EP0106692A1

EP0106692A1 - Liquid detergent containing polyethylene glycol

Info

Publication number: EP0106692A1
Application number: EP83306287A
Authority: EP
Inventors: Keith Anthony Jones
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1982-10-18
Filing date: 1983-10-17
Publication date: 1984-04-25

Abstract

Described are stable liquid detergent compositions containing polyethylene glycol and a surfactant mixture consisting essentially of nonionic, polysaccharide and cationic surfactants. The addition of the polyethylene glycol provides enhanced cleaning, especially on particulate soils.

Description

This invention relates to heavy-duty, stable liquid detergent compositions containing polyethylene glycol and -a surfactant mixture consisting essentially of selected nonionic, polysaccharide and cationic surfactants. The compositions herein exhibit surprisingly effective detergency as well as fabric softening and static control, even in the total absence of detergency builder materials. The compositions are also relatively insensitive to water hardness conditions, performing well in both hard and soft water conditions. The polyethylene glycol provides important soil, especially particulate soil, removal benefits in the present compositions.

Background Art

Other detergent compositions which utilize mixtures of selected nonionic surfactants and cationic surfactants are defined in U.S. Patents 4,259,217, Murphy, issued March 31, 1981, and 4,222,905, Cockrell, issued September 16, 1980, both of which are incorporated herein by reference. The addition of alkylpolysaccharide surfactants to such nonionic/cationic surfactant systems, and the cleaning and fabric care benefits obtained thereby, is described in U.S. Patent Application Serial No. 376,877, Cook et al, filed May 10, 1982., U.S. Patent 4,276,205, Ferry, issued June 30, 1981, discloses the addition of polyethylene glycols to detergents containing amine oxide and nonionic surfactants to improve cleaning.
Previous attempts to incorporate polyethylene glycols into heavy-duty liquid detergents containing nonionic and cationic surfactants have been unsuccessful because the polyethylene glycol ;appeared to "oil out" of the compositions, and consequently provided little or no cleaning benefits.
It has now been found that stable, single-phase isotropic liquids containing polyethylene glycol and the nonionic, polysaccharide and cationic surfactants herein can be formulated.
While not intending to be limited by theory, it is believed that the alkylpolysaccharide surfactant is a highly effective hydrotroping agent which allows for the formulation of single phase liquids in which the polyethylene glycol can peptize and aid in the removal 6f soils, especially particulate soils.

Summary of the Invention

The present invention relates to stable liquid detergent compositions comprising:

(i) from about 5% to about 50%, by weight of a surfactant mixture consisting essentially of:
- (a) a nonionic surfactant, preferably one having the formula R(OC₂H₄)_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;
- (b) an alkylpolysaccharide detergent surfactant of the formula RO(R'O) _y(Z) _x where R is an alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or mixtures thereof, said alkyl groups containing from about 8 to about 18 carbon atoms; where each R' contains from 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 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 12 to about 22 carbon atoms, or a mixture of such surfactants;
the weight ratio of (a) to (b) being from about 7: to about 0:1, preferably from about 3:1 to about 1:3, and the weight 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; and
(ii) from about 0.1% to about 10% by weight of a polyethylene glycol having an average molecular weight of from about 2000 to about 15,000.

Detailed Description of the Invention

The compositions of the present invention comprise, by weight, from about 5% to about 50%, preferably from about 10% to about 40%, and most preferably from about 15% to about 30%, by weight of a'mixture of particularly defined nonionic, alkylpolysaccharide and cationic surfactants in the ratios stated herein. Preferred compositions contain at least about 15% of the non- ioniclalkylpolysaccharide/cationic surfactant mixture and at least about 1.5% of the cationic component in order to assure the presence of a sufficient amount of both the cationic surfactant and the mixture to provide the desired cleaning and fabric conditioning benefits.
The compositions of the present invention contain the nonionic, alkylpolysaccharide and cationic surfactants, 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 about 4:1 to about 9:1, in order to achieve the best soil removal performance.
Using the mixtures of conventional nonionic detergent surfactants and polysaccharide detergent surfactants permits the use of considerably lower levels of the cationic surfactant to achieve a level of softening or antistatic effect that is achieved with a higher level of cationic surfactant when only the conventional 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 6 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 washing machine corrosion. Alkalinity sources, such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate, can be included in the compositions for this purpose. Some of the cationic/nonionic systems of the present invention attain optimum removal of greasy/oily soils at higher pH's, while attaining optimum particulate soil removal at relatively lower pH's. In these systems, overall performance can be enhanced by varying the pH of the wash solution during the laundering process. Compositions haing a pH of at least about 8 in the laundry solution provide better removal of greasy/oily and body soils. Such compositions also preferably have the ability to maintain a pH in the laundry solution of from about 8 to 11 throughout the washing operation (reserve alkalinity), which can be obtained by incorporating compounds which buffer at pH's of from about 8 to 11, such as monoethanolamine, diethanolamine or triethanolamine. However, the compositions herein preferably are formulated to provide a pH in the laundry solution of from about 6.5 to about 7.5.
Preferred compositions of the present invention are also essentially free of oily hydrocarbon materials and solvents, 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 compositions.

