CA1209005A - Low phosphate laundry detergent compositions - Google Patents

Abstract

LOW PHOSPHATE LAUNDRY DETERGENT COMPOSITIONS
Abstract of the Disclosure Detergent compositions with a mixture of a conventional nonionic detergent surfactant, an alkylpolysaccharide detergent surfactant, and a cationic fabric-softening/antistatic compound deposit the cationic material more effectively than prior compositions containing only the conventional nonionic detergent surfactant and the cationic material.

Description

LOl,V PHOSPHATE LAUNDRY DETERGENT Ct)MPOSlTlONS
Thomas E. Cook Ernest W. Dolle Technical Field This invention relates to laundry detergent compositions which exhibit surprisingly effective detergency as well as fabric softening and static control, even in the total absence of detergency builder materials. Specifically, complet~ly unbuilt compositions of the pr~sent invention have demonstrated the lQ ability to provide good ~etergency, fabric softenin~ and static control. Other detergent compositions whlch utilize mixtures of selected nonionic surfactants and cationic sus factants are defined in U.S. Pa~ent 4,259,~17 of A.P. ~phy, issued March 31, 1981, and in U.S. Patent 4,222,905 of J.B~ Cockrell, 3r., issued Sept~er 16, 1980.
The compositions of the presant invention have excell~nt cleaning capabilities and are relatively insensitive to water hardness conditions, perforrning well in both hard and soft water conditions. Finally, in addition to this cleaning performance, the present invention provides, in a single detergent product, fabric softening and static control to the laundered fabrics.
Summary of The Invention The present invention relates to low- or no-phosphate laundry detergent compositions, especially beneficial for good cleaning and the effective provision of softening and antistatic benefits, having a pH in the laundry sotution of greater than about 7, and, preferably, containing no more than about 15%
phosphate, and no more th3n about 109~ silicaee materials, which comprise from about S96 to about 100%, Iby weight, of a surfactant mixture ccnsisting essentially of:
3~ ~a) a nonionic surfactant, preferably one having the formula RlOC2H4)nOH, wherein R is a primary alkyl chain containing an average of from about 10 to about 18 carbon atoms and n is an average of from about 2 to about 9, said nonionic surfactant having an HLB of from 5 to about 14, or a mixture of such surfactants;
1 b) an alkylpolysaccharide detergent surfactant of the formula RO(R'O)y~Z),~ where R is an alkyl, hydroxy-alkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or ~' 9~05 mixtures thereof, said alkyl ~roups containing from about 8 to about 18 carbon atoms; where each R' con-tains frorn 2 to about 4 carbon atoms and y is from 0 to about 12; and where each Z is a moiety derived from a reducing saecharide containing 5 or 6 çarbon atoms, and x is a number from about 1~ to about 10; and (c) a quaternary ammonium cationic sur~ctant having 2 chains which contain an average of from about 16 to about 22 carbon atoms, or a mixture of such 1 û su rfactants;
the ratio of (a~ to ~b) being from about 7 :1 ~o about 0 :1, preferably from about 3:1 to about 1:3, and the ratio of ~a) (b) to (c~ being in the range of from about 2:1 to about 12:1, preferably from about 3:1 to about 9:1.
Disclosure of the Invention The compositions of the present invention compris2, by weigh~, from about 5 to about 100%, preferably from about 15 to about 90%, alnd most preferably from about 20 to about 80~, of a mixture of particularly defined nonionic, alkylpolysaccharide and

