IE53900B1 - Detergent compositions containing alkylpolysaccharide and non-ionic surfactant mixture and anionic optical brightener - Google Patents

Abstract

Detergent surfactant combinations comprising alkylpolyglycoside detergent surfactants and nonionic detergent surfactants provide good detergency and are compatible with anionic optical brighteners, both in built and unbuilt detergent compositions.

Description

This invention relates to surfactant combinations uhich 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 alkylmonoglueosides and suggests their utility as foam stabilizers for other surfactants. Various polyglyeoside 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? and 4,223,129.

All percentages, parts and ratios used herein are by weight unless otherwise specified.

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% of an alkylpolysaccharide detergent surfactant of the formula RO(R'O)y(Ζ)χ 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 unsaturated, 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 SS300 moiety derived from a reducing saccharide containing 5 or 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.

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 alkylpolyglycoeide surfactant, the brightener effectiveness is dramatically improved, especially on cotton.

The Alkvlpolysaccharide Surfactant It has surprisingly been found that the 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 1¾-to 10, preferably from 1¾ 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 2800 and the 2-, 3-, 4-, and/or 6 positions on the preceding saccharide units.

Optionally, and less desirably, there can be a potyatkoxide 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 8 to 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 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, and/or fructosides. Suitable alkyl monosaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, feetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, glucoses, 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 R’01c„Hj„0)y|glycsyl)). wherein ΪΓ is selected from alkyl, alkylphenyl, hydroxyalkyl, nydroxyalky lphenyl. and mixtures thereof in which said alkyl groups contain from 10 to 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 li to 10, preferably from 1¾ to 3, most preferably from 1.6 to 2.7. The glycosyi 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 glycosyi units are attached between their 1-position and the preceding glycosyi units 2-, 3-. 4- and/or 6- position, preferably predominately the 2-position.

Preferably the content of alkylmonoglycoside is low, preferably less than 60%, more preferably less than 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.

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 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 etal, issued July 25, 1967. Nonlimiting examples of suitable nonionic surfactants which may be used in the present invention are as follows: (I) 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 and diisobutylene. Examples of comppunds of this type include nonyl phenol condensed with 9.5 moles of ethylene oxide per mote 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 diiso5 octyl 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 -nroducts 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 IO moles of ethylene oxide per mole of alcohol; and the condensation product of 3 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from IO to I4 carbon atoms). Examples of commercially available nonionic surfactants in this type include Tergitoi I5-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. 14) 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 alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and 2 moieties selected from 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 caxbcn atoms and a moiety selected frcm alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.

Preferred semi-polar nonionic detergent surfactants are the amine oxide detergent surfactants having the formula O 4+5 R (OR4)xNR52 wherein R3 is an alkyl, hydroxy alkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms, R is an alkylene or hydroxy alkylene group containing from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to and each R is an alkyl or hydroxy alkyl group containing from 1 to 3' carbon atoms or a polyethylene oxide group 53SO0 containing from one to 3 ethylene oxide groups and said R$ 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 Cln .. alkyl 10-18 dimethyl amine oxide, Cg_|8 alkyl dihydroxy ethyl amine oxide, and 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 R^OC^H^OH, wherein R8 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 to 9. The nonionics have an HLB (hydrophiliclipophilic balance) of from 5 to 17, preferably from 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.

Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C(Q 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 Cj2_j3 alcohol with 6.5 moles of ethylene oxide, and the same condensa35 tion product which is stripped so as to remove substantially all 539 ΰΰ lower ethoxylate and nonethoxylated fractions; the condensation product of C|2_|3 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 C1213 alcohol with 9 moles of ethylene oxide; the condensation product of alcohol with 2.25 moles of ethylene oxide; the condensation product of alcohol with 4 moles of ethylene oxide; the condensation product of C)i»-|5 alcoho1 with 7 m0,es of ethylene oxide; and the condensation product of C|45_|S alcohol with 9 moles of ethylene oxide.

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 1:1 to to 5:1. Specific examples of surfactant mixtures useful in the present invention include a mixture of the condensation product of C|()_|5 alcohol with 3 moles of ethylene oxide (Neodol 45-3) and the condensation product of alcohol with 9 moles of ethylene oxide (Neodol 45-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from 1:1 to 1:1; a mixture of the condensation product of C|0 alcohol with 3 moles of ethylene oxide together with the condensation product of. a secondary C(5 alcohol with 9 moles of ethylene oxide (Tergitol I5-S-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from 1:1 to 4:1; a mixture of Neodol 45-3 and Tergitol I5-S-9, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from 1:1- to 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 1:1 to 3:1.