The Alkylpolysaccharide Surfactant

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 atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1
to about 10, preferably from about 11 to about 3, most preferably from about 1.6 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g. glucose, galactose and galactosyl moieties can substitute for the glucosyl moieties. (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.
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 about 10 to about 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, 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-, penta-, and hexagiucosides.
The preferred alkylpolyglycosides have the formula
wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from 1
to about 10, preferably from about 1
to about 3, most preferably from about 1.6 to about 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 I-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.
Preferably the content of alkylmonoglycoside is low, preferably less than about 60%, more preferably less than about 50%.

Nonionic Detergent Surfactant

Nonionic surfactants useful herein have an HLB (hydrophilic-lipophilic balance, as defined in Nonionic Surfactants by M. J. Schick, Marcel Dekker, Inc., 1966, pages 607-613, incorporated herein by reference) of from about 5 to about 14, and 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, both incorporated herein by reference. Nonlimiting examples of suitable nonionic surfactants which can 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 about 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 about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol 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 diisooctyl phenol condensed with about 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 about I 'to about 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 about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of about 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 IS-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 about 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 about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 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 about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type 'of nonionic surfactant include certain of the commercially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.

Preferred nonionic surfactants because of their superior biodegradaility have the formula R(OC₂H₄)_nOH, wherein R is a primary alkyl chain containing an average of from about 10 to about 18, preferably from about 10 to about 16, carbon atoms, and n is an average of from about 2 to about 9, preferably from about 2 to about 7. These nonionic surfactants have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 1'4, preferably from about 6 to about 13.
Preferred nonionic surfactants for use in the present invention include 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_12-15 alcohol with 7 moles of ethylene oxide; the condensation product of C_12-15 alcohol with 9 moles of ethylene oxide; the condensation product of C_14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C_9-11 alcohol with 8 moles of ethylene oxide, which is stripped so as to remove unethoxylated and lower ethoxylate fractions; the condensation product of C_12-13 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 20% 2-methyl branched isomers, and are commercially available, under the tradename 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 herein. ,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 C_12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C_12-15 alcohol with 7 moles of ethylene oxide, the condensation product of C14-15 alcohol with 7 moles of ethylene oxide, and mixtures thereof.
Preferred compositions of the present invention are substantially free of fatty acid polyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylene glycol-800- distearate. Such additives can be detrimental to the particulate soil removal and fabric conditioning benefits provided by the present invention.

Cationic Component

The cationic surfactants used in the compositions of the present invention are of the di-long chain quaternary ammonium type, having two chains which contain an average of from about 12 to about 22, preferably from about 16 to about 22, more preferably from about 16 to about 18, carbon atoms. The remaining groups, if any, attached to the quaternary nitrogen atom are preferably C₁ to C₄ alkyl or hydroxyalkyl groups. Although it is preferred that the long chains be alkyl groups, these chains can contain 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 above carbon atom ranges. Preferred cationic surfactants are those having the formula
wherein the R¹ and R groups contain an average of from about 16 to about 22 carbon atoms, preferably as alkyl groups, and most preferably contain an average of from about 16 to about 18 carbon atoms, R³ and R⁴ are C₁. to C₄ alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected from the group consisting of halide (e.g., chloride), hydroxide, methylsulfate, or acetate.
Mixtures of the above surfactants are also useful in the present invention. These cationic surfactants can also be mixed with other types of c₃tionic surfactants, such as sulfonium, phosphonium, and mono- or tri-long chain quaternary ammonium materials, as long as the amount of required cationic surfactant falls within the nonionic:cationic ratios. Examples of cationic surfactants which can be used together with those required herein are 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, all incorporated herein by reference.
Preferred cationic surfactants include ditaltowalkyldimethyl (or diethyl or dihydroxyethyl) ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyl (C₁₆) dimethyl (or diethyl, or dihydroxyethyl) ammonium chloride, dioctodecyl- alkyl (C₁₈)-dimethylammonium chloride, dieicosylalkyl-(C₂₀) dimethylammonium chloride, methyl (I) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate (commercially available as Varisoft 475 from Ashland Chemical Company), or mixtures of those surfactants. Particularly preferred cationic surfactants are ditallowalkyldimethylammonium methyl sulfate, methyl (1) tallowalkyl 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 formulated 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 oxide 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 particularly less than 7, ethylene oxide groups exhibit better biodegradability characteristics.