2 0 cationic sur fact~nts in the ratios stated herein . Preferred compositions contain at leas~ about t 5% of the nonlonic/alkyl-polysaccharide/cationic surfactant mixture and at least about 1~ % of the cationic component, itself, in order to assure the presen~e of a sufficient amount of both the cationic surfactant and the mixture t~ provide the desired cleaning and fabric conditioning benefits .
The compositions of the present invention contain the nonionic, alkylpolysaccharide and cationic sur~actants, defined hereinafter, within ratios of nonionic and alkylpolysaccharide to cationic surfactant of from about 2 :1 to about 12 :1, preferably from about 3:1 to about 9:1 for cleaning; and most preferably from abou~ 4:1 to about 9:17 in order to ahieve the best soil removal performance.
In addition, using the mixtures of conventional nonionic cletergent surfactants and polysaccharide detergent surfactants permits the use of considerably lower levels of the cationic ` ~
~z~ s surfactant to achieve a level of softening or antistatic effect that is achieved with a higher level of cationic surfactant when only the conventionai nonionic detergent surfactant is used. In addition, there is no loss of cleaning when the polysaccharide detergent surfactant is used.
The compositions of the present invention are formulated so as to have a pH of at least about 1 in the laundry solution, at conventional usage concentrations, in order to optimize their overall cleaning performance, to aid in their manufacturing and processing, and to minimize the possibility of vvashing machine corrosion. Alkalinity sources, such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate, may be included in the compositions for this purpose. Some of the cationic/nonionic lS systems of the present invention may attain optimum removal of greasy/oiiy soils at higher pH's, whiie attaining optimum particulate soil removai at relatively lower pH's. In these systems, overall performance may be enhanced by varying the pH
of the wash solution during the laundering process. Particularly preferred compositions have a pH of at least about 8 in the laundry solution, in order to optimize the removal of greasyloily and body soils. In addition to the higher pH in the laundry solution, these preferred compositions should also have the ability to maintain a pH in the laundry solution of from about 8 to 11 throughout the washing operation ~ reserve alkalinity) . Such a reserve alkalinity may be obtained by incorporating compounds which buffer at pH's of from about 8 to 11, such as monoethanol-amine, diethanolamine or triethanolamine.
Preferred compositions of the present invention are also essentially free of oily hydrocarbon materials and solver;ts, such as mineral oil, paraffin oil and kerosene, since these materials, which are themselves oily by nature, load the washing liquor with excessive oily material, thereby diminishing the cleaning effectiveness of the composi tions .
Description of the Preferred Embodiments -The Alkylpolysaccharide Surfactant ~o~

It has surprisingly been found that the nonionic cosurfactant interacts 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 about 6 to about 30 carbon atomsr preferably from about 10 to about 16 carbon atorns and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1~ to about 10, preferably from about 1~ to about 3, rnost 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. ~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 ~he one position of the additional saccharide units and the 2-, 3-, 4-, andlor 6 posîtions on the preceding saccharid~ units.
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 containlng from about 8 to about 18, preferably from about t 0 to about 16 carbon a~oms.
Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups andlor the polyalkoxide chain can contain up to about 10, preferably less than 5, most preferably 0, alkoxide moieties.
Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, 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-, pen~a-, and hexagiucosides.

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The preferred alkylpolyglycosides have the formula R O(CnH2nO)tl9lycosyl)x wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about lQ to about 18, preferably from about t2 to a~out 14 carbon atoms; n is 2 or

3, preferably 2; t is from 0 to about 10, preferably 0; and x is from 1~ to about 10, preferably from about 1~ to about 3, most preferably from about 1~6 to about 2.7. The glycosyl is 1() preferably derived from glucose. To prepare compounds the alcohol or alkylpolyethoxy alcohol is ~ormed first and then reacted with glucose, or a source of glucose, ~o form the glucoside lattachment at the 1-position). The additional glycosyl units are attached between their l-position and the precedin~ glycosyl units lS 2-, 3-, 4- andfor 6 position, preferably predominately the 2-position .
Preferably the content of alkylmonoglycoside is iow, preferably less than about 609~, more preferably less than about 50%.
Nonionic Deterç1ent Surfactant Nonionic: surfactants, including those having an HLB of from about 5 to about 17, are well known in the detersency 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 combinativn 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 UOS. 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:
(I) The polyethylene oxide condensates of atkyi phenols.
3s These compounds include the condensation products of aikyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain con-figuration with ethylene oxide, said ethylene oxide being present in an amount equ31 to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, ~or example, from polymerized propylene, diist)butylene, and the like. Examples of compounds of this type include nonyl phenol condensed with about g.5 moles of ethylene oxide per mole of nonyl phenol; doclecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and diiso-octyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. C:ommercially available nonionic surfactants of this type include Igepal C0-630 ,1 marketed by the C;AF Corpora-tion, 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 about I to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, pri-mary or secondary, and generaliy oontains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohoi condensed with about 10 moles of ethylene oxide per mole of alcohol; and the conden-sation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols ~Nith alkyl chains varying in length from 10 to 14 carbon atoms). Examples of commercially available nonionic surfactants in this type include Tergitol 15-5-9,3 marketed by Union Carbide Corporation, Neodol 45-9,4 Neodol 23-6.5'5Neodol 45-7 '6and Neodol 1~5-4,7marketed by Shell Chem;cal Company, and ' Kyro E0~3 8marketed by The Procter & Camble 0 Company .
(3) The condensation products of ethylene oxide with a hydrophobic base forrned by the condensation of propylene oxide with propyiene glycol. The hydrophobic portion of these com-pounds has a molecular weight of from about 1500 to 1800 ancl exhibiss water insolubility. The addition of polyoxyethylene rnoieties to Shis hydrophobic portion tends to increase the water 1 - ~ inclusive. Ihe ternlS bearing these su~erscri~t numerals are trademarks.