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 R9-0(CH-CH,0) CH-CHCH-OH 2 2 n 2; 2 OH wherein R 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.

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 The detergent compositions herein also.contain fran 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 Nazl(AlO2)2'(SiO2)y)-xH2O wherein z and y are at least 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 Mz(zAIO2'ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is I, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCOj hardness per gram of anhydrous aluminosilicate. 3 S (? Ο The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 26% 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 0.1 micron to 10 microns. Amorphous materials are often smaller, e.g., down to less than 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 CaCOj water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg. eq./g. to 352 mg. eq./g. The aluminosilicate ion exchange materials herein are stilt further characterized by their calcium ion exchange rate which is at least 2 grains Ca* /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from 2 grains/gallon/minute/gi^m/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 4 grains/gallon/minute/gram/gallon.

The amorphous aluminosilicate ion exchange materials usually have a Mg exchange capacity of at least 50 mg. eq. CaCOj/g. (12 mg. Mg++/g.) and a Mg++ exchange rate of at least 1 grain/gallon/rninute/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. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite Ρ (B),- and Zeolite -X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na12UAIO2)12{SiOpl2) xHjO wherein x is from 20 to 30, especially about 27.

Other examples of detergency builders include water-soluble neutral or alkaline salts.

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, poiyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphate having a degree of polymerization of from 6 to 21, and orthophosphate. Examples of poly phosphonate builders are the sodium and potassium salts of ethyiene-l.l-diphosphonic acid, the sodium and potassium salts of ethane l-hydroxy-l.l-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2triphosphonic 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. 53SOC Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO^ to alkali metal oxide of from 0.5 to 4.0, preferably from 1.0 to 2.4.

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, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.

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.

Other builders include the carboxylated carbohydrates of U.S. Patent 3,723,322, Diehl.

Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate, water-soluble polyacrylates (having molecular weights of from 2,000 to 200,000 for example), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.

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. This resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetai carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.

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 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 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. Use· ful cationic surfactants also include those des cribed 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.

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 53S 00 to 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.

The unsaturated fatty acid soap of this invention contains 10 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.

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, e.g. sodium, potassium, ammonium, monoethanolammonium, diethanolamonluni, triethanolammonium and tetramethylaimcnium cations. Sodium ions are preferred although in liquid formulations ammonium, and triethanolammonium cations are useful.

A level of at least 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 fran 1% to 15%, preferably fran 1% to 10% most preferably from 2% to 5%. The unsaturated fatty add soap is preferably present at a level that will provide a level of from 15 ppm to 200 ppm, preferably from 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.

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 (1954).

Preferably, the level of saturated soaps is kept as low as possible, preferably less than 60%, preferably less than 50% of the total soap is saturated soap. However, low levels of saturated soaps can be used. Tallow and palm oil soaps can be used.

Useful synthetic anionic surfactants also include the watersoluble salts, preferably the alkali metal, ammonium and alkylol- ammonium 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.

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 (Cg-C(g 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 C|j_|3LAS.

Preferred anionic detergent surfactants are the aikyl 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 particular!/ desirable for formulating heavy-duty liquid laundry detergent compositions.

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 l to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.

Other useful anionic surfactants herein include the water15 soluble salts of esters of alpha-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; water-soluble salts of 2-acyloxy-alkane-I-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 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from ' β to 20 carbdn 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 3Θ and wherein one of the aliphatic substituents contains from 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 sulfonium compounds in which one of the aliphatic substituents contains from 8 to. 18 caruon atoms.

Particularly preferred auxiliary surfactants herein include linear alkylbenzene sulfonates containing from 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 aikyldimethylammonim hydroxy 'propane sulfonates wherein the alkyl group contains from 14 to 18 carbon atoms.

Specific preferred surfactants for use herein include: sodium, potassium, mono-, di-, and triethanolammonium C^j alkyl polyethoxylate^j sulfates; sodium linear Cj|_13 alkylbenzene sulfonate; triethanolamine C|j_j3 alkylbenzene sulfonate; sodium tallow aikyl 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-N20 coconutalkylammonio)-2hydroxypropane-l-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammoniopropane-l-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)-hexanoate; and coconut aikyldimethyl amlrfe oxide.