Polyethylene Glycol

The compositions of the present invention also contain from about 0.1% to about 10%, preferably from about 0.5% to about 5%, and more preferably from about 0.8% to about 3%, by weight of a. polyethylene glycol having an average molecular weight of from about 2000 to about 15,000. The molecular weight is preferably from about 3000 to about 10,000, more preferably from about 4000 to about 8000, for optimum soil removal benefits in the present compositions.
Polyethylene glycols, which are homopolymers of ethylene oxide having the general formula HO(C₂H₄O)_nH, are well known in the art and are available from a variety of commercial sources. For example, CARBOWAX having a molecular weight of about 6000, is a preferred material made by the Union Carbide Company. Polyethylene glycols useful herein are also commercially available from Dow Chemical Company and Jefferson Chemical Corporation.
Compositions herein containing more than about 2% by weight of polyethylene glycol should contain a suitable hydrotrope to aid solubilization. A preferred hydrotrope is butyl glycoside, and it should represent from about 5% to about 10% by weight of the polysaccharide surfactant.

Optional Components

In one embodiment of the present invention, the detergent compositions additionally contain from about 1% to about 25%, preferably from about 2% to about 16%, and most preferably from about 2% to about 10% of a fatty amide surfactant, such as ammonia amides (e.g., coconut ammonia amides), diethanol-amides, and ethoxylated amides. In relation to the nonionic/cationic surfactant system, the weight ratio of the cationic/nonionic mixture 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.amides in such compositions is described in greater detail in U.S. Pat. 4,228,044, Cambre, issued October 14, 1.980, incorporated herein by reference. These amide components can also be added in small amounts, i.e., from about 2% to about 5%, to act as suds modifiers. Specifically, it is believed that they tend to boost 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 the present invention can also contain additional ingredients generally found in laundry detergent compositions, at their conventional art-established levels, as long as these ingredients are compatible with the nonionic and cationic components required herein. For example, the compositions can contain up to about 15%, preferably up to about 5%, and most preferably from 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 limited to, silicone-type suds suppressing additives which are described in U.S. Pat. 3,933,672, issued January 20, 1976, Bartolotta et al, incorporated herein by reference and the self-emulsifying silicone suds suppressors, described in U.S. Pat; 4,075,118, Gault et al, issued February 21, 1978, incorporated herein by reference. An example of such a compound is DB-544, commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
,Microcrystalline waxes having a melting point in the range from 35°C-115°C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use in the subject compositions, and are described in detail in U.S. Pat. 4,056,481, Tate, issued November 1, 1977, incorporated herein by reference.
Alkyl phosphate esters represent an additional preferred suds suppressant for use herein. These preferred 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 0% to abut 40%, preferably from about 0% to about 20%, by weight), include semi-polar nonionic (such as trialkyl amine oxides), zwitterionic and ampholytic detergency cosurfactants; detergency builders; bleaching agents; bleach activators; soil release agents; soil suspending agents; corrosion inhibitors; dyes; fillers; optical brighteners; germicides; pH adjusting agents; alkalinity sources; hydrotropes; enzymes; enzyme-stabilizing agents; perfumes; solvents; carriers; suds modifiers; opacifiers; and the like. However, because of the numerous and diverse performance advantages 6f the present invention, certain conventional components, such as detergent cosurfactants and detergency builders, as well as fabric softening and static control agents, will not 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 contain 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 invention are also substantially free of carboxymethylcellulose. Finally, while the compositions of the present invention can contain very small amounts of anionic materials, such as hydrotropes (e.g., alkali 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 the cationic surfactant, contained in the laundry solution, is complexed by the anionic material. Such a complexing of the anionic material with the cationic surfactant, decreases the overall cleaning and fabric conditioning performance of the composition. Suitable anionic materials can be selected based on their strength of complexation with the cationic material included in the composition (as indicated by their dissociation constant). Thus, when an anionic material has a dissociation constant of at least about 1 x 10 (such as sodium toluene sulfonate), it can be contained in an amount up to about 40%, by weight, of the cationic surfactant; and where the anionic material has a dissociation constant of at least about 1 x 10 , but less than about 1 x 10^-3, it can be contained in an amount up to about 15%, by weight, of the cationic surfactant. Preferred compositions are substantially or completely free of such anionic materials.