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solubility of the molecule as a whole, and the liyuid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of ~he condensation product, which corresponds to condensation with up ~o about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic surfactants, marketecl by Wyandotte Chemical Corporation.
t4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethyl-enediamine. The hydrophobic moiety of these products consists of the reaction produc:t of ethylenediamine and excess propylene oxide, said moiety having a molecular weight of from about 25û0 to about 3000. This hydrophobic moiety is condensed with ethyl-ene oxide to the extent that the condensation product contains .5 from about l~û96 to about ~09~ by weight of polyoxyathylene and has a molecular wcight of from about S,000 to about 11,000. Examples of this 'typ2 of nonionic sur~actant include certain of the commer-cially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.
The conventional nonionic detergent surfactants wh;ch are preferred for use in the compositions of the present invention are biodegradabl~s and have the formula R~OC2H4)nOH, wherein R is a primary alkyl chain containing an average of from about 10 to about 18, prefer3bly from about 10 to abou~ 16, carbon atoms, and n is an average of from about 2 to about 9, preferably from aboult 2 to about 7. These nonionic surfactants have an 51LB
thydrophilic-lipophilic balance) of from about 5 to about 14, preferably from about 6 to about 13. HLB, an indicator of a surfactant's hydrophilic or lipophilic nature, is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekicer, Inc., 1966, pages 607-613, Preferred nonionic surfactants for use in the present invention include the cvndensatlon product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconu alcohol with 6 moles of ethylene oxide; the condensation product of C12 15 alcohol with 7 moles of ethylene oxide; the condensation * ~aderrE rk ** l~ad~Dark ,, :
. . .

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product of Cl 2 15 alcohol with 9 moles of ethylene oxide; the condensation product of C14 15 aicohol with 2.25 moles of ethylene oxide; the condensation product of Cl 4-15 alcohol with 7 moles of ethylene oxide; the condensation product of Cg 11 alcohol with 8 moles of ethylene oxide, which is stripped so as to remove unethoxylated and lower ethoxylate fractions; the condensation product of C12 13 alcohol with 6~5 moles of ethylene oxide, and this same alcohol ethoxylate which is stripped so as to remove unethoxylated and lower ethoxylate fractions. A preferred class of such surfactants utilize alcohols which contain about 209~
2-methyl branched isomers, and are commercially available, under the trad~nark 'Neodol', from Shell Chemical Company. The condensation product of tallow alcohol with 9 moles of ethylene oxide is also a preferred nonionic surfactant for use ~erein.
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of Cl~ 13 alcohol with 6.5 moles of ethylene oxide, the sondensation product of S::1 2-15 alcohol with ethylene oxide, the condensation product of C1 4 15 alcohol with 7 moles of ethylene oxid~, and mixtures of those surfactants.
Other nonionic surfactants well known in the detergency art may be used, in eombination with one or more of the required nonionic surfactants, to form useful nonionic surfactant mixtures.
2S 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,û8û, Kessler et al, issued July 25, 1967, Nonlimiting examples of suitable nonionic surfactants which may be u~ed in conjunction with the required nonionic surfactants, defined above, are:
polyethylene oxide condensates of alkyl pherlols, such as ehe ' Igepal'*surfactan~s, marlceted by the GAF Corporation, and the ' Triton' sur~actants, marketed by the Rohm ~ Haas Company;
condensation products of aliphatic alcohols with from about 10 to about 25 moles of e~hylene oxide, where those alcohols are of a primary, branched or secondary alkyl chain structure;