Other adjunct components which may be included in the compositions of the present invention, in their conventional artestablished levels for use (i.e., from 0 to 90%), include, e.g., solvents, bleaching agents, bleach activators, soil-suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents (e.g. monoethanolamine, sodium carbonate, sodium hydroxide), enzymes, enzyme-stabilizing agents, perfumes, fabric softening components and static control agents.

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 hydrogen, C1-4 alkyl, hydroxy alkyl, and -(C2H4O)xH where x varies from 1 to 3.

Preferred amides are ammonia amides, monoethanolammonium, diethanolamid.es, and isopropanol amides.

From 0,01 to 2%, preferably from 0.1 to 1% optical brightener is used.

The Optical Brightener Suitable brighteners include the following: bis anilino (R) triazinyl amino stilbene sulfonate having the formula: N N wherein M is preferably Na, but can be any compatible cation such as, for exanple, potassium, amnenium and substituted anmonium, e.g. mono-, di-, and triethanolamraoniutn; X can be where R2 is selected from H, phenyl, C|_y alkyl, or C|_4 hydroxyalkyl; morpholino-, hydroxy; 2'3 '2 HCOCH.CH_j CH_NH- n -NH 'Μ-: or mixtures thereof; and R .pan be H or SO^M. In represented structures, R and X are; -n(c2h4oh)2 σΝΗ· -NH10 -HHCH2CH3 -NHCH2CHOHCH3 Γλ “Ν o -NHC H OH -N(CH3)CH2CH2OH -NHC,H,OCH_ JO 5 -NHCSOH -NHC^OC^ S 3 si -OH -nhc2h^oh -Ν o \_/ NaO3S—ΝΗ1°XD“ CH.

NHH(OCH,CH2)3CH,NH- H(OCH,CH,)qCH,NH-<^>— NH2'3 (hoch2ch2)2 NNaOjS -N H —— Μ H tetrasodium 4,4'-bis[ (4ll-bis(2'-hydroxyethyl)atnino-6-(311sulphenyl)amino-l ,3 ,5-triazin-2-yl)aminoJ-2,2'-stilbenedisulfonate; disodium-4-(6'-sulfonaphtho[l' ,2' ,d]triazol-2-yl)-2-stilbenesulfonate; disodium 4,4'-bis) (411-(2111-hydroxyethylamino)-6-anilino-111 ,3 ,5-triazin-2ll-yl)amino)-2,2'-stilbenedisulfonate; disodium 4,4'-bis[ (4l,-(2l-hydroxyethoxy)-5-anilino-ill,3 ,5-triazin-2-yl)amino]-2,2'-stilbenedisulfonate; disodium 4,4'—bis( 4—pheny I-l „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-sulfosty ry I) biphenyl; disodium 4-(2H-6-sulfonaphtho[ 1,2-d] triazol-2-y I) stilbene-2sulfonate; and disodium 3,7-bis(2,4-dimethoxybenzamido)-2,8-dibenzothiophenedisulfonate-5,5-dioxide.

Other suitable brighteners are disclosed in U.S. Patents 3,537,593 Coward et al; issued November 3, 1970 and 3,953,380 Sundby, issued April 27, 1976 .

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. 3 9b Ο All percentages, parts, and ratios herein are by weight unless otherwise specified.

The following examples illustrate the compositions and method of the present invention.

Composition of the invention: cj.2-13 alkylpolyethoxylate3/C12_15 alkylpolyglycoside2_3 at a ratio of 1:1.

EXAMPLE I Formula Parts 13.3 13.3 12.0 13.3 28.8 1.0 C12-15 alkylpolyglycoside2_3 C12-13 alkylpolyethoxylate6 g Sodium tripolyphosphate Na2co3 Polyacetaldehyde detergency builder Anionic brightener* *bis(anilino-hydroxyethylmethylamino-tr iaz inylamino)stilbene disulfonate (sodium salt).

Fluorescer Effectiveness Filtered Unfiltered lta F Soler 2A HWU HWUC12-15 alkylpolyglyco- side2_3/Neodol 23-6.5 79 111 Commercial built anionic detergent (control) 80 106 Significant technical differences: HWU=2; Soler 2A=2; and F=l.

EXAMPLE II Redeposition and Whiteness/ Brightness Test Cotton T-Shirt The following results using unbuilt mixtures of surfactants clearly demonstrate the effect of the alkylpolyglycoside in improving anionic brightener effectiveness in the presence of non10 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.