Examples of cosurfactants and detergency builders which can be used in the compositions of the present invention are found in U.S. Pat. 3,717,630, Booth, issued February 20, T973, and U.S. Pat. 4,259,217, Murphy, issued March 31, 1981, both of which are incorporated herein by reference. However, these components, particularly the anionic surfactants, should be checked with the particular nonionic/cationic surfactant system chosen, and used in an amount, so as to be certain that they will be compatible with the nonionic/cationic surfactant system.
A preferred brightener for use in the present compositions, at a level of from about 0.01% to about 3%, preferably from about 0.05% to about 1.5%, more preferably from about 0.1% to about 0.5%, is an anionic brightener of the formula
wherein each A is hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or propanamido, or taken together are morpholino or anilino; and each B is hydrogen or -SO₃M, wherein M is a compatible cation and the total number of -SO₃M groups in the molecule is from 3 to 6 with no more than 2 -S0₃M groups per anilino group.
Preferred brighteners contain from 3 to 5, and especially 4, -SO₃M groups. While M can be any suitable cation, such as potassium, ammonium, or substituted ammonium (e.g., mono-, di-, or triethanolammonium), it preferably is sodium.
Preferred brighteners are those in which A in the above formula is 2-hydroxyethyl or 2-hydroxypropyl, or taken together form a morpholino group with the nitrogen atom.
Examples of brighteners of the above class are tetrasodium 4,4'-bis{{4-[bis(2-hydroxyethyl)amino]-6-{p-sulfoanilino)-1,3,5-triazin-2-yl}amino}-2,2'-stilbene disulfonate, commercially available as Tinopal DCS (powder) from Ciba-Geigy, and as Phorwhite BBU, (powder and liquid) from Mobay; and the corresponding material in which the 2-hydroxyethyl groups are replaced with 2-hydroxypropyl groups, commercially available as Phorwhite BRU from Mobay.
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 present invention are formulated as liquids and contain up to about 20% of a lower alkyl (C₁ to C₄) alcohol, particularly ethanol. Liquid compositions containing lower levels of such alcohols (i.e., about 7 to 12%) tend 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 0.2%, and most preferably from about 0.03% to about 0.15%, of the nonionic/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.

EXAMPLE I

Heavy-duty liquid detergents of the present invention are as follows.
The glycoside units are derived from glucose. ² The alcohol and monoethoxylated alcohol have been removed. ³ Polyethylene glycol of molecular weight 6000 ⁴ Tetrasodium 4,4'-bis((4-[bis(2-hydroxyethyl)amino]-6-(p-sulfo- anilino)-1,3,5-triazin-2-yl}amino}-2,2'-stilbene disulfonate.
Other compositions of the present invention are obtained when the cationic surfactant in the above compositions is replaced, in whole or in part, by ditallowalkyldimethylammonium methyl sulfate, ditallowalkyldimethylammonium iodide, dihexadecylalkyldimethylammonium chloride, dihexadecylalkyldihydroxylethylammonium methyl sulfate, dioctadecylalkyldimethylammonium chloride, dieicosylalkyl methyl ethyl ammonium chloride, dieicosylalkyl dimethylammonium bromide, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, or mixtures of these surfactants.
Other compositions of the present, invention are also obtained where the nonionic surfactant in the above compositions is replaced, in whole or in part, by the condensation product of C_14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C_12-15 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 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_12-15 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 C_12-15 alcohol with 7 moles of ethylene oxide and the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide; and other mixtures of those surfactants.
Other compositions herein are obtained when the molecular weight of the polyethylene glycol in the above compositions is about 4000, 8000 or 12,000.
The above compositions can also contain a suds suppressor such as trimethyl-, diethyl-, dipropyl-, dibutyl-, methylethyl-, or phenylmethyl polysiloxane, or 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.