* r ~ademark ** l~ad~rark s .

condensation prvducts of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, such as Pluronic surfac~ants, marketed by Wyandotte Chemical Corporation; and condensation products of ethylene ox;de with the product resulting from the reaction ~h propylene oxide and ethylene diam;ne, such as the Tetronic surfactants, marketed by Wyandotte Chemical Corporation.
Preferred compositions of the present invention are substantially free of fatty acid poiyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylene glycol-800-distearate. Such additives offer no advantage, and possibly even result in a disadvantag~, in terms of achieving the particulate soil removal and fabric conclitioning benefits providecl by the present invention.
Cationic Component The cationic surfactants used in the compositions of the present invention are of the di-long chain guaternary ammonium type, having two chains which contain an average of from about 16 to about 22, pre~erably from about 16 to about 18, carbon atoms. The remaining groups, if any, attached to the quaternary nitrogerl at~m, are preferably Cl to C4 aikyl or hydroxyalkyl groups. Although it is preferred that the long chains be alkyl groups, these ohains can oontain hydroxy groups or can contain heteroatoms or other linkages, such as double or triple carbon-carbon bonds, and ester, amide, or ether linkages, as long as each chain falls within the carbon atoms ranges required given above. Preferred cationic surfactants are those having the formulae R4 - N+ _ R2 X~ ~ + X
R , N - CH2 R2 ~R3 wherein the R and R2 groups contain an average of from about 16 to about 22 carbon atoms, preferably 35 alkyl groups, and 35 most preferably contain an average nf from about 16 to about 18 carbon atoms, R3 and R are C1 to C4 alkyl or hydroxyalkyl ~g~

- 1o -groups, and X is any compatible anion, particularly one selected from the group consisting of a halide ~e.g., chloride~, hydroxide, methylsulfate, or acetate anions.
Mixtures of the above surfactants are also useful in the present invention. These cationic surfactants can also be mixed with other types of cationic surfactants, such as sulfonium, phosphonium, and mnno- or tri-long chain quaternary ammonium materials, as long as the amount of required cationic surfactant contained in the composition, falls with the nonionic:cationic ratio requirernents specified herein.
Examples of cationic surfactants which can be usad together with those require~ herein, include those described in U.S. Pat.

4,259,217, Murphy, U.S. Pat. 4,222,905, Cockrell, U.S. Pat.
4,260,529, Letton, and U.S. Pat. 4,228,042, Letton~
Pre~erred cationic sur~actants include ditallowalkyldimethyl (or diethyl or dihydroxyethyl) ammonium chloride, ditallowalkyl-dimethylammonium methyl sulfate, dihexadecylalkyl ~C16) dimethyl lor diethyl, or dihydroxyethyl) ammonium chloride, dioctadecyl-alkyl [C18~-dimethylammonium chioride, dieicosylalkyl-(C20) dimethylammonium chloride, methyl (I) tallowalkyl amido ethyl ~2) tallowalkyl imida~olinium methyl sulfate (com;rercially available as Varisoft 475 from Ashland Chemical Company), or mixtures of those surfactants. Particularly preferred cationlc sur~actants are ditallowalkyklimethylammonium methyl sulfate, methyl (I) tallow-alkyl amido ethyl [2) tallowalkyl imidazolinium methyl sulfate, and mixtures of those surfactants, with ditallowalkyldimethylammonium chloride being especially preferred.
The compositions of the present invention can be ~ormulated so as to be substantially free of ethoxylated cationic surfactants which contain more than an average of about 10, and preferably free of those which contain more than an average of about 7, moles of ethylene oxicle per mole of surfactant. It is to be noted that polyethoxylated cationic surfactants having relatively low levels of ethoxylation, i . e., those with less than 10, and particulariy less than 7, ethylene oxide groups exhibit better biodegradability characteristics.