CI2-I3 a,kyl~ CI2—13 alkyl- Unfiltered* polyglycoside2 polyethoxylate^ Hunter Whiteness Units ' Before After Delta Washing Washing (loss) 100 0 120 110 10 80 20 122 113 9 60 40 118 109 9 20 80 119 92 27 0 100 118 91 27 *To measure brightener effect Conditions: , Miniwasher , 6 grains mixed hardness, 100' one cycle 300 ppm total surfactant, 15 ppm of the brightener of

Claims (9)

1. CLAIMS i
1. l. A detergent composition comprising: (A) from 1% to 90% of an alkylpolysaccharide detergent surfactant of the formula R0(R'0) y (Z) 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 unsaturated, and containing from 0 to 3 hydroxy groups, where each R' is an ethylene, propylene or -CH 2 -CH(OH)-CH 2 - group, and y is from 0 to 12; and where each Z is a moiety derived from a reducing saccharide containing 5 or 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.
2. 2. The composition of Claim 1 wherein component A has the formula R 2 O(C n H 2n O) y -(gluoosyl) x wherein R 2 is selected from alkyl, alkyIphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, y is from 0 to 10, the glycosyl moiety is derived from glucose, n is 2 or 3 and x is from 1.5 to 3.
3. 3. The composition of Claim 2 wherein the nonionic surfactant has a HLB of from 5 to 17 and the anionic optical brightener is present in an amount from 0.1 to 1% by weight.
4. 4. The composition of Claim 1 wherein the anionic optical brightener is selected from: bis anilino (R) triazinyl amino stilbene sulfonate having the formula: 5. 39 0b wherein M is sodium, potassium, ammonium, substituted anroonium, or a mixture thereof; R is H or SO^M wherein M is as defined above, or R and X are: R χ -N(C 2 H 1) OH) 2 σ Η · -NH-NHCH 2 CH 3 -NHCH 2 CHOHCH 3 -N. -N(CH 3 )CH 2 CH 2 OH -NHC,H,OCH, Jo J -NHC^OCH -OH 5 3 3 ' 3 6 H(OCH 2 CH 2 ) 3 CH 2 NH- H(OCH 2 CH 2 ) 3 CH 2 NH-<2^I—NH- ; (HOCH 2 CH 2 ) 2 N- NaOjS-^^)—NH—θ—NH- ; tetrasodium 4,4’—bis[(4-bis(2'-hydroxyethyI)amino-6 ,1 -(3sulphenyl)amino-l ,3 ,5-triazin-2-yl)amino]-2,2'-stilbenedisulfonate; 5 disodium-4-(6'-suIfonaphtho[l' ,2' ,d]triazol-2-yi)-2-stilbenesulfonate; disodium 4,4 1 -bis[(4-(2 ,11 -hydroxyethylamino)-6-anilino-l 11 ,3 r 5 l '-triazin-2 ll “yl)amino)-2,2'-stilbenedisulfonate; disodium 4,4'-bis[ (4 11 -(2'-hydroxyethoxy)-6-anilino-l ,3 ,10 5-triazin-2-yl)amino]-2,2'-stilbenedisulfonate; disodium 4,4'-bis(4-phenyI-l ,2,3-triazol-2-yl)-2,2‘--stilbenedisulfonate; disodium 4,4'-bis-(2-sulfostyryl)biphenyl; sodium 4-(2H-naphtho[l,2-d]triazol-2-yl)stilbene-2-sulfonate; 15 .disodium 4-(2H-6-sulfonaphtho[l,2-d]triazol-2-yl)stilbene~2sulfonate; and disodium 3,7-bis(2,4-dinethoxybenzamido)-2,8-dibenzothiophenedisulfonate-5,5-dioxide and mixtures thereof.
5. 5. The composition of Claim 4 wherein the ratio of (A) to (B) is 20 from 1:3 to 3:1.
6. 6. The composition of Claim I wherein the detergency builder is present at a level of from 20% to 50% by weight and * s selected from hydrated Zeolites A, X, and P, having a particle size of frcm 0.01 to 10 microns, alkali metal ammonium or substituted ammonium tripolyphosphates, pyrophosphates, carbonates, silicates, borates, polymeric metaphosphates, nitrilotriaretates, citrates, and polyarctal carboxylates and mixtures thereof. 5
7. 7. A process of cleaning cotton fabrics in an aqueous detergent solution containing from 0.01% to 1% by weight of the detergent composition of Claim I.
8. 8. A detergent composition according to Claim 1, substantially as hereinbefore described with particular 10 reference to the accompanying Examples.
9. 9. A process according to Claim 7 of cleaning cotton fabrics, substantially as hereinbefore described.