EXAMPLE II

The following heavy-duty liquid detergents were prepared.

The glycoside units are derived from glucose. ²The alcohol and monoethoxylated alcohol have been removed. ³Polyethylene glycol of molecular weight 8000.
Desized cotton . terry washcloths were washed for 10 minutes in miniature agitators containing the above detergent compositions, at a level equivalent to their recommended usage of one half cup, dissolved in 1.5 gallons (5.7 I) of water at 95°F (35°C) and having 5 grains per gallon artificial hardness. The fabrics comprised 4% by weight of the washing liquor. After washing, the fabrics were spun dry and rinsed with 1.5 gallons (5.71) of water at 95°F (35°C) and having. 5 grains per gallon artificial hardness. The fabrics were then dried in miniature electric dryers.
After two treatment cycles, the fabrics were graded tactilely for softness by a panel of three judges making paired comparisons of the control and test fabrics. The graders assigned an integer grade of from 0 to 4, in which "0" means the fabrics are equal in softness, "1" means I think this fabric is softer, "2" means I know this fabric is a little softer, "3" means this fabric is a lot softer, and "4" means this fabric is a whole lot softer. The data obtained were analyzed statistically to determine the mean softness grades in panel score units (PSU) and a statistical estimate of the least significant difference (LSD) at the 95% confidence level.
The results were as follows:
These results demonstrate that the addition of 1% PEG 8000 to commercially available Composition A directionally harmed softness while the addition of 1% PEG 8000 to Composition C (thereby providing Composition D of the present invention) significantly improved softness.

Claims

1. A stable liquid detergent composition characterized by:

(i) from 5% to 50% by weight of a surfactant mixture consisting essentially of:

(a) a nonionic detergent surfactant having an HLB of from 5 to 14, or a mixture of such surfactants;

(b) an alkylpolysaccharide detergent surfactant of the formula RO(R'O)_Y(Z)_X where R is alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or mixtures thereof, said alkyl groups containing from 8 to 18 carbon atoms; where each R' contains from 2 to 4 carbon atcms and y is fran 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 1/2 to 10; and

(c) a quaternary ammonium cationic surfactant having 2 chains which contain an average of from 12 to 22 carbon atoms, or a mixture of such surfactants;

the weight ratio of (a) to (b) being from 7:1 to 0:1, and the weight ratio of (a) + (b) to (c) being in the range of from 2:1 to 12:1; and

(ii) from 0.1% to 10% by weight of a polyethylene glycol having an average molecular weight of from 2000 to 15,000.

2. A composition according to Claim 1 characterized in that the weight ratio of (a) + (b) to (c) is from 3:1 to 9:1.

3. A composition according to Claim 1 or 2 characterized in that the cationic surfactant is selected from compounds of the formula

or mixtures thereof, wherein the R¹ and R² groups contain an average of from 16 to 22 carbon atoms, R . and R⁴ are C₁ to C₄ alkyl or hydroxyalkyl groups, and X is an anion selected from halide, hydroxide, methyl sulfate, or acetate.

4. A composition according to any of Claims 1 to 3 characterized in that the nonionic surfactant has the formula R(OC₂H₄)_nCH wherein R is a primary alkyl chain containing an average of from 10 to 18 carbon atoms and n is an average of from 2 to 9.

5. A composition according to any of Claims 1 to 4 characterized in that the alkylpolysaccharide surfactant has the formula R²(C_nH_2nO)_t(glycosyl)_x, wherein R² is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, said alkyl groups containing from 10 to 18 carbon atoms, n is 2 or 3, t is from 0 to 10, the glycosyl moiety is derived from glucose, and x is from 1 1/2 to 3.

6. A composition according to any of Claims 1 to 5 characterized in that the ratio of (a) to (b) is from 3:1 to 1:3.

7. A composition according to any of Claims 1 to 6 characterized in that the polyethylene glycol has an average molecular weight of from 4000 to 8000.

8. A composition according to any of Claims 1 to 7 characterized by 15% to 30% by weight of the surfactant mixture and from 0.5% to 3% by weight of the polyethylene glycol.