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In one embodiment of the present invention, the detergent compositions additionaily contain from about 2 ~o about 25~6, preferably from about 2 to about t 6S~, and most preferably from about 2 to about 1096 of a fatty amide surfactant, such as ammonia amides ~e.g., coconut ammonia amides), diethanol arnides, and ethoxyla~ed amides. In relation to the nonionic/cationic sur~actant system, the ratio of the cationic/nonionic mix~ure to the amide component in the composition is in the range of from about 5:1 to about 50:1, preferably from about 8:1 to about 25:1. The use of amide in prior art composi~ions is deseribed in greater detail in U.S. Pat. 4,228,044, Cambre, issued October 14, 1980.
These amide compon~nts may also be added in small amounts, i . e., from about 2% to about 596, to act as suds modifiers. Specifically, it is believed ~hat they tend to b~ost the sudsing in an active system which exhibits relatively low sudsing, and depress the sudsing in an active system which exhibits relatively high sudsing.
The compositions of ~he present invention may also contain additional ingredients generally found in laundry detergent compositions, at their convent;onal art-established levels, as long as these ingredients are cornpatible with the nonionic and cationic components required herein. For example, the compositions can contain up to about 15%, preferably up to about 5D~, and most preferably ~rom about 0 . 001 to about 2~, of a suds suppressor component. Typical suds suppressors useful in the compositions of the present invention include, but are not limite~ to, silicone-type suds suppressing additives which are described in U.S. Pat. 3,933~672, issued Jan. 20, 1976, Bartolotta et al, and the self-emulsifying silicone suds suppressors, described in U.S. Pat. 4,075,118, Gault et al, An example of such a compound is DB-544,* commercially available from Dow Ccrning, which contains a siloxane/glycol copolymer together with solid silica and a siloxan2 resin.
Microcrystalline waxes having a melting point in lthe range from 35C-115C and a saponification value of less than 100 * l~ademark ,, _ 7.
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represent additional exarnples of a preferred suds regulating component for use in the subject cornpositions, and are described in detail in U.S. Pat. 4,056,481, Tate, issued Nov. 1, 1977, Alkyl phosphate esters represent an -additional preferred suds suppressant for use herein. These pre~erred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di- and trioleyl phosphates.
Other adjunct components which can be included in the compositions of the present invention, in their conventional art-established levels for use (i.e., from about O to abut 40%), include semi-polar nonionic tsuch as trialkyl amine oxides~, zwitterionic and ampholytic detergency cosurfactants; deter~ency builders; bleaching agents; bleach activatorsO soil release agents;
soil suspending agents; corrosion inhibitors; dyes; fillers; optical brighteners; germicides; pH adjusting agents; alkalinity sources;
hydrotropes; enzymes; enzyme-stabilizing a~sents; perfumes;
soivents; carriers; suds modifiers; opaci~lers; and the like.
2 0 However, because of the numerous and diverse perfonnance advantages of the present inven~ion, certain conventional componentsl such as detergent cosurfactants and detergency builders, as well as fabric softening and static control agents, will noe generally be necessary in a particular formulation, giving the compositions of the present invention a potential cost advantage over conventional detergent/softener compositions. For environmental reasons the compositions of the present invention can contain less than about 15~ phosphate materials. Preferred compositions conta;n less than 7% phosphate, and can even be substantially, or totally free of such phosphate materials, without excessively decreasing the performance of the compositions. The compositions of the present invention preferably contain less than 10%, and are preferably substantially free of, silicate materials.
Preferred compositions of the present inveneion are also substantially free of carboxymethylcellulose. Finally, while the compositions of the presen~ invention can contain very small amounts of anionic materials, such as hydrotropes le.g., alkali ~9~

