2"-yl)amino]-2,2' stilbène- disulfonate disodique;
le 4,4'-bis((4"-(2"'-hydroxyéthoxy)-6"-anilino-1",3",5"-triazine-2"-yl)amino]-2,2'-stilbènedisulfonate disodique;
le 4,4'-bis(4-phényl-1,2,3-triazol-2-yl)-2,2'-stilbènedisulfonate disodique;
le 4,4'-bis(2-sulfostyryl)biphényle disodique;
le 4-(2H-naphto[1,2-d]triazol-2-yl)stilbène-2 sulfonate disodique;
le 4-(2H-6-sulfonaphto[1,2-d]triazol-2-yl)stilbène-2 sulfonate disodique;
le 5,5-dioxyde de 3,7-bis(2,4-diméthoxybenzamido)-2,8-dibenzothiophènedisulfonate disodique et de leurs mélanges.