metal toluene sulfonates), it is preferred that particular anionic materials be contained in amounts sufficiently small such that not more than about 10%, preferably not more than about 1%, of ~he cationic surfactant, contained in the laundry solution, is com-plexed by the anionic material. Such a complexing of the anionic material with the cationic surfactant, decreases the o~erall clean-ing and fabric conditioning performance of the oomposition.
Suitable anionic materials can be selected based on their strength of complexation with the cationic material included in the compo-sition [as indicated by their dissociation constant). Thus, when an anionic ma~erial has a dissociation constant of at least about 1 x 1~ 3 (such as sodium toluene sul~onate)~ it can be contained in an amount up to about 40%, by weight, of the cationic surfactant;
and where the anionic ma~erial has a dissociation constant of at least about 1 x 10 5, but less than about 1 x 10 3, it can be contained in an amount up to about 1596, by weight~ of the cat-ionic surfactant. Preferred compositions are substantially or completely flee of such anionic mat~rials.
Examples of cosurfactants and detergency builders which can be used in l:he compositions of the present invention are found in U.S. Pat~ 3,,717,630, Booth, issued Feb. 20, 1973, and lJ.S. Pat.
4,X59,217, Murphy, i~sued March 31, 1981.
However, these components, particularly the anionic surfactants, should be checked with the particular nonionicl~
cationic surfactant system chosen, and used in an amount, so as to be certain that they will be compatible with the nonionicl-cationic surfactant system.
The compositions of the present invention can be produced in a variety of forms, including liquid, solid, granular, paste, powder or substrate compositions. In a particularly preferred embodiment, the compositions of the p~esent invention are formu-lated as liquids and contain up to about 209~ of a lower alkyl ~ Cl to C4) alcohol, particularly ethanol. Liquid compositions con-~aining lower levels of such alcohols (i.e., about 7 to 129~ tend ~Z~I90~

to exhibit less phase separation than compositions containing higher alcohol levels.
The compositions of the present invention are used in the laundering process by forming an aqueous solution containing from about 0.01 ~100 parts per million) to about 0.3~ (3,000 parts per million), preferably from about 0.02 to about U.2~, and most preferably from about 0 . 03 to about 0 .15%, of the nonionicl-cationic detergent mixture, and agitating the soiled fabrics in that solution. The fabrics are then rinsed and dried. When used in this manner, the compositions of the present invention yield exceptionally good particulate soil removal, and also provide fabric softening, static control, color fidelity, and dye transfer inhibition to the laundered fabrics, without requiring the use of any of the other conventionally-used fabric softening and/or static control laundry additives.
All percentages, parts, and ratios used herein are by weight unless otherwise specified.
The following nonlimiting examples illustrate the compositions and the method of the present invention.
;~o EXAMPLE A
The following composi~ions illustrate the advantage in softening and antistatic performance for the invention as compared to conventional compositions containing only conventional nonionic detergent surfactants.

o~ l ~5 -% by weight on~ Base A 6 C D E F G H
Ditallow di-methyl ammonium chloride 3.6 3.6 3.6 1.8 2.7 ~.7 2.7 2.7 1.8 Coconut aikyl di-methyl amine oxide 4.0 4.0 4.0 4.0 2.0 2.0 200 2.0 4.0 12-1 3 alkyl polyglyco-sidel~2)* - 9.0 18.0 9.0 20.0 14.0 10.0 6.0 9.0

5 alkyl polyethoxyl-ate(7)** 18.0 9.0 - 9.0 - 6.0 10.0 19.0 9.0 1.
Ethanol 7.5 7.S 7.5 7.5 7.5 7.5 7.5 7.5 7.5 it H;~ O and mi r~rs - -~ - ~a i~F~e - ---~ -* The giycoside units are derived from glucose. l i~
** The alcohoi and monoethoxylated alcohol have ~een removed.

The static control readinys were obtained as follows:
A load of c lothing was washed in a full size washing machine, using the composition given above at a usage concentration of about 1750 parts per miliion in 17~ gallons of 95F (35C) wa~er, having a hardness of about 7 grains per gallon. The composition had a pH of about 8 in the laundry solution. The load consisted of about 33 pieces of clol'.hing and r contained cotton, polyester/cotton, nylon and polyester materi31s, ¦
and acrylic. The washed load was subsequently placed in an automatic dryer, the drum of which had been cleaned with an alcohol-soaked cloth, and dried for a period of 60 minutes. The fabric load was then removed from the dryer and placed in a yrounded Faraday Cage. The overall charge readiny of the 35 materials in the Faraday Cage was read and recorded as inclividual items were rernoved from the (:age. When all the ~abrics had been removed, the total voitage charge for the fabric load could be determin~d.
Softening is determined by grading with expert graders who used a grading scale of 0 to 4 in whioh 0 is equal; 1 is "I think this one is better. "; 2 is " I know this one is a little better. "; 3 is "This one is a lot better."; and 4 is "This one is a whole lot bettar.l' A difference of about 3/4 is significant.
Cleaning was determined by grading standardly soiled and laundered swatches with expert graders using the standard grading scale previously described. A difference of about 3/4 is signiflcant as an average for all of the stained swatches.
The softening grades for A and B as compared to the base were 1.6 to 1.9 which are significant. C was compared to the base and was essentially equal in cleaning and static control, but was superior in softening. The grades were softening = 1;
cleaning (average) = .1; and static con~rol (total volts/clings) =
52/2 for base and 42/0 for C:. D, E, F, and G were tested against the base for softness and cleaning a~ the ~ cup level.
2C The softening results vs. base were D - -.2, E = -.2, F: = -.2, and G = 0 which are all nonsignificantO The cleaning averages were D = .7, E = .1, ~ = 0, and G - 1.0 of which only the last result is significant. The invention provides equal or better cleaning. With respect to static only, H is equivalent to the base with only one half of the antistatic agent.
Similar results are obtained when the cationic surfactant in Compositi~n A is replaced, in whole or in part, by ditallowalkyl-dimethylammonium methyl sulfate, ditallowalkyldimethylammonium iodide, dihexadecylalkyldimethylammonium chloride, dihexadecyl-aikyldihydroxylethylammonium methyl sutfate, dioctadecylalkyl-dimethylammonium chloride, dieicosylaikyl methyl ethyl ammonium chloride, dieicosylalkyl dimethylammonium bronhide, methyl (1~
tallowalkyl amido ethyl t2) tallowalkyl imidazolinium methyl sulfate, or mixtures of ~hese surfactants.
Substantially similar results are also obtained where the nonionic surfactant in Composition A is replaced, in whole or in 12CD90~35 part, by the condensation product of Cl 4 15 alcohol with 2 25 moles of ethylene oxide; the condensation product of C1 4 15 alcohol with 7 moles of ethylene oxide; the condensation product of Cl 2-15 alcohol with 9 moles of ethylene oxide; the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide~ which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the condensation product of coconu~ alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of e~hylene oxide; the condensation product of C12 15 alcohol with 7 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; a 1:1 by weight mixture of the condensation product of C12 15 alcohol with 7 moles of ethylene oxide and the condensation product of Cl 4 15 alcohol with 7 moles of ethylene oxide; and other mixtures of those surfactants.
Excellent results are also obtained where the ratio of nonionic surfactant to cationic surfactant used in Composition A is about 2:1, 3:1, 3.5:1, 4.5:1, 5:1, 6:1 or 8:1.
Excellent cleaning results are also obtained where the above composition additionally contains monoethanolamine, diethanolamine or triethanolamine, as an alkalinity source.
Similar performance is also obtained where the compositions contain a silicone suds suppressor selected from the group con-sisting of trimethyl-, diethyl-, dipropyl-, dibutyl-, methylethyl-, phenylmethyl polysiloxane, and mixtures thereof; a petrolatum or oxidized petrolatum wax a Fischer-Tropsch or oxidized Fischer-Tropsch wax; ozokerite; ceresin; montan wax; beeswax;
candelilla; or carnauba wax.

Claims (12)

1. - 18 - A low phosphate laundry detergent composition, having a pH
   in the laundry solution of greater than about 7, comprising from about 5% to about 100% of a surfactant mixture consisting essen-tially of:
   (a) an ethoxylated alcohol or alkylphenol nonionic detergent surfactant having an HLB
   of from 5 to about 14, or a mixture of such surfactants;
   (b) an alkylpolysaccharicle detergent surfactant of the formula RO(R'O)y(Z)x where R is an alkyl, hydroxy-alkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or mixtures theraof, said alkyl groups containing from about 8 to about 18 carbon atoms; where each R' con-tains from 2 to about 4 carbon atoms and y is from 0 to about 12; and where each Z i5 a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms, and x is a number from about 1? to about 10; and (c) a quaternary ammonium cationic surfactant having 2 chains which contain an average of from about 16 to about 22 carbon atoms, or a mixture of such surfac-tants;
   the ratio of (a) to (b) being from about 7:1 to about 0:1, and the ratio of (a) + (b) to (c) being in the range of from about 2:1 to about 12:1.
2. 2. A composition according to Claim 1 wherein the ratio of (a) +
   (b) to (c) is from about 3:1 to about 9:1.
3. 3. A composition according to Claim 2 wherein the cationic surfactant is selected from the group consisting of or mixtures thereof, wherein the R1 and R2 groups contain an average of from about 16 to about 22 carbon atoms, R3 and R4 are C1 to C4 alkyl or hydroxyalkyl groups, and X is an anion selected from the group consisting of halide, hydroxide, methyl sulfate, or acetate.
4. 4. A composition according to Claim 3 wherein R1 and R2 are alkyl groups.
5. 5. A composition according to Claim 4 wherein, the nonionic surfactant has the formula R(OC2H4)n OH wherein R is a primary alkyl chain containing an average of from about 10 to about 18 carbon atoms and n is an average of from about 2 to about 9.
6. 6. A composition according to Claim 5 wherein the nonionic surfactant is selected from the group consisting of the conden-sation product of C14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C12-15 alcohol with 7 moles of ethylene oxide; the condensation product of C12-15 alcohol with 9 moles of ethylene oxide; the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, and the same product which is stripped so as to remove lower ethoxylate and nonethoxyiated fractions; the condensation product of C9-11 alcohol with 8 moles of ethylene oscide, which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the conden-sation product of coconut alcohol with S moles of ethylene oxide;
   the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; and mixtures thereof.
7. 7. A composition according to Claim 6 wherein the cationic surfactant is selected from the group consisting of ditallow-alkyldimethylammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyldimethylammonium chloride, diocta-decylalkyldimethylammonium chloride, dieicosylalkyldimethyl-ammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallow-alkyl imidazolinium methyl sulfate, and mixtures thereof.
8. 8. A composition according to Claim 7 wherein the cationic surfactant is ditallowalkyldimethylammonium chloride.
9. 9. A composition according to claims 1, 2 or 3 wherein (b) has the formula R2((C2H4O)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxalkylphenyl, and mixtures thereof, t is from 0 to about 10, the glycosyl moiety is derived from glucose, and x is from about 1 1/2 to about 3.
10. 10. A composition according to claim 1 wherein the ratio of (a) to (b) is from about 3:1 to about 1:3.
11. 11. a low phosphate laundry detergent composition, having a pH in the laundry solution of greater than about 7, comprising from about 20% to about 80% by weight of a surfactant mixture consisting essentially of (a) the condensation product of a C14-15 alcohol with about 7 moles of ethylene oxide;
    (b) an alkylpolyglycoside surfactant of the formula R2O(glycosyl)x, wherein R2 is a C12-13 alkyl group and x is about 2;
    (c) ditallowalkyldimethylammonium chloride; wherein the weight ratio of (a) to (b) is from about 3:1 to 1:3, and the weight ratio of (a) + (b) to (c) is from about 3:1 to about 9:1.
12. 12. A composition according to claim 11 comprising about 2.7% by weight of ditallowalkyldimethylammonium chloride and wherein the weight ratio of (a) + (b) to (c) is about 7.4.